CN115497704A - Rare earth soft magnetic powder and preparation method thereof, soft magnetic composite material and preparation method thereof - Google Patents
Rare earth soft magnetic powder and preparation method thereof, soft magnetic composite material and preparation method thereof Download PDFInfo
- Publication number
- CN115497704A CN115497704A CN202211305852.2A CN202211305852A CN115497704A CN 115497704 A CN115497704 A CN 115497704A CN 202211305852 A CN202211305852 A CN 202211305852A CN 115497704 A CN115497704 A CN 115497704A
- Authority
- CN
- China
- Prior art keywords
- soft magnetic
- rare earth
- powder
- magnetic powder
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006247 magnetic powder Substances 0.000 title claims abstract description 108
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 106
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 106
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 53
- 239000011230 binding agent Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims description 52
- 239000000843 powder Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 27
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 18
- 229920001169 thermoplastic Polymers 0.000 claims description 18
- 239000004416 thermosoftening plastic Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000003723 Smelting Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000299 Nylon 12 Polymers 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000000696 magnetic material Substances 0.000 description 20
- 230000035699 permeability Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 229910000859 α-Fe Inorganic materials 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000005672 electromagnetic field Effects 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910008458 Si—Cr Inorganic materials 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 iron-silicon-aluminum Chemical compound 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/153—Amorphous metallic alloys, e.g. glassy metals
- H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/08—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
- H01F1/083—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together in a bonding agent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/153—Amorphous metallic alloys, e.g. glassy metals
- H01F1/15325—Amorphous metallic alloys, e.g. glassy metals containing rare earths
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0206—Manufacturing of magnetic cores by mechanical means
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides rare earth soft magnetic powder and a preparation method thereof, and a soft magnetic composite material and a preparation method thereof, wherein the rare earth soft magnetic powder comprises Ce 2 Fe 17‑x‑y Ni x T y N z Wherein T comprises any one or a combination of at least two of Si, C or B; x, y and z are the atom contents of Ni, T and N respectively, x is 0.1-0.5, y is 0.1-0.5 and z is 2-4; the soft magnetic composite material is prepared by mixing the rare earth soft magnetic powder and a binder, and can meet the use requirement of electronic devices under high-frequency working conditions.
Description
Technical Field
The invention relates to the technical field of magnetic materials, in particular to rare earth soft magnetic powder and a preparation method thereof, and a soft magnetic composite material and a preparation method thereof.
Background
In recent years, with the progress of miniaturization, multi-functionalization, high processing speed, and high driving frequency of mobile communication devices (computers, mobile phones, digital cameras, car navigation devices, etc.), there is an increasing need in the industry for soft magnetic materials that can have low loss characteristics in the change of high-frequency and ultra-high-frequency electromagnetic fields.
Common soft magnetic materials in the market at present comprise ferrite soft magnetic materials (manganese zinc and nickel zinc), metal soft magnetic materials (Fe, fe-Si-Al, fe-Si-Cr, fe-Ni and the like) and amorphous nanocrystalline soft magnetic materials. The ferrite soft magnetic material has high resistivity and small eddy current loss under a high-frequency working condition, so that the ferrite soft magnetic material can work at the frequency of 1 MHz. However, ferrite soft magnetic materials have a low saturation magnetization (< 0.5T) and are not suitable for the production of very small magnetic components. Compared with ferrite soft magnetic materials, the saturation magnetization intensity of the metal soft magnetic materials is very high, and the ferrite soft magnetic materials are suitable for miniaturization of magnetic devices. However, the metal soft magnet has small resistivity, and generates very large eddy current loss under the high-frequency working condition, so that the energy utilization efficiency is greatly reduced, and the magnetic device can also generate heat violently and reduce the service life, therefore, the work of the metal soft magnet is generally not more than 100kHz. The amorphous nanocrystalline soft magnetic material has higher saturation magnetization than ferrite soft magnetic material, higher resistivity and fine grain size, so that the eddy current loss is smaller even under high-frequency working conditions, and the amorphous nanocrystalline soft magnetic material can work under higher electromagnetic field frequency, such as nano soft magnetic powder particles subjected to good insulation coating treatment, and even can work under the frequency of 100 MHz.
In recent years, it has been found that the cut-off frequency of the easy-to-surface type rare earth-iron-nitrogen compound (e.g., ce-Fe-N, nd-Fe-N) is very high, reaching 6GHz, exceeding the cut-off frequency of microwave ferrite. However, this material has a much lower electrical resistance than a ferrite material, and has a very large eddy current loss under high-frequency operating conditions, and thus it is difficult to sufficiently exhibit its high-frequency characteristics.
CN114974786A discloses a soft magnetic composite material comprising a first soft magnetic metal powder, a first insulating coating material and an airflow crushing granulation powder. The airflow crushing granulation powder comprises second soft magnetic metal powder and a second insulating coating material, and the second insulating coating material is completely solidified. The first insulating coating material and/or the second insulating coating material in the soft magnetic composite material are/is uniformly dispersed, the soft magnetic composite material is used for preparing the metal powder core and the molded inductor, and the prepared molded inductor has high insulating resistance and initial permeability.
