CN114806157B - 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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- CN114806157B CN114806157B CN202210475238.4A CN202210475238A CN114806157B CN 114806157 B CN114806157 B CN 114806157B CN 202210475238 A CN202210475238 A CN 202210475238A CN 114806157 B CN114806157 B CN 114806157B
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- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 153
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title description 8
- 239000006247 magnetic powder Substances 0.000 claims abstract description 143
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 50
- 239000010703 silicon Substances 0.000 claims abstract description 50
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 47
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 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 13
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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 39
- 230000004048 modification Effects 0.000 claims description 35
- 238000012986 modification Methods 0.000 claims description 35
- 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
- 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
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 17
- 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
- 238000002156 mixing Methods 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 11
- 239000008116 calcium stearate Substances 0.000 claims description 11
- 235000013539 calcium stearate Nutrition 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 7
- 150000001343 alkyl silanes Chemical class 0.000 claims description 7
- -1 isocyanate alkylsilane Chemical class 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002989 phenols 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
- 239000007787 solid Substances 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000005238 degreasing Methods 0.000 description 28
- 239000000463 material Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000012459 cleaning agent Substances 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000007822 coupling agent Substances 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
- 229940048086 sodium pyrophosphate Drugs 0.000 description 8
- 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
- 235000019801 trisodium phosphate Nutrition 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 6
- 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
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 238000004140 cleaning Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 229910000077 silane Inorganic materials 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000001276 controlling effect Effects 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 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
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 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
- 239000012071 phase Substances 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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 by weight of a thermoplastic resin; 90-95 parts by weight of surface modified neodymium iron boron magnetic powder; 1-3 parts of a reactive compatibilizer; 0.1-0.5 part by weight of antioxidant; 0.3-1 part by weight of a lubricant. The invention has the advantages that: the neodymium-iron-boron magnetic powder is coated by surface silicon, grafted and modified by a silane coupling agent and grafted by a stabilizing agent, the problem of high-temperature oxidation of the neodymium-iron-boron magnetic powder is remarkably improved, one end is connected with the carboxyl end or the amino end of the thermoplastic resin in a reaction way through the bridging action of the reactive compatibilizer, and the other end is connected with the hydroxyl on the surface of the modified neodymium-iron-boron magnetic powder in a reaction way, so that the compatibility of the thermoplastic resin matrix and the neodymium-iron-boron magnetic powder and the thermal stability in the processing process are effectively enhanced, 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 (also called NdFeB magnet) is made of Neodymium, iron, boron (Nd 2 Fe 14 B) The tetragonal system crystals formed. Neodymium magnets were found by zodiac, a special metal for Sumitomo, in 1982, and the magnetic energy product (BHmax) of the magnets was larger than that of samarium cobalt magnets, which was the largest magnetic energy product worldwide at that time. Later, the powder metallurgy method (powder metallurgy process) is successfully developed by the Sumitomo special metals, and the rotary jet smelting method (melt-spinning process) is successfully developed by general motor companies, so that the NdFeB magnet can be prepared. This magnet is a permanent magnet whose magnetism is inferior to that of an absolute zero holmium magnet nowadays, and is also the most commonly used rare earth magnet. Neodymium-iron-boron magnets are widely used in the fields of electronics, electrical machinery, medical devices, toys, packaging, hardware machinery, aerospace and the like, such as hard disks, mobile phones, headphones, battery-powered tools and the like.
The magnetic composite material is a composite material with a magnetic function formed by compounding thermosetting or thermoplastic polymers and a magnetic material, and is an indispensable part of national economy development. The neodymium-iron-boron magnetic composite material is formed by compounding magnetic neodymium-iron-boron magnetic powder and non-magnetic thermosetting or thermoplastic polymer materials, has light relative density, is easy to process into products with high dimensional accuracy and complex shape, has excellent mechanical properties, and can realize mass automatic production and other outstanding advantages. Neodymium iron boron magnetic composite materials are increasingly widely applied in the fields of new energy automobile motors, household appliances, electronic technology, automatic control, computers, satellites and other high and new technology fields.
However, neodymium iron boron has higher surface activity, and in high temperature, warm humidity, electrochemical environment and hydrogen environment, the surface of neodymium iron boron is extremely easy to absorb oxygen and moisture to generate oxidation corrosion, so that the magnetic performance is reduced, and the application of neodymium iron boron in industry is severely limited. In particular, in the production process of the neodymium iron boron magnetic composite material, the molding 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 after the neodymium iron boron magnetic powder is contacted with air is more serious. Therefore, in order to obtain the neodymium iron boron magnetic composite material with good magnetic performance, the problem that the neodymium iron boron magnetic powder is easy to oxidize at high temperature must be solved.
At present, the surface of the neodymium iron boron magnetic powder is coated by forming a high 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 neodymium iron boron 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 a reaction system; the shell layer material properties are classified into a metal coating method, an inorganic coating method and an organic coating method; coating properties can be classified into physical coating and chemical coating.
Patent CN111378282a discloses a PPS-based permanent magnet composite material and a preparation method thereof, the raw materials include 85-95wt% of surface-treated magnetic powder and 5-15wt% of adhesive, the materials of the adhesive include: 0.1 to 60.0 weight percent of thermoplastic resin, 40.0 to 99.0 weight percent of polyphenylene sulfide resin, 0.1 to 10.0 weight percent of compatilizer, 0.01 to 1.0 weight percent of antioxidant and 0.01 to 1.0 weight percent of lubricant; the magnetic powder after surface treatment is prepared by surface coating 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 0.01-1.0wt% of the mass of the magnetic powder. According to the invention, the surface of the neodymium-iron-boron magnetic powder is coated by silane or titanate coupling agent, other thermoplastic resin is added into PPS to prepare the adhesive by blending, so that the adhesive neodymium-iron-boron composite material is obtained, and the purposes of mainly solving the defects of poor fluidity and difficult molding of PPS-based magnets are achieved, but the prepared composite material is slightly poor in magnetism and cannot meet application requirements in oxidation resistance.
Patent CN103258610B discloses a magnetic plastic composite material, which is prepared from the following components in parts by mass: 4-8% of nylon 6 powder, 90-95% of neodymium iron boron magnetic powder, 0.5-5% of caprolactam, 0.5-1.5% of lubricant and 0.3-1% 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 higher; 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 has uniform magnetism. Although the NdFeB magnetic powder is modified by the silane coupling agent, the obtained material has slightly poor magnetic performance, and meanwhile, 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, thereby preparing the composite material with excellent comprehensive performance, is a key for restricting the mass 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 a neodymium-iron-boron magnetic composite material and a preparation method thereof, and the neodymium-iron-boron magnetic composite material is prepared by using a reactive compatibilizer and carrying out surface coating modification on neodymium-iron-boron magnetic powder, so that on one hand, the neodymium-iron-boron magnetic powder is prevented from demagnetizing in the high-temperature processing process, and on the other hand, the neodymium-iron-boron magnetic powder and a high-molecular base material have better compatibility. 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 by weight of a thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of a reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 parts by weight of a lubricant;
the antioxidant is at least one of hindered phenols and phosphite antioxidants;
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 stabilizer functional grafting layer from inside to outside.
Further, the thermoplastic resin is polyamide 6 (PA 6), polyamide 12 (PA 12) or polyphenylene sulfide (PPS).
Further, the antioxidant is a compound antioxidant, wherein the weight ratio of hindered phenols to phosphite antioxidants is 1:2; the lubricant is a compound lubricant, wherein the weight ratio of calcium stearate to ethylene double fatty acid amide is 2:3.
further, the reactive compatibilizer is at least one of epoxy alkylsilane and isocyanate alkylsilane;
the structural formula of the epoxy alkylsilane is
Structural formula of isocyanate alkylsilane
NCO-R″Si-X 3
Wherein R 'and R' are selected from the group consisting of-CH 2 -O-(CH 2 ) 3 、-(CH 2 ) 4 - (CH) 2 ) 8 X is one of methoxy, ethoxy and acetoxy.
Further, the surface modified neodymium iron boron magnetic powder is modified through the following steps:
1) Surface silicon coating:
adopting at least one of sodium silicate and tetraethoxysilane as a surface silicon coating raw material, and carrying out surface silicon coating treatment on the neodymium iron boron magnetic powder;
2) Grafting modification of a silane coupling agent:
dispersing the neodymium iron boron magnetic powder coated with surface silicon in a solvent, adding a silane coupling agent for modification treatment, and then evaporating the solvent under reduced pressure to obtain surface modified neodymium iron boron magnetic powder;
3) Functional grafting modification of a stabilizer:
and adopting a stabilizer 3, 5-di-tert-butyl-4-hydroxybenzoic Acid (AO) to perform functional grafting modification on the NdFeB magnetic powder 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 surface silicon coating of the step 1) is performed so as to enhance the subsequent modification effect.
The degreasing step specifically comprises the following steps:
preparing an oil removal and 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, dispersing neodymium iron boron magnetic powder in the cleaning agent under the protection of nitrogen, ultrasonically cleaning for 30-90 minutes, filtering, and ultrasonically cleaning in deionized water for 5-10 minutes; and (5) vacuum drying.
The plasma surface activation treatment step specifically comprises:
controlling the vacuum degree to be 1 multiplied by 10 -2 -10×10 -2 Pa, heating to 80-120 ℃, introducing argon, and carrying out surface activation treatment on the neodymium iron boron magnetic powder by adopting argon plasma under vacuum for 1-5min.
The surface of the neodymium iron boron magnetic powder is activated by adopting an ion source, so that the potential energy of the surface of the neodymium iron boron magnetic powder can be improved by at least 1 order of magnitude, the bonding energy barrier of the subsequent modified material and the surface of the neodymium iron boron magnetic powder is obviously reduced, meanwhile, impurities and oxides on the surface of the magnetic powder can be further removed after degreasing and cleaning, the cleanliness of the magnetic powder is improved, and the bonding firmness of the subsequent modified material and the magnetic powder is improved.
Further, according to the difference of the surface silicon coating raw materials, the step 1) can be performed in two ways:
firstly, sodium silicate is adopted as a raw material in the surface silicon coating, and the method comprises the following steps:
dispersing the neodymium iron boron magnetic powder in a sodium silicate solution, slowly dropwise adding 0.5mol/L HCl solution to pH 6 at 50-90 ℃ under the protection of nitrogen, and reacting for 2-3h, wherein the sodium silicate dosage 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, and slowly dropwise adding an ethanol solution of Tetraethoxysilane (TEOS) at 50-70 ℃ under the protection of nitrogen, wherein the reaction time is 4-6h; 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 grafting modification of the silane coupling agent comprises the following steps:
dispersing neodymium iron boron powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution of a silane coupling agent at 50-70 ℃ under the protection of nitrogen, wherein the pH is 3-4, and the reaction time is 6-8h. 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 NdFeB magnetic powder.
Further, the step 3) of functional grafting of the stabilizer comprises the following steps:
ultrasonically dispersing the neodymium iron boron magnetic powder subjected to surface silicon coating and silane coupling agent grafting modification in DMF, wherein the solid content of the neodymium iron boron magnetic powder is 0.1-0.5g/mL; saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 12-14h, and the dosage of 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 raw materials according to parts by weight, and uniformly mixing:
2-9 parts by weight of a thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of a reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 parts by weight of a lubricant;
(2) Adding the mixed raw materials in the step (1) into a double-screw extruder, carrying out melting reaction at 200-320 ℃ for extrusion, cooling and granulating to obtain the neodymium-iron-boron magnetic composite material.
Further, the mixing equipment can be a kneader, the rotation speed of the kneader is 60-120 r/min, the kneading time is 25-40 min, and nitrogen is introduced during the kneading process for protection.
Further, the extruder is a sectional temperature control type extruder, preferably at least divided into five sections and a machine head section for temperature control, and more preferably divided into eight sections and a machine head section for temperature control. And the temperature of each zone is regulated according to the property difference of the raw materials, in particular the resin matrix. For example:
when the resin is polyamide 6 (PA 6), the temperatures of the respective stages are respectively: the temperature of the first zone is 200-220 ℃, preferably 210 ℃; the temperature of the second zone is 230-250 ℃, preferably 240 ℃; the temperature of the third zone is 230-250 ℃, preferably 240 ℃; the temperature of the fourth zone is 230-240 ℃, preferably 235 ℃; the temperature of the fifth zone is 230-240 ℃, preferably 235 ℃; the temperature of the six zones is 220-240 ℃, preferably 230 ℃; seven zone temperatures 220-230 ℃, preferably 225 ℃; the temperature of the eighth zone is 220-240 ℃, preferably 230 ℃; the temperature of the head is 240-250 ℃, preferably 245 ℃.
