CN112735720A - Iron nitride coated metal soft magnetic composite material and preparation method thereof - Google Patents
Iron nitride coated metal soft magnetic composite material and preparation method thereof Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 44
- 229910001337 iron nitride Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000006247 magnetic powder Substances 0.000 claims abstract description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000000748 compression moulding Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 8
- 229910005347 FeSi Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract description 3
- 125000001477 organic nitrogen group Chemical group 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000005121 nitriding Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910000920 Fe16N2 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910017389 Fe3N Inorganic materials 0.000 description 1
- 229910000727 Fe4N Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- H01F1/14766—Fe-Si based alloys
-
- 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
- H01F1/14766—Fe-Si based alloys
- H01F1/14791—Fe-Si-Al based alloys, e.g. Sendust
-
- 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
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
-
- 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
- H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Soft Magnetic Materials (AREA)
Abstract
The invention relates to the technical field of magnetic materials, in particular to an iron nitride coated metal soft magnetic composite material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) dissolving soluble ferric salt in an organic solvent, adding organic amine, and stirring at normal temperature to form a suspension; (2) adding the suspension into the metal soft magnetic powder, mixing, stirring uniformly, and drying; (3) mixing with binder and lubricant, and press molding to obtain blank; (4) heat treatment in nitrogen, cooling and spraying. According to the invention, organic amine is used as an organic nitrogen source, and Fe-N interaction is enhanced through complexation performance, so that the high-quality iron nitride is prepared. Firstly, forming a uniform organic amine-iron-organic solvent compound on the surface of magnetic powder, then, performing compression molding and high-temperature heat treatment in nitrogen, converting the organic amine-iron-organic solvent compound layer into a compact and uniform iron nitride insulating layer, and avoiding the breakage of the iron oxide insulating layer in the compression process.
Description
Technical Field
The invention relates to the technical field of magnetic materials, in particular to an iron nitride coated metal soft magnetic composite material and a preparation method thereof.
Background
The metal soft magnetic composite material (also called magnetic powder core) is widely applied to the field of electronics and electricians due to the advantages of low medium-high frequency loss, low cost, easy preparation of complex shapes and the like. With the rapid development of information technology and electromechanical industry, magnetic devices are required to be high-frequency, small, intelligent and low-loss. The insulation coating process is one of the key steps for preparing the metal soft magnetic composite material. The insulation coating is to uniformly coat an insulation film on the surface of the magnetic particles so as to reduce the loss of the metal soft magnetic composite material when the metal soft magnetic composite material is used at high frequency. From the actual production process and comprehensive performance, the insulating coating layer is generally required to be thin, uniform, high in thermal stability, high in resistivity and high in strength so as to reduce energy loss and improve comprehensive processing performance of the magnetic powder core.
The traditional preparation process of the soft magnetic composite material is to passivate with phosphoric acid to form iron phosphide, then add a binder and press the material to form, and in order to reduce hysteresis loss, anneal at a higher temperature to eliminate internal stress generated during pressing, thereby obtaining a soft magnetic powder core. Since iron phosphide decomposes at higher temperatures, resulting in a decrease in insulation properties. Therefore, in recent years, different methods for preparing magnetic powder cores coated with oxides have appeared, and for example, mitsubishi corporation invented a method for coating an MgO insulating layer on the surface of iron powder by vapor deposition. Reports of using sol-gel method to prepare oxide coated magnetic powder core have also appeared at home and abroad. The magnetic powder core prepared by the method can be annealed at a higher temperature, so that the internal stress of press forming can be eliminated.
However, the non-magnetic insulating layer causes magnetic dilution, resulting in a decrease in saturation induction of the magnetic powder core. The iron nitride material becomes an important branch of magnetic materials due to excellent mechanical strength, wear resistance, corrosion resistance, oxidation resistance and excellent magnetic performance, and has certain prospects in the aspects of magnetic recording materials, drug carriers, medical diagnosis and the like.
Iron nitrides can be classified into FeN and Fe according to their nitrogen contents2N,Fe3N,Fe4N,Fe16N2And the like. The Fe-N bond in the iron nitride material has atomic bond, ionic bond and covalent bond components at the same time, and is a more complex chemical action, so that the iron nitride material has a series of unique physical and chemical properties. E.g. Fe16N2Saturation magnetization (M)S) Can reach 230emu/g, is known to have the maximum M at presentSThe substance of (1). Fe having good soft magnetism4N is other than M of the simple substance of the comparable ironS(208emu/g, 218emu/g for iron), and also has a mechanical strength of about 550 HV. epsilon-Fe3M of NS(134emu/g) is still about 30% higher than the ferrite material. Therefore, iron nitride has been widely used for the insulating layer of the metallic soft magnetic composite material.