CN114023522A discloses a micron-sized magnetic composite material with good stability, the magnetic material comprises metal compound magnetic particles and micro-nano magnetic composite particles, wherein the micro-nano magnetic composite particles are iron particles, the iron particles contain silica particles with the average powder particle size of 10nm, and the metal compound magnetic particles comprise a composition of Fe-Si-based soft magnetic iron alloy particles, iron-aluminum-based soft magnetic iron alloy particles, iron-silicon-aluminum-based soft magnetic iron alloy particles, iron-chromium-based soft magnetic iron alloy particles, nickel-based soft magnetic alloy particles and two-dimensional magnetic moment micro powder. The magnetic particles in the micron-sized composite magnetic material prepared by the method have high doping concentration, and have the advantages of simple preparation process, high stability and the like, and meanwhile, the prepared magnetic polymer micro-nano composite particles also have good biocompatibility due to the coating effect of high molecular organic matters.
CN113724958A discloses a preparation method for producing an iron-based soft magnetic iron core based on reduced iron powder alloying, belonging to the technical field of soft magnetic materials and powder metallurgy. The method comprises the following steps: (1) hydrogen reduction of high-purity reduced iron powder; (2) Uniformly mixing high-purity reduced iron powder, alloy powder and a binder, and alloying to obtain iron-based soft magnetic powder; (3) carrying out surface inorganic insulation coating treatment; (4) Adding the coated iron-based soft magnetic powder into an acetone resin solution, heating and stirring, uniformly mixing with a release agent, and pressing to obtain an iron-based soft magnetic composite block; (5) And carrying out heat treatment on the iron-based soft magnetic composite block to obtain the iron-based soft magnetic iron core. The method has simple process and low cost, can effectively reduce the burning loss of alloy components in the smelting process, basically eliminates the defects of satellite powder, surface pits and the like, and avoids the condition of easy component segregation in the solidification process.
However, the soft magnetic material has high loss in high-frequency or ultrahigh-frequency electromagnetic fields, and the popularization and application of the soft magnetic material are limited to a certain extent. Therefore, the development of the rare earth soft magnetic powder which can meet the use requirement of electronic devices under GHz working conditions and the preparation method thereof, and the soft magnetic composite material and the preparation method thereof have important significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides the rare earth soft magnetic powder and the preparation method thereof, the soft magnetic composite material and the preparation method thereof, and the soft magnetic composite material is prepared by mixing various raw material powders, then carrying out heat treatment, vacuum heating treatment, smelting treatment and rapid cooling treatment, and strictly controlling the smelting treatment temperature to obtain a glassy state mixture; heating the glassy mixture in a nitrogen atmosphere to perform crystallization and nitridation reactions, and finally obtaining rare earth soft magnetic powder; the soft magnetic composite material prepared by mixing the rare earth soft magnetic powder and the binder has lower high-frequency eddy current loss and can meet the use requirement of electronic devices under high-frequency working conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a rare earth soft magnetic powder comprising Ce 2 Fe 17-x- y Ni x T y N z Wherein T comprises any one or a combination of at least two of Si, C or B; x, y and z are the atom contents of Ni, T and N respectively, x is 0.1-0.5, y is 0.1-0.5 and z is 2-4.
The rare earth soft magnetic powder of the present invention comprises Ce 2 Fe 17-x-y Ni x T y N z Has an easy-to-plane structure, wherein Ce is the component Ce 2 Fe 17-x-y Ni x T y N z The key substances of the compound, a proper amount of added ferromagnetic element Ni can improve the soft magnetic characteristics of the material, such as magnetic permeability, T comprises any one or the combination of at least two of Si, C or B, the eddy current loss of the material under high frequency can be reduced by adding a proper amount of the above substances, but the soft magnetic performance of the material can be reduced by adding excessive amounts of the above substances, the elements are combined according to a specific atomic ratio and act synergistically, and the soft magnetic composite material prepared from the rare earth soft magnetic powder can be applied to the high frequency environment above 1GHz and has lower eddy current loss.
In the present invention, x is 0.1 to 0.5, for example, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable; y is 0.1 to 0.5, for example, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., but is not limited to the recited values, and other values not recited within the numerical range are also applicable; z is 2 to 4, and may be, for example, 2, 2.5, 3, 3.5, 3.8 or 4, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical range are also applicable.
Preferably, the shape of the rare earth soft magnetic powder includes a flake shape.
Preferably, the average particle size of the rare earth soft magnetic powder is 50 to 100nm, and may be, for example, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm or the like, but is not limited to the enumerated values, and other unrecited values within this range of values are also applicable.
In a second aspect, the present invention also provides a method for preparing a rare earth soft magnetic powder as described in the first aspect, the method comprising the steps of:
(1) Raw material Fe 2 O 3 Powder, ce 2 O 3 Powder, ni 2 O 3 Powder, siO 2 Powder, powder C and powder B 2 O 3 Powder according to Ce 2 Fe 17-x-y Ni x T y N z Mixing to obtain mixed powder;
(2) After the mixed powder is subjected to heat treatment in a hydrogen atmosphere, the mixed powder is mixed with a reducing agent and an auxiliary agent, and vacuum heating treatment is performed to obtain an intermediate product with loose texture;
(3) The intermediate product is sequentially subjected to smelting treatment and rapid cooling treatment, and then is heated in a nitrogen atmosphere to perform crystallization and nitridation reactions, so that a reacted substance is obtained; the heating temperature is 400-550 ℃;
(4) Mixing the reacted substance with acetic acid solution, and sequentially carrying out stirring and solid-liquid separation to obtain the rare earth soft magnetic powder.
