CN114806157A - Neodymium-iron-boron magnetic composite material and preparation method thereof - Google Patents
Neodymium-iron-boron magnetic composite material and preparation method thereof Download PDFInfo
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- CN114806157A CN114806157A CN202210475238.4A CN202210475238A CN114806157A CN 114806157 A CN114806157 A CN 114806157A CN 202210475238 A CN202210475238 A CN 202210475238A CN 114806157 A CN114806157 A CN 114806157A
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- iron boron
- neodymium iron
- boron magnetic
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- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 148
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title description 9
- 239000006247 magnetic powder Substances 0.000 claims abstract description 143
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 51
- 239000010703 silicon Substances 0.000 claims abstract description 51
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 48
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- 239000000314 lubricant Substances 0.000 claims abstract description 27
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000000576 coating method Methods 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 34
- 230000004048 modification Effects 0.000 claims description 34
- 238000012986 modification Methods 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000011282 treatment Methods 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 19
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 18
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 18
- 239000008116 calcium stearate Substances 0.000 claims description 18
- 235000013539 calcium stearate Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
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- 238000002156 mixing Methods 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 13
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
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- 239000000463 material Substances 0.000 description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 16
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 8
- 239000001488 sodium phosphate Substances 0.000 description 8
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- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 8
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 8
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- 239000007822 coupling agent Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
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- 238000013329 compounding Methods 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- 230000003749 cleanliness Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
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- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The neodymium iron boron magnetic composite material comprises the following components in parts by weight: 2-9 parts of thermoplastic resin; 90-95 parts by weight of surface modified neodymium iron boron magnetic powder; 1-3 parts of reactive compatibilizer; 0.1-0.5 part by weight of antioxidant; 0.3-1 part by weight of lubricant. The invention has the advantages that: the neodymium iron boron magnetic powder is coated with surface silicon, grafted and modified by a silane coupling agent and grafted by a stabilizing agent function, the problem of high-temperature oxidation of the neodymium iron boron magnetic powder is obviously solved, one end of the neodymium iron boron magnetic powder is in reaction connection with terminal carboxyl or terminal amino of thermoplastic resin through the bridging action of a reactive compatibilizer, and the other end of the neodymium iron boron magnetic powder is in reaction connection with hydroxyl on the surface of the modified neodymium iron boron magnetic powder, so that the compatibility of a thermoplastic resin matrix and the neodymium iron boron magnetic powder is effectively enhanced, the thermal stability in the processing process is improved, and the heat resistance and the mechanical property of the composite material are improved on the basis of ensuring that the neodymium iron boron magnetic composite material has better magnetic property.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a neodymium iron boron magnetic composite material and a preparation method thereof.
Background
Neodymium magnet (Neodymium magnet), also known as Neodymium-iron-boron magnet (NdFeB magnet), is made of Neodymium, iron, boron (Nd) 2 Fe 14 B) The tetragonal system crystal is formed. The zochu real man of the special metal of sumitomo discovered a neodymium magnet in 1982, which has a magnetic energy product (BHmax) greater than that of a samarium cobalt magnet, and is the largest material in the magnetic energy product worldwide at that time. Later, Sumitomo specialty metals successfully developed powder metallurgy (powder metallurgy) and general automotive successfully developed melt-spinning (melt-spinning) processes that could produce neodymium-iron-boron magnets. This magnet is a permanent magnet that is second only to absolute zero holmium magnets in magnetism today and is also the most commonly used rare earth magnet. The neodymium iron boron magnet is widely applied to the fields of electronic products, electric power machinery, medical instruments, toys, packaging, hardware machinery, aerospace and the like, such as hard disks, mobile phones, earphones, tools powered by batteries and the like.
The magnetic composite material is a composite material with a magnetic function, which is formed by compounding a thermosetting or thermoplastic polymer and a magnetic material, and is an indispensable part for national economic development. The neodymium iron boron magnetic composite material is formed by compounding magnetic neodymium iron boron magnetic powder and a non-magnetic thermosetting or thermoplastic polymer material, has light relative density, is easy to process into products with high dimensional precision and complex shapes, and has the outstanding advantages of excellent mechanical property, realization of large-scale automatic production and the like. The neodymium iron boron magnetic composite material is more and more widely applied to the fields of new energy automobile motors, household appliances, electronic technology, automation control, computers, satellites and other high and new technologies.
However, neodymium iron boron has high surface activity, and in high temperature, warm and humid environment, electrochemical environment and environment with hydrogen, the surface of neodymium iron boron is very easy to adsorb oxygen and moisture to generate oxidation corrosion, which leads to magnetic performance reduction and severely limits the large-scale use of neodymium iron boron in industry. Particularly, in the production process of the neodymium iron boron magnetic composite material, the forming and processing temperature of the thermoplastic resin is generally more than 200 ℃, so that the neodymium iron boron magnetic powder is often in a high-temperature environment of more than 200 ℃, and the oxidation of the magnetic material is more serious after the neodymium iron boron magnetic powder is contacted with air. Therefore, in order to obtain the ndfeb magnetic composite material with better magnetic performance, the problem that the ndfeb magnetic powder is easy to oxidize at high temperature must be solved.
At present, the neodymium iron boron magnetic powder is coated on the surface by forming a polymer coating, which is an important means for improving the oxidation resistance and the magnetic property of the neodymium iron boron magnetic composite material. There are several classification methods for the surface coating technology of ndfeb magnetic powder according to different ways. For example, the method can be classified into a solid phase coating method, a liquid phase coating method, and a gas phase coating method according to the state of the reaction system; the method is divided into a metal coating method, an inorganic coating method and an organic coating method according to the properties of shell materials; the coating method can be classified into a physical coating method, a chemical coating method, and the like according to the coating property.