Chinese patent literature discloses an insulation coating treatment method for soft magnetic composite materials, and the application publication number is CN104028746A, the invention puts soft magnetic powder into a quartz tube at the center of a tube furnace, and introduces flowing nitrogen, heats to the nitriding temperature of more than 1000 ℃, keeps the temperature for more than 20min, continues to introduce nitrogen during heat preservation, cools along with the furnace to obtain the insulation coated soft magnetic powder, and the surface of the insulation coated soft magnetic powder forms an insulation film of metal nitride and oxide.
Chinese patent literature discloses a preparation method of a double-shell soft magnetic composite material, the application publication number of which is CN108057878A, and the invention prepares a nitride/oxide double-shell structure on the surface of high-purity iron powder by a chemical heat treatment process. Wherein, the inner layer oxide is used as a transition layer and is matched with the crystal lattice of the substrate; the outer layer oxide further improves the resistivity of the powder core on the basis of nitridation, and is beneficial to reducing the loss of the iron powder core. Meanwhile, the nitriding and oxidizing double-shell layers have ferromagnetism, so that the magnetic dilution effect is greatly reduced, and the saturation magnetization intensity of the composite material is improved. However, the preparation method has complicated steps, a large amount of ammonia gas or nitrogen gas flow is input, the control on the atmosphere flow rate is strict, the tail gas treatment difficulty is high, and the mass production is difficult to realize.
The Chinese patent literature discloses a preparation method of a core-shell structure soft magnetic composite material, the application publication number of which is CN104036899A, and the steps of the invention are as follows: 1) introducing high-purity hydrogen to carry out reduction reaction on the high-purity iron powder at 450-600 ℃ for 60-120 min; 2) introducing mixed gas of ammonia and hydrogen for surface nitriding, wherein the nitriding temperature is 400-650 ℃, and the nitriding time is 3-7 h; 3) after the nitriding process is finished, the mixed gas of ammonia gas and hydrogen gas is continuously introduced to finally generate the surface-coated Fe4Iron powder of N film and core-shell structure, Fe4The thickness of the N film is 0.5 to 10 μm.
The method for preparing the iron nitride by adopting ammonia gas or nitrogen gas has simple mechanism and high purity of a synthetic sample, and is the most widely researched and reported method at present. However, the method needs a long time, complicated steps, and a large amount of ammonia gas or nitrogen gas flow is input, so that the requirements on the control of the atmosphere pressure and the flow rate are high, and the environmental protection requirement on tail gas treatment is strict. In addition, the loss of a large amount of energy also limits the synthesis and application of materials to a certain extent.
Disclosure of Invention
The invention provides a preparation method of the iron nitride coated metal soft magnetic composite material, aiming at overcoming the technical problems in the prior art, and the preparation method is simple to operate, does not need ammonia gas, is environment-friendly, has low energy consumption and is suitable for industrial production.
The invention also provides the iron nitride coated metal soft magnetic composite material prepared by the preparation method, the iron nitride coated metal soft magnetic powder core has the characteristics of low loss, high magnetic conductivity and good bonding strength, and the prepared iron nitride insulating layer is thin, so that the magnetic dilution effect is reduced, and the high-frequency stability of the metal magnetic powder core is enhanced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an iron nitride coated metal soft magnetic composite material comprises the following steps:
(1) dissolving soluble ferric salt in an organic solvent, adding organic amine after the soluble ferric salt is completely dissolved, and stirring at normal temperature to form a suspension;
(2) adding the suspension obtained in the step (1) into the metal soft magnetic powder, mixing, stirring uniformly at normal temperature, and drying to obtain insulated metal soft magnetic powder;
(3) uniformly mixing the insulated metal soft magnetic powder obtained in the step (2) with a binder and a lubricant, and performing compression molding to obtain a blank;
(4) and (4) carrying out heat treatment on the blank obtained in the step (3) in nitrogen, cooling and spraying to obtain the iron nitride coated metal soft magnetic powder core. The step has high strength after heat treatment, the product has good comprehensive performance, high-temperature roasting of the iron nitride precursor by ammonia gas or nitrogen gas is avoided, the iron nitride precursor nitriding and heat treatment processes are creatively integrated, and the energy consumption is reduced.