The method for preparing the rare earth soft magnetic powder according to the present invention heat-treats the mixed powder in a hydrogen atmosphere in order to convert Fe in the mixed powder 2 O 3 Reducing to obtain superfine metal Fe powder; thereafter reducing Ce by utilizing high activity of reducing agent 2 O 3 Obtaining rare earth metal Ce; use of auxiliary agents to reduce participation in vacuum heat treatmentThe melting temperature of the raw material mixture of (1) to obtain an intermediate product with loose texture; then the intermediate product is sequentially subjected to smelting treatment and rapid cooling treatment to form a glassy mixture; heating the glassy mixture in a nitrogen atmosphere to perform crystallization and nitridation reactions to obtain a reacted substance; and finally, dissolving the nonmagnetic substances in the reacted substances into the solution by using an acetic acid solution to finally obtain the rare earth soft magnetic powder. The temperature for heating the glassy mixture in the nitrogen atmosphere is 400-550 ℃, and when the heating temperature is higher, the unformed phase component in the reacted substance is Ce 2 Fe 17-x-y Ni x T y N z The easy-surface structure of (2) and a large amount of alpha-Fe phase can be generated. When the heating temperature is low, the nitrogen content of the finally obtained rare earth soft magnetic powder is low, and the magnetic loss is obviously increased.
The heating temperature in the present invention is 400 to 550 ℃, and may be, for example, 400 ℃, 420 ℃, 450 ℃, 500 ℃, 530 ℃ or 550 ℃, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the temperature of the heat treatment of step (2) is 700 ℃.
Preferably, the time of the heat treatment is 10 hours.
Preferably, the hydrogen purity in the hydrogen atmosphere is >99.9%, and may be, for example, 99.9%, 99.91%, 99.93%, 99.95%, 99.97%, 99.99%, or the like, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the reducing agent comprises metallic calcium.
Preferably, the auxiliary agent comprises B 2 O 3 And (3) powder.
In the present invention, it is preferable that the auxiliary comprises B 2 O 3 Powder whose function is mainly to lower the melting temperature of the raw material mixture participating in the vacuum heat treatment, B 2 O 3 The addition of the powder does not affect the final Ce 2 Fe 17-x-y Ni x T y N z The composition of (1). Namely Ce 2 Fe 17-x-y Ni x T y N z T in (A) is any one or a combination of at least two of Si, C and B and is prepared from SiO as initial raw material 2 Powder, C powder or B powder 2 O 3 Powder determination.
Preferably, the reducing agent is added in an amount of 15% by mass of the mixed powder.
Preferably, the addition amount of the auxiliary agent accounts for 3% of the mass of the mixed powder.
Preferably, the vacuum degree of the vacuum heat treatment in the step (2) is 10 -2 Pa。
Preferably, the heating step of the vacuum heat treatment comprises: heating to 800 deg.C, then filling argon and heating to 1000 deg.C.
Preferably, the holding time of the vacuum heating treatment is 4h.
Preferably, the vacuum heat treatment is followed by cooling to 20-30 ℃, for example, 20 ℃, 23 ℃, 25 ℃, 27 ℃, 29 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the smelting process in step (3) is 1300 to 1500 ℃, and may be 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1470 ℃ or 1500 ℃, for example, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In the invention, the smelting treatment temperature is preferably 1300-1500 ℃, and the intermediate product with loose texture is smelted and rapidly cooled to form a glassy mixture. When the temperature of the smelting treatment is lower, the diffusion speed of each element in the material is low, the distribution of each component in the alloy is not uniform, the proportion of the soft magnetic phase in the alloy is reduced, and the magnetic loss of the soft magnetic composite material prepared from the obtained rare earth soft magnetic powder is lower, but the magnetic permeability of the soft magnetic composite material is greatly reduced. When the temperature of the smelting treatment is higher, more energy consumption is generated, and the preparation cost of the rare earth soft magnetic powder is increased.
Preferably, the rapid cooling treatment is achieved by: and (3) flowing the melted liquid after the melting treatment onto a molybdenum roller wheel rotating at a high speed through a quartz nozzle, and rapidly cooling the melted liquid to form a glassy state mixture.
The rotation speed of the molybdenum roller is preferably 20 to 25m/s, and may be, for example, 30m/s, 21m/s, 22m/s, 23m/s, 24m/s, or 25m/s, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the heating time is 6 to 10 hours, for example, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc., but the heating time is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The operation step of mixing the reacted substance and the acetic acid solution in the step (4) of the present invention may be to immerse the reacted substance in deionized water, add the acetic acid solution, and stir continuously to dissolve the non-magnetic substance in the reacted substance in water. The invention does not need to definitely limit the concentration of the acetic acid solution, as long as the nonmagnetic impurities such as CaO in the reaction substance can be completely dissolved, and then the solid-liquid separation treatment is carried out. And (5) repeating the operation in the step (4) until the content of Ca ions in the reactant is less than 0.1%.