Patent CN111378282A discloses a PPS-based permanent magnet composite material and a preparation method thereof, wherein the raw materials comprise 85-95 wt% of magnetic powder after surface treatment and 5-15 wt% of adhesive, and the adhesive comprises the following materials: 0.1-60.0 wt% of thermoplastic resin, 40.0-99.0 wt% of polyphenylene sulfide resin, 0.1-10.0 wt% of compatilizer, 0.01-1.0 wt% of antioxidant and 0.01-1.0 wt% of lubricant; the magnetic powder after surface treatment is prepared by coating the surface of the magnetic powder by using a coating material, wherein the coating material is silane or titanate coupling agent, and the dosage of the coating material is 0.01-1.0 wt% of the mass of the magnetic powder. According to the invention, the surface of the neodymium iron boron magnetic powder is coated by using silane or titanate coupling agent, and other thermoplastic resin is added into PPS to prepare the adhesive, so that the adhesive neodymium iron boron composite material is obtained, and the aims of mainly solving the defects of poor fluidity and difficult molding of PPS-based magnets are achieved, but the composite material prepared by the method has slightly poor magnetism and oxidation resistance and cannot meet the application requirements.
Patent CN103258610B discloses a magnetic plastic composite material, which is prepared from the following components in parts by mass: 4 to 8 percent of nylon 6 powder, 90 to 95 percent of neodymium iron boron magnetic powder, 0.5 to 5 percent of caprolactam, 0.5 to 1.5 percent of lubricant and 0.3 to 1 percent of silane coupling agent. The invention also discloses a preparation method of the magnetic plastic composite material. The neodymium iron boron magnetic powder reaches 90-95%, so that the magnetic strength is high; the neodymium iron boron magnetic powder and the nylon 6 powder are fully mixed, so that the neodymium iron boron magnetic powder is uniformly distributed and uniform in magnetism. Although the invention uses the silane coupling agent to modify the neodymium iron boron magnetic powder, the magnetic performance of the obtained material is slightly poor, and simultaneously the oxidation resistance of the material composite material can not be ensured.
Therefore, how to obtain the neodymium iron boron magnetic powder with good compatibility with the polymer matrix material and strong oxidation resistance so as to prepare the composite material with excellent comprehensive performance is a key for restricting the large-scale production and wide application of the neodymium iron boron magnetic powder and the composite material thereof, and is a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the neodymium iron boron magnetic composite material and the preparation method thereof. The neodymium iron boron magnetic composite material has good mechanical property, processing property and magnetic property.
Specifically, the invention provides a neodymium iron boron magnetic composite material which comprises the following components in parts by weight:
2-9 parts of thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 part by weight of lubricant;
the antioxidant is at least one of hindered phenol and phosphite antioxidant;
the lubricant is at least one of calcium stearate and ethylene bis fatty acid amide;
the surface modified neodymium iron boron magnetic powder is sequentially provided with a surface silicon coating layer, a silane coupling agent grafting modification layer and a stabilizing agent functional grafting layer from inside to outside.
Further, the thermoplastic resin is polyamide 6(PA6), polyamide 12(PA12), or polyphenylene sulfide (PPS).
Further, the antioxidant is a compound antioxidant, wherein the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 2; the lubricant is a compound lubricant, wherein the weight ratio of calcium stearate to ethylene bis fatty acid amide is 2: 3.
further, the reactive compatibilizer is at least one of alkylene oxide silane and isocyanate alkyl silane;
the structural formula of the alkylene oxide silane is
Structural formula of isocyanate alkyl silane
NCO-R″Si-X 3
Wherein R 'and R' are selected from-CH 2 -O-(CH 2 ) 3 、-(CH 2 ) 4 And- (CH) 2 ) 8 X is one of methoxyl, ethoxyl and acetoxy.
Further, the surface modified neodymium iron boron magnetic powder is modified through the following steps:
1) surface silicon coating:
at least one of sodium silicate and ethyl orthosilicate is used as a surface silicon coating raw material, and surface silicon coating treatment is carried out on the neodymium iron boron magnetic powder;
2) graft modification by a silane coupling agent:
dispersing the neodymium iron boron magnetic powder coated with the surface silicon in a solvent, adding a silane coupling agent for modification treatment, and then evaporating under reduced pressure to remove the solvent to obtain the surface modified neodymium iron boron magnetic powder;
3) functional graft modification of a stabilizer:
adopting a stabilizer 3, 5-di-tert-butyl-4-hydroxybenzoic Acid (AO) to perform functional grafting modification on the neodymium iron boron magnetic powder which is modified by the silane coupling agent.
Preferably, in order to improve the efficiency and effect of the surface modification treatment of the neodymium iron boron magnetic powder, the steps of degreasing, plasma surface activation treatment and the like are preferably performed before the silicon coating of the surface in the step 1) is performed to enhance the subsequent modification effect.