According to the invention, organic amine is used as an organic nitrogen source, and the Fe-N interaction is enhanced through the complexation performance, so that the high-quality iron nitride is prepared. Firstly, forming a uniform organic amine-iron-organic solvent compound on the surface of magnetic powder, then, performing compression molding and high-temperature heat treatment in nitrogen, converting the organic amine-iron-organic solvent compound layer into a compact and uniform iron nitride insulating layer, avoiding the high-temperature roasting process of an iron nitride precursor and the breakage of an iron oxide insulating layer in the compression process, improving the resistivity of the magnetic powder core, facilitating the release of internal stress in a blank by the high-temperature heat treatment, and greatly reducing the loss of the magnetic powder core; meanwhile, the outer iron nitride insulating layer is ferromagnetic, so that the magnetic dilution effect can be reduced, and the magnetic performance of the composite material is further improved. The preparation method disclosed by the invention is simple to operate, free of pollution, low in cost and suitable for industrial large-scale production.
Preferably, in step (1):
the soluble iron salt is selected from FeCl3、Fe2(SO4)3And Fe (NO)3)3One or more of the components are mixed; the soluble iron salts of the invention all contain Fe3+Acting on the surface of the metal soft magnetic powderForming a soluble iron salt coating.
The organic solvent is selected from one or a mixture of acetone, toluene, xylene and p-xylene; the oxygen atoms in the organic solvent ensure water, oxygen and the like in the air, and the influence on a reaction system is less.
The organic amine is selected from one or a mixture of ethylene diamine, isobutylamine, diisopropylamine, 1, 2-propane diamine and 1, 4-butane diamine. The organic amine can provide a nitrogen source for the reaction process and can react with Fe3+The lone pair electron coordination exists, and ammonia gas does not need to be decomposed or added as a nitrogen source.
Preferably, in the step (1), the stirring time is 20-40 min;
in the step (2), the drying temperature is 90-120 ℃, and the time is 20-40 min.
Preferably, in the step (2), the metallic soft magnetic powder is one selected from Fe, FeSi, FeSiAl, and FeSiB.
Preferably, the addition amount of the soluble ferric salt is 1-3 wt% based on the total mass of the metal soft magnetic powder; the addition amount of the organic solvent is 2-6 wt%, and the addition amount of the organic amine is 3-9 wt%. The addition amount of the soluble ferric salt is critical, the poor insulation property of the composite soft magnetic powder can be caused by the excessively low addition amount, the high loss can be caused, and the magnetic conductivity of the metal soft magnetic powder can be reduced by the excessively high addition amount. Too low addition of the organic solvent can lead to incomplete dissolution of the soluble ferric salt, and too high addition can lead to prolonged drying time and oxidation of the metal soft magnetic powder. The low addition of the organic amine can cause ferrite in the insulating layer, and the high addition of the organic amine can cause the over-thickness of the iron nitride insulating layer, thereby affecting the overall magnetic performance.
Preferably, in the step (3), the binder is selected from one or more of epoxy resin, silicone resin, silica, glass powder and water glass; the addition amount of the binder is 0.5-1 wt% based on the total mass of the metal soft magnetic powder. The binder is added in an amount that is too low, resulting in poor binding properties of the soft metal magnetic powder, and the binder is added in an amount that is too high, resulting in a decrease in magnetic permeability of the soft metal magnetic powder.
Preferably, in the step (3), the lubricant is selected from one or two of zinc stearate and barium stearate; the lubricant is added in an amount of 0.5-1 wt% based on the total mass of the metal soft magnetic powder.
Preferably, in the step (3), the pressure of the compression molding is 1500-2000 MPa. .
Preferably, in the step (4), the heat treatment temperature is 600-750 ℃ and the time is 0.5-2 h. The heat treatment temperature is critical, the internal stress generated in the pressing process cannot be released due to too low heat treatment temperature, the magnetic performance cannot reach the optimal value, and the binder can be damaged due to too high heat treatment temperature, so that the metal magnetic powder is further oxidized.
The iron nitride coated metal soft magnetic composite material prepared by any one of the preparation methods.
The insulating layer of the iron nitride coated metal magnetic powder core prepared by the process is thin, the magnetic dilution effect is reduced, and the high-frequency stability of the iron nitride coated metal magnetic powder core is enhanced on the premise of not obviously reducing the magnetic performance; the iron nitride coated metal magnetic powder core has the characteristics of low loss, high magnetic conductivity and good bonding strength, and can solve the problem of large eddy current loss of the metal soft magnetic powder core at medium-high frequency.
Therefore, the invention has the following beneficial effects:
(1) organic amine is used as an organic nitrogen source, and Fe-N interaction is enhanced through complexation performance, so that the high-quality iron nitride is prepared. Firstly, forming a uniform organic amine-iron-organic solvent compound on the surface of magnetic powder, then, converting the organic amine-iron-organic solvent compound layer into a compact and uniform iron nitride insulating layer through compression molding and high-temperature heat treatment in nitrogen, and avoiding the breakage of the iron oxide insulating layer in the compression process;
(2) the high-temperature roasting process of the iron nitride precursor is avoided, the high-temperature roasting process and the heat treatment process are creatively integrated, the energy consumption is reduced, the phase formation of the iron nitride can be controlled through the heat treatment temperature, and the magnetic property and the resistivity are regulated and controlled;
(3) the preparation method has simple operation, low cost and no pollution to the environment, and is suitable for large-scale industrial production;
(4) the iron nitride coated metal soft magnetic powder core prepared by the process has a thin insulating layer, has ferromagnetism, reduces the magnetic dilution effect, and enhances the high-frequency stability of the iron nitride coated metal soft magnetic powder core on the premise of not obviously reducing the magnetic performance; the iron nitride coated metal soft magnetic powder core has the characteristics of low loss, high magnetic conductivity and good bonding strength, and can solve the problem of large eddy current loss of the metal magnetic powder core at medium-high frequency.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) FeCl is added3Mixing with acetone, adding certain volume of ethylenediamine, and stirring at room temperature for 40min to obtain suspension. Taking the total mass of FeSiAl metal soft magnetic powder as a reference, FeCl3The addition amount of (B) is 3 wt%; the addition amount of acetone is 6wt%, and the addition amount of ethylenediamine is 9 wt%;
(2) adding the suspension obtained in the step (1) into FeSiAl metal soft magnetic powder, mixing, stirring uniformly at normal temperature, and drying at 120 ℃ for 40min to obtain FeSiAl metal soft magnetic powder @ ethylenediamine-Fe3+-an acetone precursor;
(3) uniformly mixing the insulated metal soft magnetic powder obtained in the step (2) with epoxy resin and zinc stearate, and performing compression molding under the pressure of 1500MPa to obtain a blank with the outer diameter of 33.00mm, the inner diameter of 19.90mm and the height of 10.7 mm; taking the total mass of the FeSiAl metal soft magnetic powder as a reference, the adding amount of the epoxy resin is 1wt%, and the adding amount of the zinc stearate is 1 wt%;
(4) and (3) carrying out heat treatment on the blank obtained in the step (3) in nitrogen, wherein the heat treatment temperature is 750 ℃, the time is 2 hours, cooling and spraying are carried out, and the FeSiAl metal magnetic powder core coated with the iron nitride is obtained, and the tested magnetic parameters are as follows:
example 2
(1) Mixing Fe2(SO4)3Mixing with toluene, adding isobutylamine in certain volume after complete dissolution, and stirring at normal temperature for 20min to form suspension. Based on the total mass of the FeSi metal soft magnetic powder, Fe2(SO4)3The addition amount of (B) is 1 wt%; the addition amount of acetone is 2 wt%; the addition amount of ethylenediamine is 3 wt%;
(2) adding the suspension obtained in the step (1) into FeSi metal soft magnetic powder for mixing, uniformly stirring at normal temperature, and drying at 90 ℃ for 20min to obtain FeSi metal soft magnetic powder @ isobutylamine-Fe3+-a toluene precursor;
(3) uniformly mixing the insulated metal soft magnetic powder obtained in the step (2) with silicone resin and barium stearate, and performing compression molding under the pressure of 2000MPa to obtain a blank with the outer diameter of 33.00mm, the inner diameter of 19.90mm and the height of 10.7 mm; taking the total mass of the FeSi metal soft magnetic powder as a reference, the adding amount of the epoxy resin is 0.5 wt%, and the adding amount of the zinc stearate is 0.5 wt%;
(4) and (3) carrying out heat treatment on the blank obtained in the step (3) in nitrogen at the heat treatment temperature of 600 ℃ for 0.5h, cooling and spraying to obtain the FeSi metal magnetic powder core coated with the iron nitride, wherein the tested magnetic parameters are as follows:
example 3
(1) Mixing Fe (NO)3)3Mixing with dimethylbenzene, adding isobutylamine with a certain volume after completely dissolving, and continuously stirring at normal temperature for 40min to form suspension. Fe (NO) based on the total mass of the FeSiB metal soft magnetic powder3)3The addition amount of (B) is 2 wt%; the addition amount of xylene was 4 wt%; the addition amount of diisopropylamine is 6 wt%;
(2) adding the suspension obtained in the step (1) into FeSiB metal soft magnetic powder, mixing, stirring uniformly at normal temperature, and drying for 30min at 100 ℃; obtaining FeSiB metal soft magnetic powder @ diisopropylamine-Fe3+-a xylene precursor;
(3) uniformly mixing the insulated metal soft magnetic powder obtained in the step (2) with silicone resin and barium stearate, and performing compression molding under the pressure of 1800MPa to obtain a blank with the outer diameter of 33.00mm, the inner diameter of 19.90mm and the height of 10.7 mm; taking the total mass of the FeSiB metal soft magnetic powder as a reference, the adding amount of the epoxy resin is 0.8 wt%, and the adding amount of the zinc stearate is 0.8 wt%;
(4) and (3) carrying out heat treatment on the blank obtained in the step (3) in nitrogen at the heat treatment temperature of 650 ℃ for 1.0h, cooling and spraying to obtain the FeSiB metal magnetic powder core coated with the iron nitride, wherein the tested magnetic parameters are as follows:
the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. The preparation method of the iron nitride coated metal soft magnetic composite material is characterized by comprising the following steps of:
(1) dissolving soluble ferric salt in an organic solvent, adding organic amine after the soluble ferric salt is completely dissolved, and stirring at normal temperature to form a suspension;
(2) adding the suspension obtained in the step (1) into the metal soft magnetic powder, mixing, stirring uniformly at normal temperature, and drying to obtain insulated metal soft magnetic powder;
(3) uniformly mixing the insulated metal soft magnetic powder obtained in the step (2) with a binder and a lubricant, and performing compression molding to obtain a blank;
(4) and (4) carrying out heat treatment on the blank obtained in the step (3) in nitrogen, cooling and spraying to obtain the iron nitride coated metal soft magnetic powder core.
2. The production method according to claim 1, wherein in step (1):
the soluble iron salt is selected from FeCl3、Fe2(SO4)3And Fe (NO)3)3One or more of the components are mixed;
the organic solvent is selected from one or a mixture of acetone, toluene, xylene and p-xylene;
the organic amine is selected from one or a mixture of ethylene diamine, isobutylamine, diisopropylamine, 1, 2-propane diamine and 1, 4-butane diamine.
3. The production method according to claim 1,
in the step (1), stirring for 20-40 min;
in the step (2), the drying temperature is 90-120 DEG C oAnd C, the time is 20-40 min.
4. The production method according to claim 1, wherein in the step (2), the metallic soft magnetic powder is one selected from the group consisting of Fe, FeSi, fesai, and FeSiB.
5. The preparation method according to claim 1, wherein the soluble iron salt is added in an amount of 1 to 3wt% based on the total mass of the metallic soft magnetic powder; the addition amount of the organic solvent is 2-6 wt%, and the addition amount of the organic amine is 3-9 wt%.
6. The preparation method according to claim 1, wherein in the step (3), the binder is one or more selected from epoxy resin, silicone resin, silica, glass powder and water glass; the addition amount of the binder is 0.5-1 wt% based on the total mass of the metal soft magnetic powder.
7. The production method according to claim 1, wherein in the step (3), the lubricant is one or two selected from zinc stearate and barium stearate; the lubricant is added in an amount of 0.5-1 wt% based on the total mass of the metal soft magnetic powder.
8. The production method according to claim 1, wherein in the step (3), the pressure of the press molding is 1500 to 2000 MPa.
9. The method according to claim 1, wherein the heat treatment temperature in step (4) is 600 to 750 ℃ for 0.5 to 2 hours.
10. An iron nitride-coated metal soft magnetic composite material prepared by the preparation method as claimed in any one of claims 1 to 9.
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