Preferably, the solid-liquid separation comprises filtration.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Raw material Fe 2 O 3 Powder, ce 2 O 3 Powder, ni 2 O 3 Powder, siO 2 Powder, powder C and powder B 2 O 3 Powder according to Ce 2 Fe 17-x-y Ni x T y N z Mixing to obtain mixed powder;
(2) The mixed powder is in purity>Heat treating at 700 deg.C for 10 hr in 99.9% hydrogen atmosphere, mixing with reducing agent and assistant, and vacuum degree of 10 -2 Heating for 4 hours under the vacuum of Pa to obtain an intermediate product with loose texture;
the reducing agent comprises metallic calcium; the auxiliary agent comprises B 2 O 3 Powder; the addition amount of the reducing agent accounts for 15% of the mass of the mixed powder; the auxiliary agentThe addition amount of (A) is 3% of the mass of the mixed powder; the heating step of the vacuum heat treatment comprises: firstly heating to 800 ℃, then filling argon and heating to 1000 ℃; cooling to 20-30 ℃ after vacuum heating treatment;
(3) The intermediate product is sequentially subjected to smelting treatment and rapid cooling treatment at the temperature of 1300-1500 ℃, and then is heated at the temperature of 400-550 ℃ for 6-10 hours in a nitrogen atmosphere to perform crystallization and nitridation reactions, so as to obtain a reacted substance;
the rapid cooling treatment is realized by the following method: the melted liquid after the smelting treatment flows to a molybdenum roller wheel which rotates at a high speed of 20 to 25m/s through a quartz nozzle, and the molybdenum roller wheel is rapidly cooled to form a glassy state mixture;
(4) And mixing the reacted substance with an acetic acid solution, and sequentially stirring and carrying out solid-liquid separation to obtain the rare earth soft magnetic powder.
In a third aspect, the present invention also provides a soft magnetic composite material prepared by mixing the rare earth soft magnetic powder according to the first aspect with a binder; the rare earth soft magnetic powder may be 20% to 70% by mass of the soft magnetic composite material, for example, 20%, 30%, 40%, 50%, 60%, or 70%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The soft magnetic composite material is prepared by mixing the rare earth soft magnetic powder of the first aspect with a binder; the binder comprises thermosetting binder epoxy resin, and also comprises thermoplastic binders such as nylon 6, nylon 12 or polyphenylene sulfide. The rare earth soft magnetic powder in the soft magnetic composite material accounts for 20-70% of the mass of the soft magnetic composite material, and when the proportion of the rare earth soft magnetic powder is lower than 20%, the magnetic conductivity of the soft magnetic composite material is low, so that the miniaturization of a magnetic device is not facilitated; when the proportion of the rare earth soft magnetic powder is more than 70%, it causes a significant increase in loss of the soft magnetic composite material at high frequencies.
In a fourth aspect, the present invention also provides a method for producing the soft magnetic composite material according to the third aspect, the method comprising the steps of:
(a) Mixing epoxy resin and acetone to obtain a mixed solution;
(b) Mixing and stirring the mixed solution and the rare earth soft magnetic powder to obtain rare earth soft magnetic powder coated with epoxy resin;
(c) And drying the rare earth soft magnetic powder coated with the epoxy resin, mixing the dried rare earth soft magnetic powder with a thermoplastic binder, mixing and granulating to obtain the soft magnetic composite material.
The preparation method of the soft magnetic composite material comprises the steps of mixing the rare earth soft magnetic powder with the mixed solution containing the epoxy resin, coating a layer of high polymer resin on the surface of the rare earth soft magnetic powder to form a protective layer, so that the rare earth soft magnetic powder is not easily oxidized in the subsequent mixing and granulating processes.
Preferably, the epoxy resin of step (a) is added in an amount of 3% by mass of the rare earth soft magnetic powder.
Preferably, the volume ratio of the mixed solution to the rare earth soft magnetic powder is 1.5 to 1, and may be, for example, 1.5.
Preferably, the temperature of the drying treatment of step (c) is 70 ℃.
Preferably, the drying treatment time is 1h.
Preferably, the thermoplastic binder comprises any one or a combination of at least two of nylon 6, nylon 12 or polyphenylene sulfide, with typical but non-limiting combinations including a combination of nylon 6 and nylon 12, a combination of polyphenylene sulfide and nylon 6 or a combination of nylon 12, polyphenylene sulfide and nylon 6.
Preferably, the thermoplastic binder is added in an amount of 17 to 67% by mass of the epoxy resin coated rare earth soft magnetic powder, for example, 17%, 20%, 30%, 50%, 60%, 67%, etc., but is not limited to the enumerated values, and other values not enumerated within the range of values are also applicable.