Wherein, the degreasing step specifically comprises:
preparing an oil-removing degreasing cleaning agent: each liter of solution contains 5-10g of sodium hydroxide, 15-30g of sodium carbonate, 30-50g of trisodium phosphate, 10-15g of sodium pyrophosphate, 1-3g of OP-10 emulsifier, 1-2g of sodium dodecyl sulfate and 0.5-1.5g of thiourea;
dispersing neodymium iron boron magnetic powder in the cleaning agent, under the protection of nitrogen, dispersing the neodymium iron boron magnetic powder in the cleaning agent, ultrasonically cleaning for 30-90 minutes, filtering, and ultrasonically cleaning in deionized water for 5-10 minutes; and (5) drying in vacuum.
The plasma surface activation treatment step specifically comprises:
controlling the vacuum degree to be 1 x 10 -2 -10×10 -2 And Pa, heating to 80-120 ℃, introducing argon, and activating the surface of the neodymium iron boron magnetic powder by using argon plasma under vacuum for 1-5 min.
The surface of the neodymium iron boron magnetic powder is subjected to activation treatment by adopting an ion source, so that the potential energy on the surface of the neodymium iron boron magnetic powder can be increased by at least 1 magnitude, the binding energy barrier of a subsequent modified material and the surface of the neodymium iron boron magnetic powder is obviously reduced, impurities and oxides on the surface of the magnetic powder can be further removed after degreasing, degreasing and cleaning, the cleanliness of the magnetic powder is improved, and the binding firmness of the subsequent modified material and the magnetic powder is favorably improved.
Further, according to the difference of the surface silicon coating raw material, the step 1) can be carried out by adopting two modes:
firstly, sodium silicate is adopted as a raw material in surface silicon coating, and the method comprises the following steps:
dispersing the neodymium iron boron magnetic powder in a sodium silicate solution, slowly and dropwise adding 0.5mol/L HCl solution under the protection of nitrogen at 50-90 ℃ until the pH value is 6, wherein the reaction time is 2-3h, and the using amount of sodium silicate is 3-7% of the weight of the neodymium iron boron magnetic powder.
Secondly, the surface silicon coating adopts tetraethoxysilane as a raw material, and comprises the following steps:
dispersing neodymium iron boron magnetic powder in ammonia water, slowly dripping ethyl orthosilicate (TEOS) ethanol solution under the protection of nitrogen at 50-70 ℃, and reacting for 4-6 h; in the ethanol solution, the volume ratio of water to ethanol is 1: (2-8); the addition amount of the tetraethyl orthosilicate (TEOS) is 2-6% of the weight of the neodymium-iron-boron magnetic powder.
Further, the step 2) of the silane coupling agent grafting modification step comprises the following steps:
ultrasonically dispersing neodymium iron boron powder coated with surface silicon in toluene, slowly adding an acetic acid solution of a silane coupling agent under the protection of nitrogen at 50-70 ℃, wherein the pH value is 3-4, and the reaction time is 6-8 h. Preferably, the silane coupling agent comprises at least one of KH550, KH602 and KH900, and the dosage of the silane coupling agent is 0.5-2.0% of the weight of the neodymium iron boron magnetic powder.
Further, the step 3) of functional grafting of the stabilizer comprises the following steps:
ultrasonically dispersing neodymium iron boron magnetic powder which is coated with silicon on the surface and is grafted and modified by a silane coupling agent in DMF, wherein the solid content of the neodymium iron boron magnetic powder is 0.1-0.5 g/mL; adding saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid for reaction for 12-14h, wherein the amount of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5-2.0% of the weight of the neodymium iron boron magnetic powder.
On the other hand, the invention also provides a preparation method of the neodymium iron boron magnetic composite material, which comprises the following steps:
(1) weighing the raw materials in parts by weight, and uniformly mixing:
2-9 parts of thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 part by weight of lubricant;
(2) and (2) adding the mixed raw materials in the step (1) into a double-screw extruder, performing melt reaction at 200-320 ℃ for extrusion, and cooling and dicing to obtain the neodymium-iron-boron magnetic composite material.
Furthermore, a kneader can be selected as the mixing equipment, the rotating speed of the kneader is 60-120 r/min, the kneading time is 25-40 min, and nitrogen is introduced for protection in the kneading process.
Further, the extruder is a segmented temperature control type extruder, preferably at least five segments and a machine head segment are used for controlling the temperature, and more preferably eight segments and a machine head segment are used for controlling the temperature. And the temperature of each zone is regulated and controlled according to the property difference of raw materials, particularly resin matrixes. For example:
when the resin is polyamide 6(PA6), the temperature of each section is respectively as follows: the temperature of the first zone is 200 ℃ and 220 ℃, and the temperature is preferably 210 ℃; the temperature of the second zone is 230 ℃ and 250 ℃, and the preference is 240 ℃; the temperature of the three zones is 230 ℃ and 250 ℃, and the preference is 240 ℃; the temperature of the four zones is 230 ℃ and 240 ℃, preferably 235 ℃; the temperature of the five zones is 230 ℃ and 240 ℃, and 235 ℃ is preferred; the temperature of the six zones is 220 ℃ and 240 ℃, and the temperature is preferably 230 ℃; the temperature of the seven zones is 220 ℃ and 230 ℃, preferably 225 ℃; the temperature of the eight regions is 220 ℃ and 240 ℃, and the temperature is preferably 230 ℃; the head temperature is 240 ℃ to 250 ℃, preferably 245 ℃.