When the resin is polyphenylene sulfide (PPS), the temperatures of the respective stages are: the temperature of the first zone is 270-290 ℃, preferably 280 ℃; the temperature of the second zone is 300-320 ℃, preferably 310 ℃; the temperature of the third zone is 300-320 ℃, preferably 310 ℃; the temperature of the fourth zone is 300-310 ℃, preferably 305 ℃; the temperature of the fifth area is 300-310 ℃, and 305 ℃ is preferred; the temperature of the six zones is 290-310 ℃, preferably 300 ℃; seven zone temperatures of 290-300 ℃, preferably 295 ℃; the temperature of the eighth zone is 290-310 ℃, preferably 300 ℃; the temperature of the handpiece is 300-320 ℃, 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 (PA 6), polyamide 12 (PA 12) 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, and the magnetic composite material with excellent comprehensive properties such as mechanical properties is obtained under the effect of high compatibility, so that a wider application space is provided for the neodymium-iron-boron magnetic powder and the magnetic composite material thereof.
2) The chemical property of the silicon material is fully developed, the silicon material has excellent properties such as high melting point, and the like, silicon particles can be deposited on the surface of the magnetic powder by coating the silicon material, so that the corrosion resistance of the silicon coating is improved, and meanwhile, the magnetism of neodymium iron boron can be maintained.
3) The comprehensive NdFeB magnetic powder surface modification scheme is designed through experimental summary, so that the NdFeB magnetic powder surface is subjected to a series of treatments of 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, degreasing and plasma activation treatment are carried out on the magnetic powder, so that the surface cleanliness and activity of the magnetic powder are improved, and the subsequent modification treatment such as antioxidation and the like on the outer surface of the magnetic powder is facilitated. Secondly, the surface modification treatment of the magnetic powder comprises the steps of surface silicon coating, silane coupling agent grafting modification and stabilizer functional grafting, and the three are organically combined to realize synergistic effect. The surface silicon coating step effectively coats sodium silicate or tetraethoxysilane 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 beneficial to compounding the magnetic powder with other materials through a molding 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 the silane coupling agent grafting modification and the stabilizer functional 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, so that the antioxidation and the corrosion resistance are improved, the demagnetizing of the neodymium-iron-boron magnetic powder in the high-temperature processing process is prevented, the problem of high-temperature oxidization of the neodymium-iron-boron magnetic powder is obviously solved, and the neodymium-iron-boron magnetic composite material is ensured to have better magnetic performance; on the other hand, the compatibility of the magnetic powder and the polymer matrix material is improved, 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 preparing a NdFeB magnetic composite material;
FIG. 2 shows a technical route for preparing modified NdFeB magnetic powder;
FIG. 3 shows a scanning electron microscope photograph of neodymium-iron-boron magnetic powder dispersed in a composite material
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1
Weighing 4 parts by weight of polyamide 6 (PA 6) resin, 94.5 parts by weight of surface modified neodymium iron boron magnetic powder, 1 part by weight of epoxy alkylsilane, 0.2 part by weight of antioxidant and 0.3 part by weight of lubricant, and sequentially adding into mixing equipment to be uniformly mixed; adding the material into a double-screw extruder through a main feeding hopper, and carrying out melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperatures of all the sections are respectively as follows: the first area temperature is 210 ℃, the second area temperature is 240 ℃, the third area temperature is 240 ℃, the fourth area temperature is 235 ℃, the fifth area temperature is 235 ℃, the sixth area temperature is 230 ℃, the seventh area temperature is 225 ℃, the eighth area temperature is 230 ℃, and the head temperature is 245 ℃.
The surface modified NdFeB magnetic powder treatment in the embodiment comprises 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; dispersing neodymium iron boron powder in a sodium silicate solution in the surface silicon coating process, slowly dropwise adding an HCl solution with the concentration of 0.5mol/L to the pH value of 6 at the temperature of 90 ℃ under the protection of nitrogen, reacting for 2 hours, wherein the weight of the neodymium iron boron magnetic powder is 7wt% of the sodium silicate; dispersing neodymium iron boron magnetic powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution (pH 3-4) of a silane coupling agent at 70 ℃ under the protection of nitrogen, reacting for 6 hours, wherein the dosage of the silane coupling agent is 2.0wt% of the weight of the neodymium iron boron magnetic powder, and KH550 is selected as the silane coupling agent; and (3) ultrasonically dispersing the neodymium iron boron magnetic powder coated with surface silicon and grafted and modified by an aminosilane coupling agent in DMF, and adding a saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, wherein the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 2.0wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidants in this example were 1010 and 168 in a weight ratio of 1:2.
The lubricant in this example is a combination of calcium stearate and ethylene bis fatty acid amide in a weight ratio of 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 epoxy alkylsilane, 0.2 part by weight of antioxidant and 0.3 part by weight of lubricant, and sequentially adding into mixing equipment to be uniformly mixed; adding the material into a double-screw extruder through a main feeding hopper, and carrying out melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperatures of all the sections are respectively as follows: the first zone temperature is 280 ℃, the second zone temperature is 310 ℃, the third zone temperature is 310 ℃, the fourth zone temperature is 305 ℃, the fifth zone temperature is 305 ℃, the sixth zone temperature is 300 ℃, the seventh zone temperature is 295 ℃, the eighth zone temperature is 300 ℃, and the machine head temperature is 310 ℃.
The surface modified NdFeB magnetic powder treatment in the embodiment comprises 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; dispersing neodymium iron boron powder in a sodium silicate solution in the surface silicon coating process, slowly dropwise adding an HCl solution with the concentration of 0.5mol/L to the pH value of 6 at the temperature of 90 ℃ under the protection of nitrogen, reacting for 2 hours, wherein the weight of the neodymium iron boron magnetic powder is 7wt% of the sodium silicate; dispersing neodymium iron boron magnetic powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution (pH 3-4) of a silane coupling agent at 70 ℃ under the protection of nitrogen, reacting for 6 hours, wherein the dosage of the silane coupling agent is 2.0wt% of the weight of the neodymium iron boron magnetic powder, and KH550 is selected as the silane coupling agent; and (3) ultrasonically dispersing the neodymium iron boron magnetic powder coated with surface silicon and grafted and modified by an aminosilane coupling agent in DMF, and adding a saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, wherein the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 2.0wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidants in this example were 1010 and 168 in a weight ratio of 1:2.
The lubricant in this example is a combination of calcium stearate and ethylene bis fatty acid amide in a weight ratio of 2:3.
Example 3
Weighing 7 parts by weight of polyamide 6 (PA 6) resin, 89.2 parts by weight of surface modified neodymium iron boron magnetic powder, 3 parts by weight of epoxy alkylsilane, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, and sequentially adding into mixing equipment to be uniformly mixed; adding the material into a double-screw extruder through a main feeding hopper, and carrying out melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperatures of all the sections are respectively as follows: the first area temperature is 210 ℃, the second area temperature is 240 ℃, the third area temperature is 240 ℃, the fourth area temperature is 235 ℃, the fifth area temperature is 235 ℃, the sixth area temperature is 230 ℃, the seventh area temperature is 225 ℃, the eighth area temperature is 230 ℃, and the head temperature is 245 ℃.
The surface modified NdFeB magnetic powder treatment in the embodiment comprises 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 emulsifying agent, 1g of sodium dodecyl sulfate and 0.5g of thiourea; dispersing neodymium iron boron powder in ammonia water in the surface silicon coating process, slowly dropwise adding an ethanol solution of TEOS at 70 ℃ under the protection of nitrogen, reacting for 4 hours, wherein the ratio of water to ethanol is 1:3, and the weight of the neodymium iron boron magnetic powder is 2wt% of the TEOS; dispersing neodymium iron boron magnetic powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution (pH 3-4) of a silane coupling agent at 70 ℃ under the protection of nitrogen, reacting for 6 hours, wherein the dosage of the silane coupling agent is 0.5wt% of the weight of the neodymium iron boron magnetic powder, and KH550 is selected as the silane coupling agent; and (3) ultrasonically dispersing the neodymium iron boron magnetic powder coated with surface silicon and grafted and modified by an aminosilane coupling agent in DMF, and adding a saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, wherein the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidants in this example were 1010 and 168 in a weight ratio of 1:2.
The lubricant in this example is a combination of calcium stearate and ethylene bis fatty acid amide in a weight ratio of 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 alkylsilane, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, and sequentially adding into mixing equipment to be uniformly mixed; adding the material into a double-screw extruder through a main feeding hopper, and carrying out melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperatures of all the sections are respectively as follows: the first zone temperature is 280 ℃, the second zone temperature is 310 ℃, the third zone temperature is 310 ℃, the fourth zone temperature is 305 ℃, the fifth zone temperature is 305 ℃, the sixth zone temperature is 300 ℃, the seventh zone temperature is 295 ℃, the eighth zone temperature is 300 ℃, and the machine head temperature is 310 ℃.
The surface modified NdFeB magnetic powder treatment in the embodiment comprises 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 emulsifying agent, 1g of sodium dodecyl sulfate and 0.5g of thiourea; dispersing neodymium iron boron powder in ammonia water in the surface silicon coating process, slowly dropwise adding an ethanol solution of TEOS at 70 ℃ under the protection of nitrogen, reacting for 4 hours, wherein the ratio of water to ethanol is 1:3, and the weight of the neodymium iron boron magnetic powder is 2wt% of the TEOS; dispersing neodymium iron boron magnetic powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution (pH 3-4) of a silane coupling agent at 70 ℃ under the protection of nitrogen, reacting for 6 hours, wherein the dosage of the silane coupling agent is 0.5wt% of the weight of the neodymium iron boron magnetic powder, and KH550 is selected as the silane coupling agent; and (3) ultrasonically dispersing the neodymium iron boron magnetic powder coated with surface silicon and grafted and modified by an aminosilane coupling agent in DMF, and adding a saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, wherein the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidants in this example were 1010 and 168 in a weight ratio of 1:2.
The lubricant in this example is a combination of calcium stearate and ethylene bis fatty acid amide in a weight ratio of 2:3.
Comparative example 1
Weighing 5 parts by weight of polyamide 6 (PA 6) 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, sequentially adding into mixing equipment, and uniformly mixing; adding the material into a double-screw extruder through a main feeding hopper, and carrying out melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperatures of all the sections are respectively as follows: the first area temperature is 210 ℃, the second area temperature is 240 ℃, the third area temperature is 240 ℃, the fourth area temperature is 235 ℃, the fifth area temperature is 235 ℃, the sixth area temperature is 230 ℃, the seventh area temperature is 225 ℃, the eighth area temperature is 230 ℃, and the head temperature is 245 ℃.
The surface modified NdFeB magnetic powder treatment in the embodiment comprises 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; dispersing neodymium iron boron powder in a sodium silicate solution in the surface silicon coating process, slowly dropwise adding an HCl solution with the concentration of 0.5mol/L to the pH value of 6 at the temperature of 90 ℃ under the protection of nitrogen, reacting for 2 hours, wherein the weight of the neodymium iron boron magnetic powder is 7wt% of the sodium silicate; dispersing neodymium iron boron magnetic powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution (pH 3-4) of a silane coupling agent at 70 ℃ under the protection of nitrogen, reacting for 6 hours, wherein the dosage of the silane coupling agent is 2.0wt% of the weight of the neodymium iron boron magnetic powder, and KH550 is selected as the silane coupling agent; and (3) ultrasonically dispersing the neodymium iron boron magnetic powder coated with surface silicon and grafted and modified by an aminosilane coupling agent in DMF, and adding a saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, wherein the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 2.0wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidants in this example were 1010 and 168 in a weight ratio of 1:2.
The lubricant in this example is a combination of calcium stearate and ethylene bis fatty acid amide in a weight ratio of 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 into mixing equipment to be uniformly mixed; adding the material into a double-screw extruder through a main feeding hopper, and carrying out reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperatures of all the sections are respectively as follows: the first zone temperature is 280 ℃, the second zone temperature is 310 ℃, the third zone temperature is 310 ℃, the fourth zone temperature is 305 ℃, the fifth zone temperature is 305 ℃, the sixth zone temperature is 300 ℃, the seventh zone temperature is 295 ℃, the eighth zone temperature is 300 ℃, and the machine head temperature is 310 ℃.
The surface modified NdFeB magnetic powder treatment in the embodiment comprises 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 emulsifying agent, 1g of sodium dodecyl sulfate and 0.5g of thiourea; dispersing neodymium iron boron powder in ammonia water in the surface silicon coating process, slowly dropwise adding an ethanol solution of TEOS at 70 ℃ under the protection of nitrogen, reacting for 4 hours, wherein the ratio of water to ethanol is 1:3, and the weight of the neodymium iron boron magnetic powder is 2wt% of the TEOS; dispersing neodymium iron boron magnetic powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution (pH 3-4) of a silane coupling agent at 70 ℃ under the protection of nitrogen, reacting for 6 hours, wherein the dosage of the silane coupling agent is 0.5wt% of the weight of the neodymium iron boron magnetic powder, and KH550 is selected as the silane coupling agent; and (3) ultrasonically dispersing the neodymium iron boron magnetic powder coated with surface silicon and grafted and modified by an aminosilane coupling agent in DMF, and adding a saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, wherein the reaction time is 14h, and the dosage of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5wt% of the weight of the neodymium iron boron magnetic powder.
The antioxidants in this example were 1010 and 168 in a weight ratio of 1:2.
The lubricant in this example is a combination of calcium stearate and ethylene bis fatty acid amide in a weight ratio of 2:3.
Comparative example 3
Weighing 5 parts by weight of polyamide 6 (PA 6) 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 into mixing equipment to be uniformly mixed; adding the material into a double-screw extruder through a main feeding hopper, and carrying out melt reaction extrusion and granulation through the double-screw extruder to obtain the neodymium iron boron magnetic composite material, wherein the temperatures of all the sections are respectively as follows: the first area temperature is 210 ℃, the second area temperature is 240 ℃, the third area temperature is 240 ℃, the fourth area temperature is 235 ℃, the fifth area temperature is 235 ℃, the sixth area temperature is 230 ℃, the seventh area temperature is 225 ℃, the eighth area temperature is 230 ℃, and the head temperature is 245 ℃.
The neodymium iron boron magnetic powder treatment in the comparative example is degreasing and degreasing, 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 emulsifying agent, 1g of sodium dodecyl sulfate and 0.5g of thiourea.
The antioxidants in this example were 1010 and 168 in a weight ratio of 1:2.
The lubricant in this example is a combination of calcium stearate and ethylene bis fatty acid amide in a weight ratio of 2:3.
The magnetic properties and compressive strength of the neodymium iron boron magnetic composite materials 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): magnetic polarization intensity coercivity value
(BH)max(kJ/m 3 ): maximum magnetic energy product of material
TABLE 1 magnetic Properties and compressive Strength of NdFeB magnetic composite materials
| 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 test data, the remanence induction strength Br of the composite materials of the embodiments 1-4 is larger than 450mT; the magnetic polarization intensity coercivity values jHc are all larger than 690kA/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 material in the comparative example, and is particularly superior to that of the surface unmodified neodymium iron boron magnetic composite material in the comparative example 3. In general, as the degree of the surface modification treatment of the magnetic powder is higher, the magnetic performance is improved relatively more, which also shows the necessity of surface modification of the neodymium iron boron magnetic powder, and the feasibility and scientificity of the invention for carrying out stepwise layered surface modification on the magnetic powder and selecting a high-performance matrix material.
From the test data of examples and comparative examples, it can be found that: comparative examples 1 and 2, although using neodymium-iron-boron modified magnetic powder, did not use a reactive compatibilizer, resulting in slightly lower compatibility between the magnetic powder and the matrix material, and macroscopically exhibited lower compressive strength than the above examples; in contrast, comparative example 3 uses neither surface-unmodified neodymium-iron-boron magnetic powder nor reactive compatibilizer, so that the compressive strength of the composite material is obviously lower than that of the above-mentioned examples while the magnetic performance is poor; compared with the composite materials in comparative examples 1 and 2, which only adopt the modified neodymium iron boron magnetic powder and do not use the reactive compatibilizer, the compression strength of the neodymium iron boron magnetic composite materials in examples 1 to 4, which use the modified neodymium iron boron magnetic powder and the reactive compatibilizer simultaneously, is above 90Mpa, the composite materials have obvious mechanical property advantages, and as can be seen from the scanning electron microscope pictures of the neodymium iron boron magnetic powder dispersed in the composite materials in fig. 3, the magnetic powder is not obviously exposed, and the matrix presents complete and uniform images. On the other hand, in examples 1 to 4, the magnetic properties of the composite material tended to be slightly lowered as the content of the nonmagnetic substance such as the resin was increased, but the compressive strength was improved to some extent, and according to this rule, the magnetic properties and mechanical properties of the composite material could be adjusted in actual production to suit the requirements of the use environment.
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 functional grafting modification, so that the oxidation loss of the neodymium-iron-boron magnetic powder in the high-temperature melt 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, the reactive compatibilizer is further used for uniformly dispersing and bridging the magnetic powder into the high-performance matrix material, so that the magnetic powder has a reinforcing effect on the matrix while the matrix protects the magnetic powder, and the mechanical properties such as compressive strength of the composite material are improved.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. The neodymium iron boron magnetic composite material is characterized by comprising the following components in parts by weight:
2-9 parts by weight of a thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of a reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 parts by weight of a lubricant;
the thermoplastic resin is polyamide 6, polyamide 12 or polyphenylene sulfide;
the antioxidant is at least one of hindered phenols and phosphite antioxidants;
the lubricant is at least one of calcium stearate and ethylene bis fatty acid amide;
the reactive compatibilizer is at least one of epoxy alkylsilane and isocyanate alkylsilane, wherein the structural formula of the epoxy alkylsilane is as follows:
；
the structural formula of the isocyanate alkylsilane:
NCO-R″Si-X 3
wherein R 'and R' are selected from- (CH) 2 ) 4 - (CH) 2 ) 8 X is one of methoxy, ethoxy and acetoxy;
the surface modified neodymium iron boron magnetic powder sequentially comprises a surface silicon coating layer, a silane coupling agent grafting modification layer and a stabilizer functional grafting layer from inside to outside, and is modified through the following steps:
1) Surface silicon coating:
adopting at least one of sodium silicate and tetraethoxysilane as a surface silicon coating raw material, and carrying out surface silicon coating treatment on the neodymium iron boron magnetic powder;
2) Grafting modification of a silane coupling agent:
dispersing the neodymium iron boron magnetic powder coated with surface silicon in a solvent, adding a silane coupling agent KH550 for modification treatment, and then evaporating the solvent under reduced pressure to obtain surface modified neodymium iron boron magnetic powder;
3) Functional grafting modification of a stabilizer:
and adopting a stabilizer 3, 5-di-tert-butyl-4-hydroxybenzoic acid to perform functional grafting modification on the NdFeB magnetic powder grafted and modified by the silane coupling agent.
2. The neodymium iron boron magnetic composite material according to claim 1, wherein: the antioxidant is a compound antioxidant, wherein the weight ratio of hindered phenols to phosphite antioxidants is 1:2; the lubricant is a compound lubricant, wherein the weight ratio of calcium stearate to ethylene double fatty acid amide is 2:3.
3. the neodymium iron boron magnetic composite material according to claim 1, wherein sodium silicate is used as a raw material in the surface silicon coating in step 1), and the method comprises the following steps:
dispersing the neodymium iron boron magnetic powder in a sodium silicate solution, slowly dropwise adding 0.5mol/L HCl solution to pH 6 at 50-90 ℃ under the protection of nitrogen, and reacting for 2-3h, wherein the sodium silicate dosage is 3-7% of the weight of the neodymium iron boron magnetic powder.
4. The neodymium iron boron magnetic composite material of claim 1, wherein step 1) adopts tetraethoxysilane as a raw material in the surface silicon cladding, and comprises the following steps:
dispersing neodymium iron boron magnetic powder in ammonia water, and slowly dropwise adding an ethanol solution of tetraethoxysilane at 50-70 ℃ under the protection of nitrogen for 4-6 hours; in the ethanol solution, the volume ratio of water to ethanol is 1: (2-8); the addition amount of the tetraethoxysilane is 2-6% of the weight of the neodymium-iron-boron magnetic powder.
5. The neodymium iron boron magnetic composite material according to claim 3 or 4, wherein the step 2) of grafting modification of the silane coupling agent comprises:
dispersing neodymium iron boron powder coated with surface silicon in toluene by ultrasonic, slowly adding acetic acid solution of a silane coupling agent at 50-70 ℃ under the protection of nitrogen, wherein the pH is 3-4, and the reaction time is 6-8h.
6. A neodymium iron boron magnetic composite material according to claim 3 or 4, wherein the step 3) of functional grafting of the stabilizer comprises:
ultrasonically dispersing the neodymium iron boron magnetic powder subjected to surface silicon coating and silane coupling agent grafting modification in DMF, wherein the solid content of the neodymium iron boron magnetic powder is 0.1-0.5g/mL; saturated sodium carbonate solution of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is added, the reaction time is 12-14h, and the dosage of 3, 5-di-tert-butyl-4-hydroxybenzoic acid is 0.5-2.0% of the weight of the neodymium iron boron magnetic powder.
7. The method for preparing a neodymium iron boron magnetic composite material according to any one of claims 1 to 6, comprising the following steps:
(1) Weighing raw materials according to parts by weight, and uniformly mixing:
2-9 parts by weight of a thermoplastic resin;
90-95 parts by weight of surface modified neodymium iron boron magnetic powder;
1-3 parts of a reactive compatibilizer;
0.1-0.5 part by weight of antioxidant;
0.3-1 parts by weight of a lubricant;
(2) Adding the mixed raw materials in the step (1) into a double-screw extruder, performing melt reaction at 200-320 ℃ to extrude, cooling and granulating to obtain the NdFeB magnetic composite material.
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