Preferably, the kneading temperature is 5 to 10 ℃ higher than the softening temperature of the thermoplastic binder, and may be, for example, 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃ or 10 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, argon is introduced for protection during the mixing process.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(a) Mixing epoxy resin and acetone to obtain a mixed solution; mixing and stirring the mixed solution and the rare earth soft magnetic powder to obtain the rare earth soft magnetic powder coated with the epoxy resin;
the addition amount of the epoxy resin accounts for 3% of the mass of the rare earth soft magnetic powder; the volume ratio of the mixed solution to the rare earth soft magnetic powder is 1.5;
(b) Drying the epoxy resin coated rare earth soft magnetic powder for 1h at the temperature of 70 ℃, mixing the epoxy resin coated rare earth soft magnetic powder with a thermoplastic binder, mixing and granulating to obtain the soft magnetic composite material;
the thermoplastic binder comprises any one or a combination of at least two of nylon 6, nylon 12 or polyphenylene sulfide; the addition amount of the thermoplastic binder accounts for 17-67% of the mass of the rare earth soft magnetic powder coated with the epoxy resin; the mixing temperature is 5-10 ℃ higher than the softening temperature of the thermoplastic binder; and introducing argon for protection in the mixing process.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) According to the preparation method of the rare earth soft magnetic powder, the rare earth soft magnetic powder with the fine particle size is prepared, and the soft magnetic composite material prepared from the rare earth soft magnetic powder can be applied to a high-frequency environment above 1GHz and has low eddy current loss;
(2) The preparation method of the rare earth soft magnetic powder and the preparation method of the soft magnetic composite material provided by the invention have the advantages of simple operation process, low preparation cost and large-scale popularization and application prospect.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
The present embodiment provides a method for preparing a rare earth soft magnetic powder, the method comprising the steps of:
(1) Raw material Fe 2 O 3 Powder, ce 2 O 3 Powder, ni 2 O 3 Powder, siO 2 Powder according to Ce 2 Fe 17-x-y Ni x T y N z Mixing to obtain mixed powder; wherein x =0.2,y =0.2,t is Si element;
(2) The mixed powder is charged into a tube furnace to obtain a pure mixture>Heat treatment is carried out for 10 hours at the temperature of 700 ℃ in the atmosphere of 99.9 percent hydrogen, and then the mixture is mixed with reducing agent metal calcium and auxiliary agent B 2 O 3 Mixing the powders, and keeping the vacuum degree at 10 -2 Heating for 4 hours under the vacuum of Pa to obtain an intermediate product with loose texture;
the addition amount of the reducing agent accounts for 15% of the mass of the mixed powder; the addition amount of the auxiliary agent accounts for 3% of the mass of the mixed powder; the heating step of the vacuum heat treatment comprises: firstly heating to 800 ℃, and then filling argon and heating to 1000 ℃; cooling to 25 ℃ after the vacuum heating treatment;
(3) Putting the intermediate product into a smelting furnace, carrying out smelting treatment at the temperature of 1300 ℃ to completely melt the intermediate product, then flowing the molten liquid onto a molybdenum roller rotating at a high speed of 20m/s through a quartz nozzle, and carrying out rapid cooling treatment to form a glassy state mixture; placing the glassy state mixture in a nitrogen atmosphere treatment furnace, heating for 6 hours at the temperature of 500 ℃, and carrying out crystallization and nitridation reactions to obtain a reacted substance;
(4) And soaking the reacted substance into deionized water, adding an acetic acid solution, and sequentially stirring and filtering to obtain the rare earth soft magnetic powder.
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.6 Ni 0.2 Si 0.2 N 2.8 The average particle size was 80nm.
The present embodiment also provides a soft magnetic composite material prepared by mixing the above-mentioned rare earth soft magnetic powder with a binder, the preparation method comprising the steps of:
(a) Mixing epoxy resin and acetone to obtain a mixed solution; mixing and stirring the mixed solution and the rare earth soft magnetic powder to obtain the rare earth soft magnetic powder coated with the epoxy resin;
the addition amount of the epoxy resin accounts for 3% of the mass of the rare earth soft magnetic powder; the volume ratio of the mixed solution to the rare earth soft magnetic powder is 1.5;
(b) Drying the epoxy resin-coated rare earth soft magnetic powder for 1h at the temperature of 70 ℃, mixing the epoxy resin-coated rare earth soft magnetic powder with a thermoplastic binder nylon 6, and mixing and granulating in a double-screw granulator to obtain the soft magnetic composite material;
the addition amount of the thermoplastic binder accounts for 40% of the mass of the rare earth soft magnetic powder coated with the epoxy resin; the mixing temperature is 8 ℃ higher than the softening temperature of the thermoplastic binder; argon is introduced for protection in the mixing process.
The soft magnetic composite material obtained in this embodiment is prepared into a ring sample, and a vector network analyzer is used for testing at a frequency of 1GHz, so that magnetic permeability μ' =4.22 and magnetic loss tan δ μ =0.11 are obtained.
Example 2
This example provides a method for producing a rare-earth soft magnetic powder, which is the same as in example 1 except that x =0.1, y =0.1 in step (1).
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.8 Ni 0.1 Si 0.1 N 2.8 The average particle size was 82nm.
This example also provides a soft magnetic composite material prepared by mixing the above-described rare earth soft magnetic powder with a binder, the preparation method being the same as in example 1.
The soft magnetic composite material obtained in this example was prepared into a circular ring sample, and tested by a vector network analyzer at a frequency of 1GHz, with a magnetic permeability μ' =4.33 and a magnetic loss tan δ μ =0.13.
Example 3
This example provides a method of producing a rare-earth soft magnetic powder, which is the same as in example 1 except that x =0.5 and y =0.5 in step (1).
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.0 Ni 0.5 Si 0.5 N 2.8 The average particle size was 75nm.
This example also provides a soft magnetic composite material prepared by mixing the above-described rare earth soft magnetic powder with a binder, the preparation method being the same as in example 1.
The soft magnetic composite material obtained in this example was prepared into a circular ring sample, and tested by a vector network analyzer at a frequency of 1GHz, with a magnetic permeability μ' =3.75, and a magnetic loss tan δ μ =0.10.
Example 4
This example provides a method for producing a rare earth soft magnetic powder, which is the same as in example 1 except that the temperature of the melting treatment in step (3) is 1500 ℃.