When the resin is polyphenylene sulfide (PPS), the temperature of each section is respectively as follows: the temperature of the first zone is 270 ℃ and 290 ℃, and the temperature is preferably 280 ℃; the temperature of the second zone is 300 ℃ and 320 ℃, and the temperature is preferably 310 ℃; the temperature of the three zones is 300-320 ℃, and preferably 310 ℃; the temperature of the four zones is 300-310 ℃, preferably 305 ℃; the temperature of the five zones is 300-310 ℃, and the priority is 305 ℃; the temperature of the six zones is 290 ℃ and 310 ℃, and the temperature is preferably 300 ℃; the temperature of the seven zones is 290 ℃ and 300 ℃, and preferably 295 ℃; the temperature of the eight zones is 290 ℃ and 310 ℃, and the temperature is preferably 300 ℃; the head temperature is 300 ℃ to 320 ℃, preferably 310 ℃.
The invention has the beneficial effects that:
1) the modified neodymium iron boron magnetic powder is compounded with high-performance thermoplastic matrix materials, such as polyamide 6(PA6), polyamide 12(PA12) and polyphenylene sulfide (PPS), and by means of the bridging effect of the reactive compatibilizer, the high magnetic performance, heat resistance and oxidation resistance of the neodymium iron boron magnetic powder are guaranteed, the magnetic composite material with excellent comprehensive performances such as mechanical properties is obtained under the action of high compatibility, and a wider application space is provided for the neodymium iron boron magnetic powder and the magnetic composite material thereof.
2) The silicon material has stable chemical properties, has excellent performances such as high melting point and the like, and can be coated by silicon to enable silicon particles to be deposited on the surface of magnetic powder to improve the corrosion resistance of a silicon coating and simultaneously keep the magnetism of neodymium iron boron.
3) A comprehensive neodymium iron boron magnetic powder surface modification scheme is designed through experimental summary, so that the neodymium iron boron magnetic powder surface is subjected to a series of treatments of oil removal and degreasing, surface activation, surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting, and preparation is made for subsequent processing and compounding processes. Firstly, the magnetic powder is subjected to oil removal and degreasing and plasma activation treatment, so that the surface cleanliness and activity of the magnetic powder are improved, and the subsequent modification treatment such as oxidation resistance and the like on the outer surface of the magnetic powder is facilitated. Secondly, the magnetic powder surface modification treatment comprises surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting step by step, and the three are organically combined and act synergistically. In the surface silicon coating step, sodium silicate or tetraethoxysilane is effectively coated on the outer surface of the magnetic powder, and the coating material has better heat resistance and strength, can effectively improve the heat resistance and strength performance of the magnetic powder, is favorable for compounding the magnetic powder with other materials through a forming process, and is used in high-temperature environments such as motors, generators and the like; however, the coating material has the defect of larger hygroscopicity, so that silane coupling agent grafting modification and stabilizer function grafting are further carried out on the outer surface of the coating material, on one hand, the hygroscopicity of the coating material can be reduced, the oxidation resistance and the corrosion resistance are improved, the neodymium iron boron magnetic powder is prevented from demagnetizing in the high-temperature processing process, the problem of high-temperature oxidation of the neodymium iron boron magnetic powder is obviously improved, and the neodymium iron boron magnetic composite material is ensured to have better magnetic performance; on the other hand, the magnetic powder is also favorable for improving the compatibility of the magnetic powder and the polymer matrix material, and the compressive strength of the magnetic composite material is improved while the better magnetic performance is ensured.
Drawings
FIG. 1 shows a flow chart for the preparation of a neodymium iron boron magnetic composite;
FIG. 2 shows a technical route for preparing modified NdFeB magnetic powder;
FIG. 3 shows the SEM photograph of the dispersion of Nd-Fe-B magnetic powder in composite material
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
Example 1
Weighing 4 parts by weight of polyamide 6(PA6) resin, 94.5 parts by weight of surface modified neodymium iron boron magnetic powder, 1 part by weight of alkylene oxide silane, 0.2 part by weight of antioxidant and 0.3 part by weight of lubricant, and sequentially adding the materials into a mixing device for uniformly mixing; adding the neodymium iron boron magnetic composite material into a double-screw extruder through a main feeding hopper, and performing melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperature of each section is as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 240 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 235 ℃, the temperature of the fifth zone is 235 ℃, the temperature of the sixth zone is 230 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the eighth zone is 230 ℃ and the temperature of the head is 245 ℃.
The surface modified neodymium iron boron magnetic powder treatment in the embodiment comprises oil removal and degreasing, surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting; wherein each liter of solution of the degreasing and degreasing cleaning agent comprises 10g of sodium hydroxide, 30g of sodium carbonate, 50g of trisodium phosphate, 15g of sodium pyrophosphate, 3g of OP-10 emulsifier, 2g of sodium dodecyl sulfate and 1.5g of thiourea; the surface silicon coating process is that neodymium iron boron powder is dispersed in sodium silicate solution, 0.5mol/L HCl solution is slowly dripped to the pH value of 6 under the protection of nitrogen at the temperature of 90 ℃, the reaction time is 2 hours, and the dosage of the sodium silicate is 7 wt% of the weight of the neodymium iron boron magnetic powder; ultrasonically dispersing neodymium iron boron magnetic powder coated with silicon on the surface in toluene, slowly adding an acetic acid solution (pH is 3-4) of a silane coupling agent under the protection of nitrogen at 70 ℃, reacting for 6 hours, wherein the using amount of the silane coupling agent is 2.0 wt% of the weight of the neodymium iron boron magnetic powder, and the silane coupling agent is KH 550; the neodymium iron boron magnetic powder with the surface coated by silicon and grafted and modified by aminosilane coupling agent is dispersed in DMF by ultrasonic, saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 2.0 wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidant in this example is 1010 and 168 in a weight ratio of 1: 2.