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.6 Ni 0.2 Si 0.2 N 2.7 The average particle diameter was 85nm.
This example also provides a soft magnetic composite material prepared by mixing the above-described rare earth soft magnetic powder with a binder, the preparation method being the same as in example 1.
The soft magnetic composite material obtained in this embodiment is prepared into a circular ring sample, and is measured by a vector network analyzer at a frequency of 1GHz, and the magnetic permeability μ' =4.25, and the magnetic loss tan δ μ =0.13.
Example 5
This example provides a method for preparing a rare earth soft magnetic powder, which is the same as example 1 except that the heating temperature in step (3) is 400 deg.c and the time is 10 hours.
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.6 Ni 0.2 Si 0.2 N 2.5 The average particle size was 55nm.
This example also provides a soft magnetic composite material prepared by mixing the above-described rare earth soft magnetic powder with a binder, the preparation method being the same as in example 1.
The soft magnetic composite material obtained in this embodiment is prepared into a circular ring sample, and is measured by a vector network analyzer at a frequency of 1GHz, and the magnetic permeability μ' =3.83, and the magnetic loss tan δ μ =0.07.
Example 6
This example provides a method for preparing a rare earth soft magnetic powder, which is the same as example 1 except that the heating temperature in step (3) is 550 ℃ and the time is 6 hours.
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.6 Ni 0.2 Si 0.2 N 3.2 The average particle diameter was 100nm.
This example also provides a soft magnetic composite material prepared by mixing the above-described rare earth soft magnetic powder with a binder, the preparation method being the same as in example 1.
The soft magnetic composite material obtained in this example was prepared into a circular ring sample, and tested by a vector network analyzer at a frequency of 1GHz, and the magnetic permeability μ' =4.83, and the magnetic loss tan δ μ =0.13.
Example 7
This example provides a soft magnetic composite material prepared by mixing the rare earth soft magnetic powder described in example 1 with a binder, which was the same as in example 1 except that nylon 6, a thermoplastic binder, was added in an amount of 17% by mass of the rare earth soft magnetic powder coated with an epoxy resin.
The soft magnetic composite material obtained in this example was prepared into a circular ring sample, and tested by a vector network analyzer at a frequency of 1GHz, with a magnetic permeability μ' =6.30 and a magnetic loss tan δ μ =0.21.
Example 8
This example provides a soft magnetic composite material prepared by mixing the rare earth soft magnetic powder described in example 1 with a binder, which was the same as in example 1 except that nylon 6, a thermoplastic binder, was added in an amount of 67% by mass of the rare earth soft magnetic powder coated with an epoxy resin.
The soft magnetic composite material obtained in this embodiment is prepared into a circular ring sample, and is measured by a vector network analyzer at a frequency of 1GHz, and the magnetic permeability μ' =2.18, and the magnetic loss tan δ μ =0.03.
Example 9
This example provides a method for preparing a rare earth soft magnetic powder, except for SiO as a raw material in step (1) 2 The powder was replaced with powder C, and the rest was the same as in example 1 except that T was the element C.
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.6 Ni 0.2 C 0.2 N 2.8 The average particle size was 82nm.
This example also provides a soft magnetic composite material prepared by mixing the above-described rare earth soft magnetic powder with a binder, the preparation method being the same as in example 1.
The soft magnetic composite material obtained in this example was prepared into a circular ring sample, and tested by a vector network analyzer at a frequency of 1GHz, with a magnetic permeability μ' =4.38, and a magnetic loss tan δ μ =0.11.
Comparative example 1
This comparative example provides a production method of a rare earth soft magnetic powder, which is the same as example 1 except that the heating temperature in step (3) is 700 deg.c and the time is 10 hours.
The rare earth soft magnetic powder obtained by the comparative example had no phase formation of Ce 2 Fe 17-x-y Ni x T y N z The rare earth soft magnetic powder has a large amount of alpha-Fe phases.
Comparative example 2
This comparative example provides a production method of a rare earth soft magnetic powder, which is the same as example 1 except that the heating temperature in step (3) is 350 ℃ and the time is 10 hours.
The composition of the rare earth soft magnetic powder obtained in this example was Ce 2 Fe 16.6 Ni 0.2 C 0.2 N 1.1 The average particle diameter was 41nm.
The present comparative example also provides a soft magnetic composite material prepared by mixing the above-described rare earth soft magnetic powder with a binder, the preparation method being the same as in example 1.
The soft magnetic composite material obtained in the comparative example was prepared into a circular ring sample, and the magnetic permeability μ' =4.08 and the magnetic loss tan δ μ =0.28 were measured by a vector network analyzer at a frequency of 1 GHz. The soft magnetic composite material obtained by the comparative example has low nitrogen content and obviously increased magnetic loss.
In conclusion, the preparation method of the rare earth soft magnetic powder and the preparation method of the soft magnetic composite material provided by the invention are simple to operate and low in preparation cost, and the finally obtained soft magnetic composite material is suitable for high-frequency working conditions and can particularly meet the use requirements of electronic devices under GHz working conditions.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (10)
1. A rare earth soft magnetic powder, characterized in that the rare earth soft magnetic powder comprises Ce 2 Fe 17-x-y Ni x T y N z Wherein T comprises any one of Si, C or B or the combination of at least two of the Si, C and B; x, y,z is the atomic content of Ni, T and N, x is 0.1-0.5, y is 0.1-0.5, and z is 2-4.