The lubricant in the embodiment is a composition of calcium stearate and ethylene bis-fatty acid amide, and the weight ratio of the calcium stearate to the ethylene bis-fatty acid amide is 2: 3.
Example 2
Weighing 3 parts by weight of polyphenylene sulfide (PPS) resin, 94.5 parts by weight of surface modified neodymium iron boron magnetic powder, 2 parts by weight of alkylene oxide silane, 0.2 part by weight of antioxidant and 0.3 part by weight of lubricant, and sequentially adding the materials into a mixing device for uniform mixing; adding the neodymium iron boron magnetic composite material into a double-screw extruder through a main feeding hopper, and performing melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperature of each section is as follows: the temperature in the first zone is 280 ℃, the temperature in the second zone is 310 ℃, the temperature in the third zone is 310 ℃, the temperature in the fourth zone is 305 ℃, the temperature in the fifth zone is 305 ℃, the temperature in the sixth zone is 300 ℃, the temperature in the seventh zone is 295 ℃, the temperature in the eighth zone is 300 ℃ and the temperature in the head is 310 ℃.
The surface modified neodymium iron boron magnetic powder treatment in the embodiment comprises oil removal and degreasing, surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting; wherein each liter of solution of the degreasing and degreasing cleaning agent comprises 10g of sodium hydroxide, 30g of sodium carbonate, 50g of trisodium phosphate, 15g of sodium pyrophosphate, 3g of OP-10 emulsifier, 2g of sodium dodecyl sulfate and 1.5g of thiourea; the surface silicon coating process is that neodymium iron boron powder is dispersed in sodium silicate solution, 0.5mol/L HCl solution is slowly dripped to the pH value of 6 under the protection of nitrogen at the temperature of 90 ℃, the reaction time is 2 hours, and the dosage of the sodium silicate is 7 wt% of the weight of the neodymium iron boron magnetic powder; ultrasonically dispersing neodymium iron boron magnetic powder coated with silicon on the surface in toluene, slowly adding an acetic acid solution (pH is 3-4) of a silane coupling agent under the protection of nitrogen at 70 ℃, reacting for 6 hours, wherein the using amount of the silane coupling agent is 2.0 wt% of the weight of the neodymium iron boron magnetic powder, and the silane coupling agent is KH 550; the neodymium iron boron magnetic powder with the surface coated by silicon and grafted and modified by aminosilane coupling agent is dispersed in DMF by ultrasonic, saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 2.0 wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidant in this example is 1010 and 168 in a weight ratio of 1: 2.
The lubricant in the embodiment is a composition of calcium stearate and ethylene bis-fatty acid amide, and the weight ratio of the calcium stearate to the ethylene bis-fatty acid amide is 2: 3.
Example 3
Weighing 7 parts by weight of polyamide 6(PA6) resin, 89.2 parts by weight of surface modified neodymium iron boron magnetic powder, 3 parts by weight of alkylene oxide silane, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, and sequentially adding the materials into a mixing device for uniformly mixing; adding the neodymium iron boron magnetic composite material into a double-screw extruder through a main feeding hopper, and performing melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperature of each section is as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 240 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 235 ℃, the temperature of the fifth zone is 235 ℃, the temperature of the sixth zone is 230 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the eighth zone is 230 ℃ and the temperature of the head is 245 ℃.
The surface modified neodymium iron boron magnetic powder treatment in the embodiment comprises oil removal and degreasing, surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting; wherein, each liter of solution of the degreasing and degreasing cleaning agent comprises 5g of sodium hydroxide, 15g of sodium carbonate, 30g of trisodium phosphate, 10g of sodium pyrophosphate, 1g of OP-10 emulsifier, 1g of sodium dodecyl sulfate and 0.5g of thiourea; the surface silicon coating process is that neodymium iron boron powder is dispersed in ammonia water, and under the protection of nitrogen at 70 ℃, an ethanol solution of TEOS is slowly dripped, the reaction time is 4 hours, the proportion of water to ethanol is 1:3, and the amount of TEOS is 2 wt% of the weight of neodymium iron boron magnetic powder; ultrasonically dispersing neodymium iron boron magnetic powder coated with silicon on the surface in toluene, slowly adding an acetic acid solution (pH is 3-4) of a silane coupling agent under the protection of nitrogen at 70 ℃, reacting for 6 hours, wherein the using amount of the silane coupling agent is 0.5 wt% of the weight of the neodymium iron boron magnetic powder, and the silane coupling agent is KH 550; the neodymium iron boron magnetic powder with the surface coated by silicon and grafted and modified by aminosilane coupling agent is dispersed in DMF by ultrasonic, saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5 wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidant in this example is 1010 and 168 in a weight ratio of 1: 2.
The lubricant in the embodiment is a composition of calcium stearate and ethylene bis-fatty acid amide, and the weight ratio of the calcium stearate to the ethylene bis-fatty acid amide is 2: 3.
Example 4
Weighing 4 parts by weight of polyphenylene sulfide (PPS) resin, 94.2 parts by weight of surface modified neodymium iron boron magnetic powder, 1 part by weight of isocyanate alkyl silane, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, and sequentially adding the materials into a mixing device for uniform mixing; adding the neodymium iron boron magnetic composite material into a double-screw extruder through a main feeding hopper, and performing melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperature of each section is as follows: the temperature in the first zone is 280 ℃, the temperature in the second zone is 310 ℃, the temperature in the third zone is 310 ℃, the temperature in the fourth zone is 305 ℃, the temperature in the fifth zone is 305 ℃, the temperature in the sixth zone is 300 ℃, the temperature in the seventh zone is 295 ℃, the temperature in the eighth zone is 300 ℃ and the temperature in the head is 310 ℃.
The surface modified neodymium iron boron magnetic powder treatment in the embodiment comprises oil removal and degreasing, surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting; wherein, each liter of solution of the degreasing and degreasing cleaning agent comprises 5g of sodium hydroxide, 15g of sodium carbonate, 30g of trisodium phosphate, 10g of sodium pyrophosphate, 1g of OP-10 emulsifier, 1g of sodium dodecyl sulfate and 0.5g of thiourea; the surface silicon coating process is that neodymium iron boron powder is dispersed in ammonia water, and under the protection of nitrogen at 70 ℃, an ethanol solution of TEOS is slowly dripped, the reaction time is 4 hours, the proportion of water to ethanol is 1:3, and the amount of TEOS is 2 wt% of the weight of neodymium iron boron magnetic powder; ultrasonically dispersing neodymium iron boron magnetic powder coated with silicon on the surface in toluene, slowly adding an acetic acid solution (pH is 3-4) of a silane coupling agent under the protection of nitrogen at 70 ℃, reacting for 6 hours, wherein the using amount of the silane coupling agent is 0.5 wt% of the weight of the neodymium iron boron magnetic powder, and the silane coupling agent is KH 550; the neodymium iron boron magnetic powder with the surface coated by silicon and grafted and modified by aminosilane coupling agent is dispersed in DMF by ultrasonic, saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5 wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidant in this example is 1010 and 168 in a weight ratio of 1: 2.
The lubricant in the embodiment is a composition of calcium stearate and ethylene bis-fatty acid amide, and the weight ratio of the calcium stearate to the ethylene bis-fatty acid amide is 2: 3.
Comparative example 1
Weighing 5 parts by weight of polyamide 6(PA6) resin, 94.5 parts by weight of surface modified neodymium iron boron magnetic powder, 0.2 part by weight of antioxidant and 0.3 part by weight of lubricant, and sequentially adding the materials into a mixing device for uniform mixing; adding the neodymium iron boron magnetic composite material into a double-screw extruder through a main feeding hopper, and performing melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperature of each section is as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 240 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 235 ℃, the temperature of the fifth zone is 235 ℃, the temperature of the sixth zone is 230 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the eighth zone is 230 ℃ and the temperature of the head is 245 ℃.
The surface modified neodymium iron boron magnetic powder treatment in the embodiment comprises oil removal and degreasing, surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting; wherein each liter of solution of the degreasing and degreasing cleaning agent comprises 10g of sodium hydroxide, 30g of sodium carbonate, 50g of trisodium phosphate, 15g of sodium pyrophosphate, 3g of OP-10 emulsifier, 2g of sodium dodecyl sulfate and 1.5g of thiourea; the surface silicon coating process is that neodymium iron boron powder is dispersed in sodium silicate solution, 0.5mol/L HCl solution is slowly dripped to the pH value of 6 under the protection of nitrogen at the temperature of 90 ℃, the reaction time is 2 hours, and the dosage of the sodium silicate is 7 wt% of the weight of the neodymium iron boron magnetic powder; ultrasonically dispersing neodymium iron boron magnetic powder coated with silicon on the surface in toluene, slowly adding an acetic acid solution (pH is 3-4) of a silane coupling agent under the protection of nitrogen at 70 ℃, reacting for 6 hours, wherein the using amount of the silane coupling agent is 2.0 wt% of the weight of the neodymium iron boron magnetic powder, and the silane coupling agent is KH 550; the neodymium iron boron magnetic powder with the surface coated by silicon and the amino silane coupling agent graft modification is dispersed in DMF by ultrasonic, saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 14h, and the using amount of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 2.0 wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidant in this example is 1010 and 168 in a weight ratio of 1: 2.
The lubricant in the embodiment is a composition of calcium stearate and ethylene bis-fatty acid amide, and the weight ratio of the calcium stearate to the ethylene bis-fatty acid amide is 2: 3.
Comparative example 2
Weighing 5 parts by weight of polyphenylene sulfide (PPS) resin, 94.2 parts by weight of surface modified neodymium iron boron magnetic powder, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, and sequentially adding the materials into a mixing device for uniform mixing; adding the neodymium iron boron magnetic composite material into a double-screw extruder through a main feeding hopper, and performing reactive extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperature of each section is as follows: the temperature in the first zone is 280 ℃, the temperature in the second zone is 310 ℃, the temperature in the third zone is 310 ℃, the temperature in the fourth zone is 305 ℃, the temperature in the fifth zone is 305 ℃, the temperature in the sixth zone is 300 ℃, the temperature in the seventh zone is 295 ℃, the temperature in the eighth zone is 300 ℃ and the temperature in the head is 310 ℃.
The surface modified neodymium iron boron magnetic powder treatment in the embodiment comprises oil removal and degreasing, surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting; wherein, each liter of solution of the degreasing and degreasing cleaning agent comprises 5g of sodium hydroxide, 15g of sodium carbonate, 30g of trisodium phosphate, 10g of sodium pyrophosphate, 1g of OP-10 emulsifier, 1g of sodium dodecyl sulfate and 0.5g of thiourea; the surface silicon coating process is that neodymium iron boron powder is dispersed in ammonia water, and under the protection of nitrogen at 70 ℃, an ethanol solution of TEOS is slowly dripped, the reaction time is 4 hours, the proportion of water to ethanol is 1:3, and the amount of TEOS is 2 wt% of the weight of neodymium iron boron magnetic powder; ultrasonically dispersing neodymium iron boron magnetic powder coated with silicon on the surface in toluene, slowly adding an acetic acid solution (pH is 3-4) of a silane coupling agent under the protection of nitrogen at 70 ℃, reacting for 6 hours, wherein the using amount of the silane coupling agent is 0.5 wt% of the weight of the neodymium iron boron magnetic powder, and the silane coupling agent is KH 550; the neodymium iron boron magnetic powder with the surface coated by silicon and grafted and modified by aminosilane coupling agent is dispersed in DMF by ultrasonic, saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5 wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidant in this example is 1010 and 168 in a weight ratio of 1: 2.
The lubricant in the embodiment is a composition of calcium stearate and ethylene bis-fatty acid amide, and the weight ratio of the calcium stearate to the ethylene bis-fatty acid amide is 2: 3.
Comparative example 3
Weighing 5 parts by weight of polyamide 6(PA6) resin, 94.5 parts by weight of neodymium iron boron magnetic powder, 0.2 part by weight of antioxidant and 0.3 part by weight of lubricant, and sequentially adding the materials into a mixing device for uniform mixing; adding the neodymium iron boron magnetic composite material into a double-screw extruder through a main feeding hopper, and performing melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperature of each section is as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 240 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 235 ℃, the temperature of the fifth zone is 235 ℃, the temperature of the sixth zone is 230 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the eighth zone is 230 ℃ and the temperature of the head is 245 ℃.
The neodymium iron boron magnetic powder treatment in the comparative example is oil removal and degreasing, wherein each liter of solution of the oil removal and degreasing cleaning agent comprises 5g of sodium hydroxide, 15g of sodium carbonate, 30g of trisodium phosphate, 10g of sodium pyrophosphate, 1g of OP-10 emulsifier, 1g of sodium dodecyl sulfate and 0.5g of thiourea.
The antioxidant in this example is 1010 and 168 in a weight ratio of 1: 2.
The lubricant in the embodiment is a composition of calcium stearate and ethylene bis-fatty acid amide, and the weight ratio of the calcium stearate to the ethylene bis-fatty acid amide is 2: 3.
The magnetic properties and compressive strength of the ndfeb magnetic composites prepared in the above examples and comparative examples were tested and the results are shown in table 1.
Br (mt): residual magnetic induction intensity
jHc (kA/m): coercivity value of magnetic polarization strength
(BH)max(kJ/m 3 ): maximum magnetic energy product of material
TABLE 1 magnetic Properties and compressive Strength of NdFeB magnetic composites
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Br(mT) | 469 | 476 | 457 | 463 | 443 | 440 | 421 |
| jHc(kA/m) | 714 | 728 | 694 | 708 | 675 | 670 | 643 |
| (BH)max(kJ/m 3 ) | 39.1 | 38.3 | 37.2 | 37.5 | 37.1 | 35.8 | 34.5 |
| Compressive strength (MPa) | 98.2 | 97.5 | 103.1 | 93.7 | 89.8 | 87.9 | 65.9 |
From the test data, the composite materials of examples 1-4 of the present invention all had a remanence Br greater than 450 mT; the magnetic polarization strength coercive force values jHc are all larger than 690 kA/m; the maximum magnetic energy product (BH) max of the material is more than 37kJ/m 3 The overall magnetic performance is superior to that of the comparative material, in particular superior to that of the surface unmodified NdFeB magnetic composite material in the comparative example 3. In general, the magnetic properties are improved relatively more as the degree of surface modification treatment of the magnetic powder is higher, which also shows the necessity of surface modification of the neodymium iron boron magnetic powder, and the feasibility and scientificity of the invention to perform step-by-step layered surface modification of the magnetic powder and to select high-performance matrix materials.
In terms of mechanical properties of the composite material, it can be found from the test data of the examples and comparative examples that: comparative examples 1 and 2, although neodymium iron boron modified magnetic powder was used, no reactive compatibilizer was used, resulting in slightly lower compatibility between the magnetic powder and the matrix material, and macroscopically lower compressive strength than in the above examples; the comparative example 3 neither adopts the surface unmodified neodymium iron boron magnetic powder nor uses the reactive compatibilizer, so that the compressive strength of the composite material is obviously lower than that of the embodiment while the magnetic property is poor; compared with the composite material prepared by only adopting the modified neodymium iron boron magnetic powder and not using the reactive compatibilizer in the comparative examples 1 and 2, the compressive strength of the neodymium iron boron magnetic composite material prepared by simultaneously using the modified neodymium iron boron magnetic powder and the reactive compatibilizer in the examples 1 to 4 is over 90Mpa, so that the composite material has obvious mechanical property advantages, and the magnetic powder is not obviously exposed, and the matrix presents a complete and uniform image as seen from a scanning electron microscope photo of the dispersion of the neodymium iron boron magnetic powder in the composite material shown in fig. 3. On the other hand, in examples 1 to 4, as the content of the non-magnetic substance such as resin is increased, the magnetic property of the composite material tends to be decreased slightly, but the compressive strength is increased to a certain extent.
In conclusion, the three-layer protection structure with excellent oxidation resistance and heat resistance is formed on the surface of the neodymium iron boron magnetic powder through surface silicon coating, silane coupling agent grafting modification and stabilizer function grafting modification, so that the oxidation loss of the neodymium iron boron magnetic powder in the high-temperature melting reaction extrusion processing process is obviously reduced, and the composite material has better magnetic performance; in addition, on the basis of selecting a high-performance matrix material, a reactive compatibilizer is further used to uniformly disperse and bridge magnetic powder into the high-performance matrix material, so that the magnetic powder is protected by the matrix and simultaneously forms a reinforcing effect on the matrix, and the mechanical properties such as compressive strength and the like of the composite material are improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The neodymium-iron-boron magnetic composite material is characterized by comprising the following components in parts by weight:
2-9 parts of thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 part by weight of lubricant;
the antioxidant is at least one of hindered phenol and phosphite antioxidant;
the lubricant is at least one of calcium stearate and ethylene bis fatty acid amide;
the surface modified neodymium iron boron magnetic powder is sequentially provided with a surface silicon coating layer, a silane coupling agent grafting modification layer and a stabilizing agent functional grafting layer from inside to outside.
2. The ndfeb magnetic composite material according to claim 1, wherein: the thermoplastic resin is polyamide 6(PA6), polyamide 12(PA12) or polyphenylene sulfide (PPS).
3. The ndfeb magnetic composite material according to claim 2, wherein: the antioxidant is a compound antioxidant, wherein the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 2; the lubricant is a compound lubricant, wherein the weight ratio of calcium stearate to ethylene bis fatty acid amide is 2: 3.
4. the ndfeb magnetic composite material according to claim 2, wherein: the reactive compatibilizer is at least one of alkylene oxide silane and isocyanate alkyl silane;
the structural formula of the alkylene oxide silane is:
the structural formula of the isocyanate alkylsilane:
NCO-R″Si-X 3
wherein R 'and R' are selected from-CH 2 -O-(CH 2 ) 3 、-(CH 2 ) 4 And- (CH) 2 ) 8 X is one of methoxyl, ethoxyl and acetoxy.
5. The ndfeb magnetic composite material according to any of claims 1 to 4, wherein the surface modified ndfeb magnetic powder is modified by:
1) surface silicon coating:
at least one of sodium silicate and ethyl orthosilicate is used as a surface silicon coating raw material, and surface silicon coating treatment is carried out on the neodymium iron boron magnetic powder;
2) graft modification by a silane coupling agent:
dispersing the neodymium iron boron magnetic powder coated with the surface silicon in a solvent, adding a silane coupling agent for modification treatment, and then evaporating under reduced pressure to remove the solvent to obtain the surface modified neodymium iron boron magnetic powder;
3) functional graft modification of a stabilizer:
adopting a stabilizer 3, 5-di-tert-butyl-4-hydroxybenzoic Acid (AO) to perform functional graft modification on the neodymium iron boron magnetic powder which is graft-modified by the silane coupling agent.
6. The neodymium iron boron magnetic composite material according to claim 5, characterized in that sodium silicate is adopted as a raw material in the step 1) surface silicon coating, and the method comprises the following steps:
dispersing the neodymium iron boron magnetic powder in a sodium silicate solution, slowly and dropwise adding 0.5mol/L HCl solution under the protection of nitrogen at 50-90 ℃ until the pH value is 6, wherein the reaction time is 2-3h, and the using amount of sodium silicate is 3-7% of the weight of the neodymium iron boron magnetic powder.
7. The neodymium iron boron magnetic composite material of claim 5, wherein tetraethoxysilane is adopted as a raw material in the silicon coating of the surface in the step 1), and the method comprises the following steps:
dispersing neodymium iron boron magnetic powder in ammonia water, slowly dripping ethyl orthosilicate (TEOS) ethanol solution under the protection of nitrogen at 50-70 ℃, and reacting for 4-6 h; in the ethanol solution, the volume ratio of water to ethanol is 1: (2-8); the addition amount of the tetraethyl orthosilicate (TEOS) is 2-6% of the weight of the neodymium-iron-boron magnetic powder.
8. The ndfeb magnetic composite material according to claim 6 or 7, wherein the step 2) of silane coupling agent graft modification comprises:
ultrasonically dispersing neodymium iron boron powder coated with surface silicon in toluene, slowly adding an acetic acid solution of a silane coupling agent under the protection of nitrogen at 50-70 ℃, wherein the pH value is 3-4, and the reaction time is 6-8 h.
9. The ndfeb magnetic composite material according to claim 6 or 7, wherein step 3) the step of grafting the stabilizer function comprises:
ultrasonically dispersing neodymium iron boron magnetic powder which is coated with silicon on the surface and is grafted and modified by a silane coupling agent in DMF, wherein the solid content of the neodymium iron boron magnetic powder is 0.1-0.5 g/mL; adding saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid for reaction for 12-14h, wherein the amount of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5-2.0% of the weight of the neodymium iron boron magnetic powder.
10. A method of producing a neodymium iron boron magnetic composite material according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) weighing the raw materials in parts by weight, and uniformly mixing:
2-9 parts of thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 part by weight of lubricant;
(2) and (2) adding the mixed raw materials in the step (1) into a double-screw extruder, performing melt reaction at 200-320 ℃ for extrusion, and cooling and dicing to obtain the neodymium-iron-boron magnetic composite material.
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