2. The rare earth soft magnetic powder as claimed in claim 1, wherein the shape of the rare earth soft magnetic powder comprises a flake shape;
preferably, the average particle size of the rare earth soft magnetic powder is 50 to 100nm.
3. A production method of the rare earth soft magnetic powder according to claim 1 or 2, characterized by comprising the steps of:
(1) Raw material Fe 2 O 3 Powder, ce 2 O 3 Powder, ni 2 O 3 Powder of SiO 2 Powder, powder C and powder B 2 O 3 Powder according to Ce 2 Fe 17-x- y Ni x T y N z Mixing to obtain mixed powder;
(2) After the mixed powder is subjected to heat treatment in a hydrogen atmosphere, the mixed powder is mixed with a reducing agent and an auxiliary agent, and vacuum heating treatment is performed to obtain an intermediate product with loose texture;
(3) The intermediate product is sequentially subjected to smelting treatment and rapid cooling treatment, and then is heated in a nitrogen atmosphere to perform crystallization and nitridation reactions, so that a reacted substance is obtained; the heating temperature is 400-550 ℃;
(4) Mixing the reacted substance with acetic acid solution, and sequentially carrying out stirring and solid-liquid separation to obtain the rare earth soft magnetic powder.
4. The method according to claim 3, wherein the hydrogen purity in the hydrogen atmosphere of step (2) is >99.9%;
preferably, the reducing agent comprises metallic calcium;
preferably, the auxiliary agent comprises B 2 O 3 And (3) powder.
5. The production method according to claim 3 or 4, wherein the heating step of the vacuum heat treatment of step (2) includes: firstly heating to 800 ℃, then filling argon and heating to 1000 ℃;
preferably, the vacuum heating treatment is followed by cooling to 20-30 ℃.
6. The production method according to any one of claims 3 to 5, wherein the temperature of the smelting treatment in the step (3) is 1300 to 1500 ℃;
preferably, the rapid cooling treatment is achieved by: the melted liquid after the smelting treatment flows onto a molybdenum roller wheel rotating at high speed through a quartz nozzle, and the melted liquid is rapidly cooled to form a glassy state mixture;
preferably, the rotating speed of the molybdenum roller is 20-25 m/s;
preferably, the heating time is 6 to 10 hours.
7. A soft magnetic composite material characterized by being produced by mixing the rare earth soft magnetic powder according to claim 1 or 2 with a binder; the rare earth soft magnetic powder accounts for 20-70% of the mass of the soft magnetic composite material.
8. A method for the preparation of soft magnetic composite material according to claim 7, characterized in that it comprises the steps of:
(a) Mixing epoxy resin and acetone to obtain a mixed solution; mixing and stirring the mixed solution and the rare earth soft magnetic powder to obtain rare earth soft magnetic powder coated with epoxy resin;
(b) And drying the rare earth soft magnetic powder coated with the epoxy resin, mixing the dried rare earth soft magnetic powder with a thermoplastic binder, mixing and granulating to obtain the soft magnetic composite material.
9. The production method according to claim 8, wherein the volume ratio of the mixed solution of step (a) to the rare earth soft magnetic powder is 1.5.
10. The method of claim 8 or 9, wherein the thermoplastic binder of step (b) comprises any one of nylon 6, nylon 12 or polyphenylene sulfide or a combination of at least two thereof;
preferably, the addition amount of the thermoplastic binder accounts for 17-67% of the mass of the rare earth soft magnetic powder coated with the epoxy resin;
preferably, the mixing temperature is 5-10 ℃ higher than the softening temperature of the thermoplastic binder; preferably, argon is introduced for protection during the mixing process.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211305852.2A CN115497704A (en) | 2022-10-24 | 2022-10-24 | Rare earth soft magnetic powder and preparation method thereof, soft magnetic composite material and preparation method thereof |
| PCT/CN2023/097141 WO2024087621A1 (en) | 2022-10-24 | 2023-05-30 | Rare earth soft magnetic powder and preparation method therefor, and soft magnetic composite material and preparation method therefor |
| EP23866682.0A EP4394812A1 (en) | 2022-10-24 | 2023-05-30 | Rare earth soft magnetic powder and preparation method therefor, and soft magnetic composite material and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211305852.2A CN115497704A (en) | 2022-10-24 | 2022-10-24 | Rare earth soft magnetic powder and preparation method thereof, soft magnetic composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115497704A true CN115497704A (en) | 2022-12-20 |
Family
ID=84473904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211305852.2A Pending CN115497704A (en) | 2022-10-24 | 2022-10-24 | Rare earth soft magnetic powder and preparation method thereof, soft magnetic composite material and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP4394812A1 (en) |
| CN (1) | CN115497704A (en) |
| WO (1) | WO2024087621A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024087621A1 (en) * | 2022-10-24 | 2024-05-02 | 横店集团东磁股份有限公司 | Rare earth soft magnetic powder and preparation method therefor, and soft magnetic composite material and preparation method therefor |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104036905A (en) * | 2014-05-28 | 2014-09-10 | 浙江大学 | Soft magnetic composite material and preparation method thereof |
| JP2018056337A (en) * | 2016-09-29 | 2018-04-05 | 住友金属鉱山株式会社 | Method for manufacturing rare earth-iron-nitrogen based magnet powder, resin composition for bond magnet using the same, and bond magnet |
| CN108777931B (en) * | 2018-05-23 | 2020-01-14 | 中国科学院宁波材料技术与工程研究所 | High-permeability electromagnetic wave absorbing material and preparation method thereof |
| CN111575598B (en) * | 2019-02-19 | 2021-11-05 | 有研稀土新材料股份有限公司 | Yttrium-added rare earth permanent magnet material and preparation method thereof |
| CN110551941A (en) * | 2019-08-30 | 2019-12-10 | 西安交通大学 | Mixed rare earth-based refrigerating material and preparation method and application thereof |
| CN111540558B (en) * | 2020-05-08 | 2022-02-18 | 横店集团东磁股份有限公司 | Composite soft magnetic material and preparation method thereof |
| CN112735721B (en) * | 2020-12-21 | 2022-05-27 | 横店集团东磁股份有限公司 | High-frequency low-loss composite soft magnetic material and preparation method and application thereof |
| CN113724958B (en) | 2021-08-31 | 2024-04-16 | 安徽工业大学 | Preparation method for producing iron-based soft magnetic iron core based on reduced iron powder alloying |
| CN114023522A (en) | 2021-10-26 | 2022-02-08 | 天津市晨洁华美科技发展有限公司 | Micron-sized magnetic composite material with good stability and preparation method thereof |
| CN114974786A (en) | 2022-06-21 | 2022-08-30 | 苏州锦鳞电子科技有限公司 | Soft magnetic composite material and preparation method thereof, metal powder core and preparation method thereof, and molded inductor and preparation method thereof |
| CN115497704A (en) * | 2022-10-24 | 2022-12-20 | 横店集团东磁股份有限公司 | Rare earth soft magnetic powder and preparation method thereof, soft magnetic composite material and preparation method thereof |
-
2022
- 2022-10-24 CN CN202211305852.2A patent/CN115497704A/en active Pending
-
2023
- 2023-05-30 EP EP23866682.0A patent/EP4394812A1/en active Pending
- 2023-05-30 WO PCT/CN2023/097141 patent/WO2024087621A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024087621A1 (en) * | 2022-10-24 | 2024-05-02 | 横店集团东磁股份有限公司 | Rare earth soft magnetic powder and preparation method therefor, and soft magnetic composite material and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024087621A1 (en) | 2024-05-02 |
| EP4394812A1 (en) | 2024-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5892662B2 (en) | L10 type FeNi alloy particles and method for producing the same, magnetic composition and magnet | |
| US10410773B2 (en) | Synthesis and annealing of manganese bismuth nanoparticles | |
| CN105689726B (en) | A kind of preparation method for mixing rare earth high-coercive force manganese bismuth alloy magnetic | |
| CN102969112B (en) | Rare earth permanent magnet powder and preparation method thereof and magnet prepared therefrom and magnetic device | |
| CN104599802B (en) | Rare earth permanent-magnetic material and preparation method thereof | |
| CN115497704A (en) | Rare earth soft magnetic powder and preparation method thereof, soft magnetic composite material and preparation method thereof | |
| CN111540558B (en) | Composite soft magnetic material and preparation method thereof | |
| CN112735721B (en) | High-frequency low-loss composite soft magnetic material and preparation method and application thereof | |
| CN117809925A (en) | Nanocrystalline magnetic core material of high-frequency transformer and preparation method thereof | |
| JP2005005286A (en) | FINE COMPOSITE STRUCTURE MAGNETIC SUBSTANCE ABSORBING GHz BAND RADIO WAVE AND RADIO WAVE ABSORBING MATERIAL | |
| CN114038641B (en) | Silver-containing mixed rare earth iron boron sintered permanent magnet and preparation method thereof | |
| CN103406545B (en) | Micron-particle-size FeCo particles and preparation method thereof | |
| CN109817405B (en) | Preparation method of nano magnetic particles | |
| CN101707108B (en) | Thmn12 type soft magnetic material and preparation method thereof | |
| CN111014714B (en) | Preparation method of samarium-iron alloy powder integrating spray pyrolysis and iron oxide reduction in one step | |
| CN103794355B (en) | A kind of preparation method of the neodymium iron boron magnetic body with high-Curie-point | |
| CN103489556A (en) | Extremely anisotropic annular sintering ferrite rotor magnet and manufacturing method thereof | |
| KR20200023107A (en) | Manufacturing method of sintered magnetic and sintered magnetic manufactured by the same | |
| CN111653403B (en) | High-resistivity sintered R-Fe-B permanent magnet and preparation method thereof | |
| CN115798908B (en) | Preparation method of ultrathin-layer rare earth coated neodymium-iron-boron alloy powder | |
| JPH06188110A (en) | Nitride for refemen permanent magnet, refeme alloy to be used in the nitride, and permanent magnet using the nitride | |
| CN106876075B (en) | A kind of magnetic material and preparation method thereof | |
| CN113035559B (en) | Preparation method of high-performance neodymium iron boron isotropic magnetic powder | |
| KR100285350B1 (en) | Manufacturing method of permanent magnet for resin magnet | |
| TW202329169A (en) | High-magnetic-induction magnetic powder core based on amorphous crystallization bifunctional element and preparation method and application of high-magnetic-induction magnetic powder core |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |