JP2022104855A - Corrosion-resistant neodymium iron-boron magnet, surface treatment method, and usage of hydroxyl group compound - Google Patents
Corrosion-resistant neodymium iron-boron magnet, surface treatment method, and usage of hydroxyl group compound Download PDFInfo
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- JP2022104855A JP2022104855A JP2021048778A JP2021048778A JP2022104855A JP 2022104855 A JP2022104855 A JP 2022104855A JP 2021048778 A JP2021048778 A JP 2021048778A JP 2021048778 A JP2021048778 A JP 2021048778A JP 2022104855 A JP2022104855 A JP 2022104855A
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- neodymium iron
- boron magnet
- corrosion
- hydroxyl group
- surface treatment
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 147
- -1 hydroxyl group compound Chemical class 0.000 title claims abstract description 74
- 230000007797 corrosion Effects 0.000 title claims abstract description 69
- 238000005260 corrosion Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004381 surface treatment Methods 0.000 title claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 21
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 12
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 12
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 57
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229910001868 water Inorganic materials 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 238000005237 degreasing agent Methods 0.000 description 15
- 239000013527 degreasing agent Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 238000005238 degreasing Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000005498 polishing Methods 0.000 description 9
- 238000004506 ultrasonic cleaning Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 6
- 235000019801 trisodium phosphate Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- PXAWCNYZAWMWIC-UHFFFAOYSA-N [Fe].[Nd] Chemical compound [Fe].[Nd] PXAWCNYZAWMWIC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/026—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets protecting methods against environmental influences, e.g. oxygen, by surface treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
- Hard Magnetic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本発明は、耐食性ネオジム鉄ホウ素磁石、表面処理方法および水酸基化合物の使用に関する。 The present invention relates to corrosion resistant neodymium iron boron magnets, surface treatment methods and the use of hydroxyl compounds.
近年、超高エネルギー密度を有するネオジム鉄ホウ素(NdFeB)磁石は電子製品、電動/ハイブリッド自動車、家電製品、産業用モーター、風力発電、核磁気共鳴などの分野で広く利用されており、強い市場需要がある。また、希土類磁石技術革新は日進月歩であり、生産量及び性能が絶えず向上しており、現代技術と情報産業の発展を強力に促進している。しかし、ネオジム鉄ボロン磁石表面におけるNd原子とFe原子は空気中の酸素と反応してNd2O3、FeO、Fe2O3、Fe3O4を形成する。ネオジム鉄ホウ素磁石は、湿度の高い環境においてより腐食し易くなる。このため、耐食性を向上させるために、耐食処理を施す必要がある。 In recent years, neodymium iron boron (NdFeB) magnets with ultra-high energy density have been widely used in fields such as electronic products, electric / hybrid automobiles, home appliances, industrial motors, wind power generation, and nuclear magnetic resonance, and there is strong market demand. There is. In addition, the technological innovation of rare earth magnets is advancing day by day, and the production volume and performance are constantly improving, which strongly promotes the development of modern technology and information industry. However, the Nd and Fe atoms on the surface of the neodymium iron boron magnet react with oxygen in the air to form Nd 2 O 3 , FeO, Fe 2 O 3 , and Fe 3 O 4 . Neodymium iron boron magnets are more susceptible to corrosion in humid environments. Therefore, in order to improve the corrosion resistance, it is necessary to perform a corrosion resistance treatment.
現在、ネオジム鉄ホウ素磁石の表面に保護層を形成する方法として、金属めっき、めっき-無電解めっき、電着塗装、不動態化などが広く採用されている。ネオジム鉄ボロン磁石は多孔質構造であるため、金属めっき法ではめっき中にめっき液が素材内部に入り込み、内部の粒界腐食を引き起こし、得られる保護層の厚さが不均一で寿命が短く、深い穴で複雑な部品には適していない。めっき-無電解めっき法により得られる保護層は、基体との密着性が悪く、剥離しやすく、また汚水が発生する。電着法による塗層の厚さは不均一である。 Currently, metal plating, plating-electroless plating, electrodeposition coating, passivation, etc. are widely adopted as methods for forming a protective layer on the surface of a neodymium iron boron magnet. Since the neodymium iron boron magnet has a porous structure, in the metal plating method, the plating solution enters the inside of the material during plating, causing intergranular corrosion inside, and the resulting protective layer has a non-uniform thickness and a short life. Not suitable for complex parts with deep holes. Plating-The protective layer obtained by the electroless plating method has poor adhesion to the substrate, is easily peeled off, and generates sewage. The thickness of the coating layer by the electrodeposition method is non-uniform.
不動態化とは、金属の表面に安定で緻密で基体と密着が強固な膜を形成するプロセスである。この膜は、金属マトリックスを腐食媒体から分離し、それにより金属の更なる腐食を防止する。このような膜はパッシベーション膜と呼ばれる。 Passivation is the process of forming a stable, dense, and tightly adhered film on the surface of a metal. This membrane separates the metal matrix from the corrosive medium, thereby preventing further corrosion of the metal. Such a membrane is called a passivation membrane.
CN102084438Aには、R-Fe-B系焼結磁石を湿度変化環境において450℃~900℃の温度範囲で酸化熱処理した後、その表面に処理液を塗布し、その後乾燥して、構成元素として少なくともFe、Zr、Nd、フッ素、酸素を含有する化成皮膜を形成することで、ネオジム鉄ホウ素の耐食性を向上させる耐食性磁石の製造方法が開示されている。しかし、この方法では、処理液を安定に保存することが困難であり、現場での準備が必要となり、作業の煩雑さが増す。また、処理液は温度に敏感であり、処理液を塗布する温度が80℃を超えると、処理液の安定性に影響を与え、さらにネオジム鉄ホウ素の耐食性に影響を与える。 For CN102084438A, an R-Fe-B-based sintered magnet is oxidatively heat-treated in a humidity-changing environment in a temperature range of 450 ° C to 900 ° C, a treatment liquid is applied to the surface thereof, and then dried to at least as a constituent element. A method for producing a corrosion-resistant magnet that improves the corrosion resistance of neodymium iron boron by forming a chemical conversion film containing Fe, Zr, Nd, fluorine, and oxygen is disclosed. However, with this method, it is difficult to stably store the treatment liquid, which requires on-site preparation and increases the complexity of the work. Further, the treatment liquid is sensitive to temperature, and when the temperature at which the treatment liquid is applied exceeds 80 ° C., it affects the stability of the treatment liquid and further affects the corrosion resistance of neodymium iron boron.
CN101809690Bには、磁石を200~600℃で、酸素分圧を102~105Pa、水蒸気分圧を0.1~1000Paに制御して熱処理することにより、表層がヘマタイトを主成分とする表面改質層を含む希土類焼結磁石の製造方法が開示されている。このような方法で改質された希土類焼結磁石は、耐食性が酸素分圧及び水蒸気分圧の影響を大きく受ける。処理室に前述の分圧環境を作り出すためには、酸化ガスを導入する必要があり、製造コストが高くなるだけでなく、装置の密閉性にも厳しい要件がある。
CN105839045Aには、ネオジム鉄ホウ素磁石を真空炉に入れ、20Pa以下まで排気した後、0.1~0.2MPaの窒素ガスを充填し、さらに排気することを2~3回繰り返し、そして、真空炉の温度を400~750℃に昇温し、窒素ガスを圧力1×103~1×105Paになるまで導入し、2~24時間処理することにより、磁石表面に厚さ1~50μmの窒素元素を含む化合物の耐食層を形成することが開示されている。この方法は設備に対する要求が厳しい要件があり、設備の投資コストが増大し、かつ処理時間が長い。
For CN101809690B, the surface layer is surface-modified with hematite as the main component by heat-treating the magnet at 200 to 600 ° C, controlling the oxygen partial pressure to 10 2 to 105 Pa and the water vapor partial pressure to 0.1 to 1000 Pa. A method for manufacturing a rare earth sintered magnet including a layer is disclosed. The corrosion resistance of the rare earth sintered magnet modified by such a method is greatly affected by the oxygen partial pressure and the water vapor partial pressure. In order to create the above-mentioned partial pressure environment in the processing chamber, it is necessary to introduce an oxidizing gas, which not only increases the manufacturing cost but also has strict requirements for the airtightness of the device.
In CN105839045A, put a neodymium iron boron magnet in a vacuum furnace, exhaust it to 20 Pa or less, fill it with nitrogen gas of 0.1 to 0.2 MPa, repeat exhausting 2-3 times, and adjust the temperature of the vacuum furnace. By raising the temperature to 400 to 750 ° C, introducing nitrogen gas until the pressure reaches 1 × 10 3 to 1 × 10 5 Pa, and treating for 2 to 24 hours, nitrogen elements with a thickness of 1 to 50 μm are formed on the magnet surface. It is disclosed to form a corrosion resistant layer of the containing compound. This method has strict requirements for equipment, increases the investment cost of equipment, and requires a long processing time.
CN111441017Aには、ネオジム鉄ホウ素磁石の表面に複合コーティングを蒸着させることによって、ネオジム鉄ホウ素磁石の表面に防食コーティングを製造する方法が開示されている。この方法では、めっき層と基体との密着性を高めることができるものの、設備の投資が大きい、生産効率が悪い、複雑な部品を処理できないなどの欠点がある。 CN111441017A discloses a method for producing an anticorrosion coating on the surface of a neodymium iron boron magnet by depositing a composite coating on the surface of the neodymium iron boron magnet. Although this method can improve the adhesion between the plating layer and the substrate, it has disadvantages such as large investment in equipment, poor production efficiency, and inability to process complicated parts.
EP0326088A3には、アルカリ性溶液に磁石を洗浄する工程、洗浄した磁石をまず水洗い、次に酸性洗浄溶液で洗浄し、最後に水で洗浄する工程、洗浄した磁石をリン酸亜鉛含有メッキ液にて清浄処理してリン酸亜鉛保護層を形成し、表面腐食を抑制する工程、および、リン酸亜鉛保護層表面にアミドイミドコーティング層をコーティングすることにより耐食性のある耐久コーティング層を施して腐食から保護する工程を含む、ネオジムボンド磁石に十分な腐食防止を提供する方法が開示されている。この方法は操作が複雑で生産効率が低く、構造が複雑なネオジム鉄ホウ磁石を操作することができない。 EP0326088A3 has a step of washing the magnet in an alkaline solution, a step of first washing the washed magnet with water, then a step of washing with an acidic washing solution, and finally a step of washing with water, and cleaning the washed magnet with a zinc phosphate-containing plating solution. A step of treating to form a zinc phosphate protective layer to suppress surface corrosion, and a corrosion-resistant durable coating layer by coating the surface of the zinc phosphate protective layer with an amidoimide coating layer to protect it from corrosion. Disclosed are methods of providing sufficient corrosion protection for neozim bond magnets, including steps. This method is complicated to operate, has low production efficiency, and cannot operate a neodymium iron hoax magnet having a complicated structure.
US4917778Bには、ネオジム鉄ホウ素系焼結磁石を、酸化性を有する酸に含浸して表面を活性化させ、1000kgf/cm2以下の内部応力を有するニッケルで磁石をメッキし、カチオン電着塗装を施るネオジム鉄ホウ素系焼結磁石の製造方法が開示されている。この方法では、得られる塗膜の厚さが不均一で、塗膜と基体との密着性が悪く、作業が煩雑で設備投資にコストが高い。 US4917778B is impregnated with neodymium iron-boron-based sintered magnet to activate the surface by impregnating it with an oxidizing acid, and the magnet is plated with nickel having an internal stress of 1000 kgf / cm 2 or less, and cationic electrodeposition coating is applied. A method for manufacturing a neodymium iron-boron-based sintered magnet to be applied is disclosed. In this method, the thickness of the obtained coating film is not uniform, the adhesion between the coating film and the substrate is poor, the work is complicated, and the cost for capital investment is high.
以上のように、上記方法は、工程が複雑で、サイクルが長く、設備に対する要求が高く、環境汚染、生産コストの増加、量産効率が低く、且つ製造されたコーティングの厚さが均一でなく、マトリックスとの結合力が弱く、脱落し易いなどの多くの技術的問題点を有する。 As described above, in the above method, the process is complicated, the cycle is long, the demand for equipment is high, environmental pollution, the increase in production cost, the mass production efficiency is low, and the thickness of the manufactured coating is not uniform. It has many technical problems such as weak binding force to the matrix and easy falling off.
これを考慮して、本発明の目的は、ネオジム鉄ホウ素磁石の耐食性を改善するための水酸基化合物の用途を提供することである。本発明は、水酸基化合物がネオジム鉄ホウ素磁石の耐食性を改善できることを見出した。 In view of this, an object of the present invention is to provide a use of a hydroxyl group compound for improving the corrosion resistance of a neodymium iron boron magnet. The present invention has found that a hydroxyl compound can improve the corrosion resistance of a neodymium iron-boron magnet.
本発明のもう1つの目的は、ネオジム鉄ホウ素磁石の表面処理方法を提供することである。当該方法は、プロセスが簡単で、処理サイクルが短く、かつ、環境を汚染しにくい。 Another object of the present invention is to provide a surface treatment method for neodymium iron boron magnets. The method has a simple process, a short processing cycle, and is less likely to pollute the environment.
本発明の他の目的は前述した方法で得られた耐食性ネオジム鉄ホウ素磁石を提供することである。前述した方法で処理した後、ネオジム鉄ホウ素磁石は表面から空孔まで緻密な酸化物層が形成されているため、酸素ガスから効果的にブロックされ、より高い耐食性を有する。 Another object of the present invention is to provide a corrosion-resistant neodymium iron-boron magnet obtained by the above-mentioned method. After the treatment by the method described above, the neodymium iron-boron magnet has a dense oxide layer formed from the surface to the pores, so that it is effectively blocked from oxygen gas and has higher corrosion resistance.
一方、本発明は、ネオジム鉄ホウ素磁石の耐食性を向上させるための式(I)に示される構造を有する水酸基化合物の使用を提供する。
(そのうち、RはC2~C15の炭化水素基から選ばれたものであり、nは1~3の自然数である。)
On the other hand, the present invention provides the use of a hydroxyl group compound having a structure represented by the formula (I) for improving the corrosion resistance of a neodymium iron boron magnet.
(Of these, R is selected from the hydrocarbon groups of C2 to C15, and n is a natural number of 1 to 3.)
本発明の使用によれば、前記水酸基化合物は、一価アルコールまたは二価アルコールであり、RはC2~C15のアルキルから選ばれたものであり、nが1または2であることが好ましい。 According to the use of the present invention, the hydroxyl compound is a monohydric alcohol or a dihydric alcohol, R is selected from alkyls of C2 to C15, and n is preferably 1 or 2.
本発明の使用によれば、前記水酸基化合物は、一価アルコールであり、RはC3~C6のアルキルから選ばれたものであり、nが1であることが好ましい。 According to the use of the present invention, the hydroxyl compound is a monohydric alcohol, R is selected from alkyls of C3 to C6, and n is preferably 1.
本発明の使用によれば、前記水酸基化合物は、エタノール、N-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、n-ペンタノール、イソアミルアルコール、ネオペンチルアルコール、n-ヘキサノールまたはイソヘキサノールであることが好ましい。 According to the use of the present invention, the hydroxyl compound may be ethanol, N-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-hexanol or isohexanol. preferable.
また、本発明は、ネオジム鉄ホウ素磁石の表面に式(I)に示される構造を有する水酸基化合物の層を形成してプリフォームを得る工程を含むネオジム鉄ホウ素磁石の表面処理方法を提供する。
(そのうち、RはC2~C15の炭化水素基から選ばれたものであり、nは1~3の自然数である。)
The present invention also provides a surface treatment method for a neodymium iron boron magnet, which comprises a step of forming a layer of a hydroxyl group compound having a structure represented by the formula (I) on the surface of the neodymium iron boron magnet to obtain a preform.
(Of these, R is selected from the hydrocarbon groups of C2 to C15, and n is a natural number of 1 to 3.)
本発明に係る表面処理方法によれば、前記水酸基化合物は一価アルコールまたは二価アルコールであり、RはC2~C15のアルキルから選ばれたものであり、nは1または2であることが好ましい。 According to the surface treatment method according to the present invention, the hydroxyl compound is a monohydric alcohol or a dihydric alcohol, R is selected from alkyls of C2 to C15, and n is preferably 1 or 2. ..
本発明に係る表面処理方法によれば、ネオジム鉄ホウ素磁石を前記水酸基化合物に含浸し、取り出した後ブロー乾燥してプリフォームを得ることは、好ましい。 According to the surface treatment method according to the present invention, it is preferable to impregnate the hydroxyl group compound with a neodymium iron-boron magnet, take it out, and then blow-dry it to obtain a preform.
本発明に係る表面処理方法によれば、さらにプリフォームを熱処理してネオジム鉄ホウ素磁石表面に酸化物層を形成する工程を含むことは、好ましい。 According to the surface treatment method according to the present invention, it is preferable to further include a step of heat-treating the preform to form an oxide layer on the surface of the neodymium iron boron magnet.
本発明に係る表面処理方法によれば、前記熱処理は、プリフォームをトンネル加熱炉に入れ、380~450℃で25~50min加熱し、加熱中トンネル加熱炉に窒素ガスを流し、窒素ガスの流量を25~100L/minに制御することが好ましい。 According to the surface treatment method according to the present invention, in the heat treatment, the preform is placed in a tunnel heating furnace, heated at 380 to 450 ° C. for 25 to 50 minutes, nitrogen gas is passed through the tunnel heating furnace during heating, and the flow rate of nitrogen gas is reached. Is preferably controlled to 25 to 100 L / min.
また、本発明は、さらに前記酸化物層の厚さが0.6~3.5μmであり、GB/T 10125-2012《人工雰囲気腐食試験・塩水噴霧試験》に従って35℃、5wt%NaClの条件で測定した前記耐食性のネオジム鉄ホウ素磁石が腐食し始めるまでの時間が45分間超え、GB/T2423.3-2006に従って85℃、85%RHの条件で測定した前記耐食性のネオジム鉄ホウ素磁石が腐食し始めるまでの時間が1.2時間超える前記の方法で得られた耐食性のネオジム鉄ホウ素磁石を提供する。 Further, in the present invention, the thickness of the oxide layer was 0.6 to 3.5 μm, and the measurement was performed under the conditions of 35 ° C. and 5 wt% NaCl according to GB / T 10125-2012 << Artificial Atmosphere Corrosion Test / Salt Spray Test >>. The time until the corrosion-resistant neodymium iron boron magnet begins to corrode exceeds 45 minutes, and until the corrosion-resistant neodymium iron boron magnet begins to corrode as measured under the conditions of 85 ° C and 85% RH according to GB / T2423.3-2006. Provided is a corrosion-resistant neodymium iron boron magnet obtained by the above-mentioned method for which the time exceeds 1.2 hours.
水酸基化合物は、通常、有機溶剤として使用されるものであるが、本発明は、ネオジム鉄ホウ素磁石の耐食性を向上させることができることを見出した。水酸基化合物層が付着したネオジム鉄ホウ素磁石は、加熱処理を行うことにより、その表面に酸化鉄を主成分とする緻密な酸化物層を形成する。この緻密な酸化物層は、磁石との密着力が強い。塩水噴霧試験および一定湿度での熱試験によれば、当該酸化物層は、水酸基化合物層を付着せずに形成されたフィルムよりも優れた耐食性を有することが示された。本発明は、水酸基化合物を利用してネオジム鉄ホウ素磁石表面を処理し、プロセスは単純であり、温度および窒素の流量を適当に制御すれば、製造期間が短く、環境が汚染されない。 The hydroxyl group compound is usually used as an organic solvent, but the present invention has found that the corrosion resistance of a neodymium iron-boron magnet can be improved. The neodymium iron-boron magnet to which the hydroxyl group compound layer is attached is heat-treated to form a dense oxide layer containing iron oxide as a main component on the surface thereof. This dense oxide layer has a strong adhesion to the magnet. A salt spray test and a thermal test at a constant humidity showed that the oxide layer had better corrosion resistance than the film formed without the hydroxyl compound layer attached. In the present invention, the neodymium iron-boron magnet surface is treated using a hydroxyl compound, the process is simple, and if the temperature and the flow rate of nitrogen are appropriately controlled, the production period is short and the environment is not polluted.
以下、具体的な実施例を挙げて本発明をさらに説明するが、本発明の範囲はこれらに限定されるものではない。 Hereinafter, the present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
ネオジム鉄ホウ素磁石は、酸化による腐食しやすい。磁石の耐食性を向上させるための従来の方法では、コストが高く、工程が複雑である。不動態保護膜は磁石の耐食性を向上させることができるが、効果が十分ではない。本発明者らは、驚くべきことに、通常有機溶媒として使用される水酸基化合物がネオジム鉄ホウ素磁石の耐食性を向上させることを見出し、本発明を完成するに至った。 Neodymium iron boron magnets are prone to corrosion due to oxidation. Conventional methods for improving the corrosion resistance of magnets are expensive and complicated in process. The passivation protective film can improve the corrosion resistance of the magnet, but the effect is not sufficient. Surprisingly, the present inventors have found that a hydroxyl group compound usually used as an organic solvent improves the corrosion resistance of a neodymium iron-boron magnet, and have completed the present invention.
<水酸基化合物の使用>
本発明は、ネオジム鉄ホウ素磁石の耐食性を向上させるための水酸基化合物の使用を提供する。ネオジム鉄ホウ素磁石はネオジム鉄ホウ素永久磁石またはネオジム鉄ホウ素永久磁材と呼ばられる。ネオジム鉄ホウ素磁石は、主成分がNd、Fe及びBであり、さらに他の遷移金属元素、他の希土類元素およびC、OおよびNなどの不可避の不純物を含む。これらは当技術分野で周知なことであるため、ここではその詳細な説明を省略する。ネオジム鉄ホウ素磁石は、ボンド磁石または焼結磁石であってもよく、好ましくは焼結磁石である。特に、焼結磁石は多孔質構造を有する可能性が高いため、本発明は特に焼結ネオジム鉄ホウ素磁石が好適である。本発明の好ましい実施形態によれば、焼結ネオジム鉄ホウ素磁石の耐食性を向上させるための水酸基化合物の使用を提供する。
<Use of hydroxyl compound>
The present invention provides the use of hydroxyl compounds to improve the corrosion resistance of neodymium iron boron magnets. Neodymium iron boron magnets are called neodymium iron boron permanent magnets or neodymium iron boron permanent magnets. Neodymium iron boron magnets are mainly composed of Nd, Fe and B, and further contain other transition metal elements, other rare earth elements and unavoidable impurities such as C, O and N. Since these are well known in the art, detailed description thereof will be omitted here. The neodymium iron boron magnet may be a bonded magnet or a sintered magnet, and is preferably a sintered magnet. In particular, since the sintered magnet is likely to have a porous structure, the sintered neodymium iron-boron magnet is particularly suitable for the present invention. According to a preferred embodiment of the present invention, the use of a hydroxyl group compound for improving the corrosion resistance of a sintered neodymium iron boron magnet is provided.
以下、主に一般式( I )で示される構造を有する水酸基化合物について説明する。
(そのうち、RはC2~C15の炭化水素基から選ばれたものであり、nは1~3の自然数である。)
Hereinafter, a hydroxyl group compound having a structure represented by the general formula (I) will be mainly described.
(Of these, R is selected from the hydrocarbon groups of C2 to C15, and n is a natural number of 1 to 3.)
本発明に係る水酸基化合物は、融点が15℃未満であってもよく、好ましくは10℃未満であり、より好ましくは5℃未満である。本発明に係る水酸基化合物は、沸点が35℃超えてもよく、好ましくは75℃超え、より好ましくは80℃超える。本発明に係る水酸基化合物は、常温で液状であり、例えば、15~30℃で液状である。これはネオジム鉄ホウ素磁石表面に均一な水酸基化合物層を形成するのに有利であり、完全に揮発しにくいため、水酸基化合物がネオジム鉄ホウ素磁石表面の空孔に浸漬し、耐食性を向上させるのにも有利である。従来の加熱処理ではネオジム鉄ホウ素磁石表面の空孔に耐食層を形成することは確保できない。水酸基化合物はネオジム鉄ホウ素磁石表面の空孔に侵入したため、従来の加熱処理では達成できなかった耐食性を実現できる。 The hydroxyl compound according to the present invention may have a melting point of less than 15 ° C, preferably less than 10 ° C, and more preferably less than 5 ° C. The hydroxyl compound according to the present invention may have a boiling point of more than 35 ° C, preferably more than 75 ° C, more preferably more than 80 ° C. The hydroxyl group compound according to the present invention is liquid at room temperature, for example, at 15 to 30 ° C. This is advantageous for forming a uniform hydroxyl compound layer on the surface of the neodymium iron boron magnet, and since it is difficult to completely volatilize, the hydroxyl compound is immersed in the pores on the surface of the neodymium iron boron magnet to improve corrosion resistance. Is also advantageous. With conventional heat treatment, it is not possible to ensure that a corrosion-resistant layer is formed in the pores on the surface of the neodymium iron-boron magnet. Since the hydroxyl group compound penetrates into the pores on the surface of the neodymium iron-boron magnet, it is possible to realize corrosion resistance that could not be achieved by conventional heat treatment.
本発明に係る水酸基化合物はアルコール系であってもよく、アルコール系として一価アルコール、二価アルコールまたは三価アルコールを含むがこれらに限定されていない。本発明は、アルコール系が磁石の耐食性向上に有利であり、特に一価アルコールがより効果的であることを見出した。nは1~3の自然数であり、好ましくは、nが1または2であり、より好ましくは、nが1である。 The hydroxyl compound according to the present invention may be an alcohol-based compound, and the alcohol-based compound includes, but is not limited to, a monohydric alcohol, a divalent alcohol, or a trihydric alcohol. The present invention has found that alcohols are advantageous for improving the corrosion resistance of magnets, and monohydric alcohols are particularly effective. n is a natural number of 1 to 3, preferably n is 1 or 2, and more preferably n is 1.
本発明において、RはC2~C15の炭化水素基から選ばれたものであってもよい。炭化水素基はアルキル、アルケニル又はアルキニルであってもよく、好ましくはアルキルである。本発明の1つの実施態様によれば、RはC2~C15のアルキルから選ばれたものであり、好ましくはC3~C9のアルキルであり、より好ましくはC3~C6のアルキルである。アルキルは直鎖アルキルまたは分枝鎖アルキルであってもよい。アルキルの例としてメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシルなどを含むがこれらに限定されていない。 In the present invention, R may be selected from the hydrocarbon groups of C2 to C15. The hydrocarbon group may be alkyl, alkenyl or alkynyl, preferably alkyl. According to one embodiment of the invention, R is selected from C2-C15 alkyls, preferably C3-C9 alkyls, more preferably C3-C6 alkyls. The alkyl may be straight chain alkyl or branched chain alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylic, dodecyl, tridecylic, tetradecyl, pentadecyl and the like.
本発明の1つの実施態様によれば、前記水酸基化合物は一価アルコールまたは二価アルコールであり、RはC2~C15のアルキルであり、nは1または2である。本発明の他の実施態様によれば、前記水酸基化合物は一価アルコールであり、RはC3~C6のアルキルから選ばれたものであり、nは1である。 According to one embodiment of the invention, the hydroxyl compound is a monohydric alcohol or a dihydric alcohol, R is an alkyl of C2-C15 and n is 1 or 2. According to another embodiment of the present invention, the hydroxyl compound is a monohydric alcohol, R is selected from the alkyls of C3 to C6, and n is 1.
水酸基化合物の例として、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、n-ペンタノール、イソアミルアルコール、ネオペンチルアルコール、n-ヘキサノール、イソヘキサノール、n-ヘプタノール、n-オクタノール、n-ノナノールなどを含むがこれらに限定されない。本発明の1つの実施態様によれば、水酸基化合物はエタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、n-ペンタノール、イソアミルアルコール、ネオペンチルアルコール、n-ヘキサノールまたはイソヘキサノールである。本発明の1つの具体的な実施態様によれば、前記水酸基化合物はn-プロパノールである。これにより、ネオジム鉄ホウ素磁石の耐食性を著しく向上させることができ、常温での成膜が可能となり、コストの低減、プロセスの簡略化が可能となる。 Examples of hydroxyl group compounds are ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-hexanol, isohexanol, n-heptanol, n-octanol, n-. Including, but not limited to, nonanol and the like. According to one embodiment of the invention, the hydroxyl compound is ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-hexanol or isohexanol. According to one specific embodiment of the present invention, the hydroxyl compound is n-propanol. As a result, the corrosion resistance of the neodymium iron-boron magnet can be remarkably improved, the film can be formed at room temperature, the cost can be reduced, and the process can be simplified.
本発明の使用によれば、下記の工程でネオジム鉄ホウ素磁石表面を処理してもよい。
(1)ネオジム鉄ホウ素磁石素材を前処理してネオジム鉄ホウ素磁石を形成する工程、
(2)ネオジム鉄ホウ素磁石の表面に水酸基化合物層を形成してプリフォームを得る工程、および、
(3)プリフォームを熱処理してネオジム鉄ホウ素磁石表面に酸化物層を形成する工程。
詳細な工程及びプロセスパラメータは以下と同じ、ここでは説明を省略する。
According to the use of the present invention, the neodymium iron boron magnet surface may be treated by the following steps.
(1) A process of pretreating a neodymium iron-boron magnet material to form a neodymium iron-boron magnet.
(2) A process of forming a hydroxyl group compound layer on the surface of a neodymium iron boron magnet to obtain a preform, and
(3) The process of heat-treating the preform to form an oxide layer on the surface of the neodymium iron-boron magnet.
The detailed process and process parameters are the same as the following, and description thereof will be omitted here.
<表面処理方法>
本発明に係るネオジム鉄ホウ素磁石の表面処理方法はネオジム鉄ホウ素磁石の表面に水酸基化合物層を形成してプリフォームを得る工程を含み、さらに、プリフォームを熱処理してネオジム鉄ホウ素磁石の表面に酸化物層を形成する工程を含んでもよい。また、本発明に係る方法はネオジム鉄ホウ素磁石の前処理工程を含んでもよい。詳細は後述する。
<Surface treatment method>
The surface treatment method for a neodymium iron boron magnet according to the present invention includes a step of forming a hydroxyl group compound layer on the surface of the neodymium iron boron magnet to obtain a preform, and further heat-treating the preform on the surface of the neodymium iron boron magnet. It may include a step of forming an oxide layer. Further, the method according to the present invention may include a pretreatment step of a neodymium iron-boron magnet. Details will be described later.
前処理工程
ネオジム鉄ホウ素磁石素材を、面取り研磨、化学脱脂、酸洗、超音波洗浄、水洗処理などの前処理工程を経てネオジム鉄ホウ素磁石を得、これをプリフォーム形成工程に供する。ネオジム鉄ホウ素磁石は、Nd、Fe、Bを主成分とし、他の遷移金属元素、他の希土類元素、C、O、Nなどの不可避不純物を含んでいてもよい。これらは当分野で周知なことであり、ここではその詳細な説明を省略する。焼結磁石は多孔質構造である可能性が高いという観点から、本発明に係るネオジム鉄ホウ素磁石は、焼結ネオジム鉄ホウ素磁石であることが好ましい。
Pretreatment Step The neodymium iron boron magnet material is subjected to pretreatment steps such as chamfering, chemical degreasing, pickling, ultrasonic washing, and water washing to obtain a neodymium iron boron magnet, which is used in the preform forming step. The neodymium iron-boron magnet contains Nd, Fe, and B as main components, and may contain other transition metal elements, other rare earth elements, and unavoidable impurities such as C, O, and N. These are well known in the art, and detailed description thereof will be omitted here. From the viewpoint that the sintered magnet is likely to have a porous structure, the neodymium iron-boron magnet according to the present invention is preferably a sintered neodymium iron-boron magnet.
前記面取り研磨工程では、前記ネオジム鉄ホウ素磁石素材をラッピングすることによって研磨および面取りを行う。なお、面取り加工は、通常の方法で行えばよく、ここではその説明を省略する。 In the chamfering polishing step, polishing and chamfering are performed by wrapping the neodymium iron-boron magnet material. The chamfering process may be performed by a normal method, and the description thereof will be omitted here.
化学脱脂工程では、アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面の油汚れを除去する。アルカリ性脱脂剤は水酸化ナトリウム、炭酸ナトリウム、リン酸三ナトリウムおよびケイ酸ナトリウムから選ばれた1種または複数種である。本発明の1つの実施態様によれば、アルカリ性脱脂剤は水酸化ナトリウム、リン酸三ナトリウム、炭酸水素ナトリウムおよび水からなる溶液である。具体的に、アルカリ性脱脂剤は水酸化ナトリウム20~30g/L、炭酸水素ナトリウム20~30g/Lおよびリン酸三ナトリウム3~10g/Lを含む。本発明の1つの実施態様によれば、アルカリ性脱脂剤は、水酸化ナトリウム、炭酸ナトリウム、リン酸三ナトリウム、ケイ酸ナトリウムおよび水からなる溶液である。具体的に、アルカリ性脱脂剤は、水酸化ナトリウム10~15g/L、炭酸ナトリウム20~30g/L、リン酸三ナトリウム50~70g/Lおよびケイ酸ナトリウム1~5g/Lを含む。前述したアルカリ性脱脂剤を用いると、脱脂効果が高く、更に水酸基化合物層の形成が促進され、耐食性が向上する。 In the chemical degreasing step, an alkaline degreasing agent is used to remove oil stains on the surface of the neodymium iron boron magnet material. The alkaline degreasing agent is one or more selected from sodium hydroxide, sodium carbonate, trisodium phosphate and sodium silicate. According to one embodiment of the invention, the alkaline degreasing agent is a solution consisting of sodium hydroxide, trisodium phosphate, sodium hydrogen carbonate and water. Specifically, the alkaline degreasing agent contains 20-30 g / L of sodium hydroxide, 20-30 g / L of sodium hydrogen carbonate and 3-10 g / L of trisodium phosphate. According to one embodiment of the invention, the alkaline degreasing agent is a solution consisting of sodium hydroxide, sodium carbonate, trisodium phosphate, sodium silicate and water. Specifically, the alkaline degreasing agent contains 10 to 15 g / L of sodium hydroxide, 20 to 30 g / L of sodium carbonate, 50 to 70 g / L of trisodium phosphate and 1 to 5 g / L of sodium silicate. When the above-mentioned alkaline degreasing agent is used, the degreasing effect is high, the formation of the hydroxyl group compound layer is promoted, and the corrosion resistance is improved.
酸洗工程では、脱脂後のネオジム鉄ホウ素磁石素材を水洗し、次いで酸洗して錆を除去する。酸洗工程で用いる酸性溶液は、塩酸溶液でも硝酸溶液でもよいが、硝酸溶液が好ましい。硝酸溶液は、濃度が1~10wt%であってもよく、好ましくは2~8wt%であり、より好ましくは3~6wt%である。これにより、錆を効果的に除去することができ、水酸基化合物層を形成して耐食性を向上させることに有利である。 In the pickling step, the neodymium iron boron magnet material after degreasing is washed with water, and then pickled to remove rust. The acidic solution used in the pickling step may be a hydrochloric acid solution or a nitric acid solution, but a nitric acid solution is preferable. The nitric acid solution may have a concentration of 1 to 10 wt%, preferably 2 to 8 wt%, and more preferably 3 to 6 wt%. This makes it possible to effectively remove rust, which is advantageous in forming a hydroxyl group compound layer and improving corrosion resistance.
超音波洗浄工程では、従来の超音波洗浄装置を使用し、さびおよび残留酸性溶液を十分に除去することができる。水洗処理は、残った酸性溶液をさらに除去し、プリフォーム形成工程用のネオジム鉄ホウ素磁石を得る工程である。 In the ultrasonic cleaning step, a conventional ultrasonic cleaning device can be used to sufficiently remove rust and residual acidic solution. The washing treatment is a step of further removing the remaining acidic solution to obtain a neodymium iron-boron magnet for the preform forming step.
プリフォーム形成工程
ネオジム鉄ホウ素磁石の表面に水酸基化合物層を形成してプリフォームを得る。水酸基化合物層は、耐食性に影響を与えない限り、他の物質を含んでもよい。好ましくは、水酸基化合物層が水酸基化合物のみからなる。これにより、耐食性を十分に確保できる。本発明に係る水酸基化合物は、下記の式(I)に示される構造を有する。
(そのうち、RはC2~C15の炭化水素基であり、nは1~3の自然数である。)
水酸基化合物は、融点が15℃未満であってもよく、好ましくは10℃未満であり、より好ましくは5℃未満である。水酸基化合物は、沸点が35℃超えてもよく、好ましくは75℃超え、より好ましくは80℃超える。水酸基化合物は、常温で、例えば、15~30℃で液状である。これにより、ネオジム鉄ホウ素磁石表面に均一な水酸基化合物層を形成し、水酸基化合物は、完全に揮発しにくいため、ネオジム鉄ホウ素磁石表面の空孔に浸漬し、耐食性をさらに向上された。水酸基化合物は、ネオジム鉄ホウ素磁石表面の空孔に浸漬するため、耐食性をさらに向上できる。
Preform forming step A hydroxyl group compound layer is formed on the surface of a neodymium iron boron magnet to obtain a preform. The hydroxyl group compound layer may contain other substances as long as it does not affect the corrosion resistance. Preferably, the hydroxyl compound layer comprises only the hydroxyl compound. As a result, sufficient corrosion resistance can be ensured. The hydroxyl group compound according to the present invention has a structure represented by the following formula (I).
(Of these, R is a hydrocarbon group of C2 to C15, and n is a natural number of 1 to 3.)
The hydroxyl compound may have a melting point of less than 15 ° C, preferably less than 10 ° C, more preferably less than 5 ° C. The hydroxyl compound may have a boiling point of more than 35 ° C, preferably more than 75 ° C, more preferably more than 80 ° C. The hydroxyl group compound is liquid at room temperature, for example, at 15 to 30 ° C. As a result, a uniform hydroxyl compound layer was formed on the surface of the neodymium iron-boron magnet, and since the hydroxyl compound was not completely volatilized, it was immersed in the pores on the surface of the neodymium iron-boron magnet to further improve the corrosion resistance. Since the hydroxyl group compound is immersed in the pores on the surface of the neodymium iron-boron magnet, the corrosion resistance can be further improved.
水酸基化合物は、好ましくはアルコール系であり、例えば、一価アルコール,二価アルコールまたは三価アルコールである。アルコール、特により良い効果を有する一価アルコールは、本発明に非常に適している。nは1~3の自然数であり、好ましくはnが1または2であり、より好ましくは、nが1である。 The hydroxyl compound is preferably an alcohol-based compound, for example, a monohydric alcohol, a divalent alcohol or a trihydric alcohol. Alcohols, especially monohydric alcohols with better effects, are very suitable for the present invention. n is a natural number from 1 to 3, preferably n is 1 or 2, and more preferably n is 1.
RはC2~C15の炭化水素基から選ばれたものであってもよい。炭化水素基はアルキル、アルケニル又はアルキニルであってもよく、好ましくはアルキルである。本発明のある実施態様によれば、RはC2~C15のアルキルから選ばれたものであってもよく、好ましくはC3~C9のアルキルであり、より好ましくはC3~C6のアルキルである。アルキルは直鎖アルキルまたは分枝鎖アルキルであってもよい。アルキルの実例としてメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシルなどを含むがこれらに限定されていない。ある実施態様によれば、前記水酸基化合物は一価アルコールまたは二価アルコールであり、RはC2~C15のアルキルから選ばれたものであり、nは1または2である。別の実施態様によれば、前記水酸基化合物は一価アルコールであり、RはC3~C6のアルキルから選ばれたものであり、nは1である。 R may be selected from the hydrocarbon groups C2-C15. The hydrocarbon group may be alkyl, alkenyl or alkynyl, preferably alkyl. According to one embodiment of the invention, R may be selected from alkyls of C2 to C15, preferably alkyls of C3 to C9, and more preferably alkyls of C3 to C6. The alkyl may be straight chain alkyl or branched chain alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylic, dodecyl, tridecylic, tetradecyl, pentadecyl and the like. According to one embodiment, the hydroxyl compound is a monohydric alcohol or a divalent alcohol, R is selected from the alkyls of C2-C15, and n is 1 or 2. According to another embodiment, the hydroxyl compound is a monohydric alcohol, R is selected from the alkyls of C3 to C6, and n is 1.
本発明に係る水酸基化合物の実例としてエタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、n-ペンタノール、イソアミルアルコール、ネオペンチルアルコール、n-ヘキサノール、イソヘキサノール、n-ヘプタノール、n-オクタノール、n-ノナノールなどを含むがこれらに限定されていない。ある実施態様によれば、水酸基化合物はエタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、n-ペンタノール、イソアミルアルコール、ネオペンチルアルコール、n-ヘキサノールまたはイソヘキサノールである。他の実施態様によれば、前記水酸基化合物はn-プロパノールである。これにより、ネオジム鉄ホウ素磁石の表面及び空孔での水酸基化合物層の成膜に有利であり、かつ、コストの低減、プロセスの簡略化が可能となる。 Examples of the hydroxyl group compound according to the present invention include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-hexanol, isohexanol, n-heptanol, n-octanol. , N-nonanol, etc., but not limited to these. According to one embodiment, the hydroxyl compound is ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-hexanol or isohexanol. According to another embodiment, the hydroxyl compound is n-propanol. This is advantageous for forming a hydroxyl group compound layer on the surface and pores of a neodymium iron-boron magnet, and enables cost reduction and simplification of the process.
ネオジボンド磁石の表面に溶射、含浸などの各種の方法で水酸基化合物層を形成することができる。含浸工程は、水酸基化合物をネオジム鉄ホウ素磁石に十分に密着させることができ、ネオジム鉄ホウ素磁石の空隙にも水酸基化合物を充填させることができるため、耐食性を向上させるのに本発明により適していることを見出した。従って、本発明に係る表面処理方法は、焼結ネオジム鉄ホウ素磁石の耐食性を向上させるのに極めて好適である。 A hydroxyl group compound layer can be formed on the surface of a neodibond magnet by various methods such as thermal spraying and impregnation. In the impregnation step, the hydroxyl group compound can be sufficiently adhered to the neodymium iron-boron magnet, and the voids of the neodymium iron-boron magnet can also be filled with the hydroxyl group compound, so that the present invention is more suitable for improving corrosion resistance. I found that. Therefore, the surface treatment method according to the present invention is extremely suitable for improving the corrosion resistance of the sintered neodymium iron boron magnet.
本発明の1つの実施態様によれば、ネオジム鉄ホウ素磁石を前記水酸基化合物に含浸し、取り出した後ブロー乾燥してプリフォームを得る。含浸時間は、水酸基化合物をネオジム鉄ホウ素磁石表面に十分結合させ、ネオジム鉄ホウ素磁石の空孔に十分浸漬するように、必要な時間であればよい。ネオジム鉄ホウ素磁石を水酸基化合物に完全に含浸する必要がある。含浸時間は5~60minであってもよく、好ましくは10~50minであり、より好ましくは20~30minである。これにより、水酸基化合物をネオジム鉄ホウ素磁石の表面に十分に結合させ、ネオジム鉄ホウ素磁石の空孔に十分に浸漬できるとともに、生産性が向上する。なお、ブロー乾燥は常法により行われるが、水酸基化合物層の破壊を避けるために、真空での操作を用いることは推奨されない。 According to one embodiment of the present invention, a neodymium iron boron magnet is impregnated into the hydroxyl compound, taken out, and then blow-dried to obtain a preform. The impregnation time may be any time necessary so that the hydroxyl group compound is sufficiently bonded to the surface of the neodymium iron-boron magnet and sufficiently immersed in the pores of the neodymium iron-boron magnet. It is necessary to completely impregnate the hydroxyl compound with a neodymium iron boron magnet. The impregnation time may be 5 to 60 min, preferably 10 to 50 min, and more preferably 20 to 30 min. As a result, the hydroxyl group compound can be sufficiently bonded to the surface of the neodymium iron-boron magnet, and can be sufficiently immersed in the pores of the neodymium iron-boron magnet, and the productivity is improved. Although blow drying is performed by a conventional method, it is not recommended to use a vacuum operation in order to avoid destruction of the hydroxyl group compound layer.
酸化物層形成工程
ネオジム鉄ホウ素磁石表面に酸化物層を形成するためにプリフォームを熱処理する。酸化物層の厚さは0.6~3.5μmであってもよく、好ましくは1~3μmであり、より好ましくは2~3μmである。
プリフォームをトンネル加熱炉に入れて熱処理し、加熱工程において、トンネル加熱炉に窒素ガスを流す。トンネル加熱炉は当業界に汎用な設備を採用すばれよく、ここではその説明を省略する。
Oxide layer formation step The preform is heat treated to form an oxide layer on the surface of the neodymium iron boron magnet. The thickness of the oxide layer may be 0.6 to 3.5 μm, preferably 1 to 3 μm, and more preferably 2 to 3 μm.
The preform is placed in a tunnel heating furnace and heat-treated, and nitrogen gas is passed through the tunnel heating furnace in the heating step. The tunnel heating furnace may be equipped with general-purpose equipment in the industry, and the description thereof is omitted here.
トンネル加熱炉は、熱処理温度が380~450℃であってもよく、好ましくは好ましくは400~450℃であり、より好ましくは420~450℃である。熱処理が高すぎると、製造コストの増加及び酸化物層の均一性の低下をもたらす。熱処理温度が低すぎると、形成される酸化物層の空隙率が大きく、厚みが不均一となり、磁石結合力が弱く、脱落しやすくなる。熱処理時間は25~50minであってもよく、好ましくは27~40minであり、より好ましくは30~40minである。熱処理時間が長すぎると、製造コストの増加および酸化物層の厚さの均一性の低下をもたらす。熱処理時間が短すぎると、空孔に酸化物層が形成されず、耐食性が劣化する。 The heat treatment temperature of the tunnel heating furnace may be 380 to 450 ° C, preferably 400 to 450 ° C, and more preferably 420 to 450 ° C. If the heat treatment is too high, the manufacturing cost will increase and the uniformity of the oxide layer will decrease. If the heat treatment temperature is too low, the porosity of the formed oxide layer is large, the thickness is non-uniform, the magnet bonding force is weak, and the oxide layer is likely to fall off. The heat treatment time may be 25 to 50 min, preferably 27 to 40 min, and more preferably 30 to 40 min. If the heat treatment time is too long, the manufacturing cost will increase and the uniformity of the thickness of the oxide layer will decrease. If the heat treatment time is too short, the oxide layer is not formed in the pores and the corrosion resistance is deteriorated.
加熱において、トンネル加熱炉に窒素ガスを流し、窒素ガスの流量を25~100L/minに制御する。好ましくは、前記窒素ガスの流量を40~60L/minに制御する。より好ましくは、前記窒素ガスの流量を45~55L/minに制御する。窒素ガスの流量が高すぎると、ネオジム鉄ホウ素磁石の周囲の酸素濃度が低くなりすぎて緻密な酸化物層を形成することができない。窒素ガスの流量が少なすぎるとネオジム鉄ホウ素磁石の周囲の酸素濃度が高くなりすぎ、酸化反応速度が速くなりすぎて均一な酸化物層を形成することができない。 In heating, nitrogen gas is passed through a tunnel heating furnace, and the flow rate of nitrogen gas is controlled to 25 to 100 L / min. Preferably, the flow rate of the nitrogen gas is controlled to 40 to 60 L / min. More preferably, the flow rate of the nitrogen gas is controlled to 45 to 55 L / min. If the flow rate of nitrogen gas is too high, the oxygen concentration around the neodymium iron-boron magnet becomes too low to form a dense oxide layer. If the flow rate of nitrogen gas is too small, the oxygen concentration around the neodymium iron-boron magnet becomes too high, and the oxidation reaction rate becomes too fast to form a uniform oxide layer.
<耐食性ネオジム鉄ホウ素磁石>
前述した表面処理方法により、耐食性のネオジム鉄ホウ素磁石を得た。酸化物層の厚さは0.6~3.5μmであってもよく、好ましくは1~3.5μmであり、より好ましくは1.2~3.5μmである。これにより、ネオジム鉄ホウ素磁石の耐食性をより高めることができる。酸化物層の厚さが薄すぎると、厚さが不均一で空隙率が大きくなり、また、酸化物層の厚さが薄いため、酸化物層の腐食防止期間が短くなる。酸化物層の厚さが厚すぎると、熱処理時間を長くする必要があり、生産コストが高くなる。
<Corrosion resistant neodymium iron boron magnet>
Corrosion-resistant neodymium iron-boron magnets were obtained by the surface treatment method described above. The thickness of the oxide layer may be 0.6 to 3.5 μm, preferably 1 to 3.5 μm, and more preferably 1.2 to 3.5 μm. Thereby, the corrosion resistance of the neodymium iron boron magnet can be further improved. If the thickness of the oxide layer is too thin, the thickness is non-uniform and the porosity is large, and since the thickness of the oxide layer is thin, the corrosion prevention period of the oxide layer is shortened. If the thickness of the oxide layer is too thick, the heat treatment time needs to be long, and the production cost increases.
GB/T 10125-2012《人工雰囲気腐食試験・塩水噴霧試験》に従って35℃、5wt%NaClの条件で測定した前記耐食性のネオジム鉄ホウ素磁石が腐食し始めるまでの時間は、45分間超え、好ましくは1時間超え、より好ましくは1.5時間超え、例えば、1.5~2時間である。 The time until the corrosion-resistant neodymium iron-boron magnet started to corrode, measured under the conditions of 35 ° C and 5 wt% NaCl according to GB / T 10125-2012 << Artificial Atmosphere Corrosion Test / Salt Spray Test >>, exceeds 45 minutes, preferably. Over 1 hour, more preferably over 1.5 hours, for example 1.5-2 hours.
GB/T2423.3-2006に従って85℃、85%RHの条件で測定された前記耐食性ネオジム鉄ホウ素磁石が腐食し始めるまでの時間は1.2時間超え、好ましくは1.5時間超え、より好ましくは2時間超え、例えば2~3時間である。 The time until the corrosion-resistant neodymium iron boron magnet, measured at 85 ° C. and 85% RH according to GB / T2423.3-2006, begins to corrode exceeds 1.2 hours, preferably more than 1.5 hours, more preferably more than 2 hours. For example, 2-3 hours.
以下、下記の実施例および比較例に使用された原料を説明する。
アルカリ性脱脂剤:水酸化ナトリウム25g/L、炭酸水素ナトリウム25g/Lおよびリン酸三ナトリウム5g/Lを含む水溶液。
Hereinafter, the raw materials used in the following examples and comparative examples will be described.
Alkaline degreasing agent: An aqueous solution containing 25 g / L of sodium hydroxide, 25 g / L of sodium hydrogen carbonate and 5 g / L of trisodium phosphate.
以下、実施例および比較例に使用された測定方法を説明する。
塩水噴霧試験:GB/T 10125-2012《人工雰囲気腐食試験・塩水噴霧試験》に従って35℃、5wt%NaClの条件でネオジム鉄ホウ素磁石が腐食し始めるまでの時間を測定し、記録した。
Hereinafter, the measurement methods used in Examples and Comparative Examples will be described.
Salt spray test: The time until the neodymium iron boron magnet started to corrode was measured and recorded under the conditions of 35 ° C and 5 wt% NaCl according to GB / T 10125-2012 << Artificial atmosphere corrosion test / salt spray test >>.
恒温恒湿試験:GB/T2423.3-2006に従って85℃、85%RH条件でネオジム鉄ホウ素磁石が腐食し始めるまでの時間を測定し、記録した。 Constant temperature and humidity test: The time until the neodymium iron boron magnet started to corrode was measured and recorded under the conditions of 85 ° C and 85% RH according to GB / T2423.3-2006.
実施例1
研磨加工を採用して50枚の焼結ネオジム鉄ホウ素磁石素材(長さ55mm、幅さ21.4mm、高さ1.8mm)を面取り研磨した。アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面を脱脂した。脱脂した後のネオジム鉄ホウ素磁石素材を水洗い、そして3wt%硝酸溶液によって酸洗し、表面の酸化物を除去した。最後に超音波洗浄および水洗することを2回繰り返し、ネオジム鉄ホウ素磁石を得た。
ネオジム鉄ホウ素磁石をイソプロパノールに20分間含浸し、これを取り出してブロー乾燥し、プリフォームを得た。前記プリフォームを銅網の上に整然と並べ、トンネル加熱炉をオンにして温度380℃に加熱し、窒素バルブを開き、炉内の窒素ガス流量を50L/minに制御し、1分間後にプリフォーム入り銅網をベルトのフィード口に置き、ベルトからトンネル加熱炉内に送り、25min加熱して表面に酸化物層を有するネオジム鉄ホウ素磁石を得た。酸化物層の厚さは1μmであった。
Example 1
Using polishing, 50 sintered neodymium iron boron magnet materials (length 55 mm, width 21.4 mm, height 1.8 mm) were chamfered and polished. The surface of the neodymium iron boron magnet material was degreased using an alkaline degreasing agent. After degreasing, the neodymium iron boron magnet material was washed with water and pickled with a 3 wt% nitric acid solution to remove surface oxides. Finally, ultrasonic cleaning and washing with water were repeated twice to obtain neodymium iron-boron magnets.
The neodymium iron boron magnet was impregnated with isopropanol for 20 minutes, which was taken out and blow-dried to obtain a preform. Arrange the preforms neatly on a copper net, turn on the tunnel heating furnace, heat to a temperature of 380 ° C, open the nitrogen valve, control the nitrogen gas flow rate in the furnace to 50 L / min, and preform after 1 minute. A copper net was placed in the feed port of the belt, sent from the belt into a tunnel heating furnace, and heated for 25 min to obtain a neodymium iron-boron magnet having an oxide layer on the surface. The thickness of the oxide layer was 1 μm.
実施例2
研磨加工を採用して50枚の焼結ネオジム鉄ホウ素磁石素材(長さ55mm、幅さ21.4mm、高さ1.8mm)を面取り研磨した。アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面を脱脂した。脱脂した後のネオジム鉄ホウ素磁石素材を水洗い、そして3wt%硝酸溶液によって酸洗し、表面の酸化物を除去した。最後に超音波洗浄および水洗することを2回繰り返して、ネオジム鉄ホウ素磁石を得た。
ネオジム鉄ホウ素磁石をイソプロパノールに20分間含浸し、そして取り出してブロー乾燥し、プリフォームを得た。前記プリフォームを銅網の上に整然と並べ、トンネル加熱炉をオンにして温度400℃に加熱し、窒素バルブを開き、炉内の窒素ガス流量を50L/minに制御し、1分間後にプリフォーム入り銅網をベルトのフィード口に置き、ベルトからトンネル加熱炉内に送り、30min加熱して表面に酸化物層を有するネオジム鉄ホウ素磁石を得た。酸化物層の厚さは2μmであった。
Example 2
Using polishing, 50 sintered neodymium iron boron magnet materials (length 55 mm, width 21.4 mm, height 1.8 mm) were chamfered and polished. The surface of the neodymium iron boron magnet material was degreased using an alkaline degreasing agent. After degreasing, the neodymium iron boron magnet material was washed with water and pickled with a 3 wt% nitric acid solution to remove surface oxides. Finally, ultrasonic cleaning and washing with water were repeated twice to obtain neodymium iron-boron magnets.
Neodymium iron boron magnets were impregnated in isopropanol for 20 minutes and then removed and blow dried to give a preform. Arrange the preforms neatly on a copper net, turn on the tunnel heating furnace, heat to a temperature of 400 ° C, open the nitrogen valve, control the nitrogen gas flow rate in the furnace to 50 L / min, and preform after 1 minute. A copper net was placed in the feed port of the belt, sent from the belt into a tunnel heating furnace, and heated for 30 minutes to obtain a neodymium iron boron magnet having an oxide layer on the surface. The thickness of the oxide layer was 2 μm.
実施例3
研磨加工を採用して50枚の焼結ネオジム鉄ホウ素磁石素材(長さ55mm、幅さ21.4mm、高さ1.8mm)を面取り研磨した。アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面を脱脂した。脱脂した後のネオジム鉄ホウ素磁石素材を水洗い、そして3wt%硝酸溶液によって酸洗し、表面の酸化物を除去した。最後に超音波洗浄および水洗することを2回繰り返して、ネオジム鉄ホウ素磁石を得た。
ネオジム鉄ホウ素磁石をイソプロパノールに20分間含浸し、そして取り出してブロー乾燥し、プリフォームを得た。前記プリフォームを銅網の上に整然と並べ、トンネル加熱炉をオンにして温度420℃に加熱し、窒素バルブを開き、炉内の窒素ガス流量を45L/minに制御し、1分間後にプリフォーム入り銅網をベルトのフィード口に置き、ベルトからトンネル加熱炉内に送り、40min加熱して表面に酸化物層を有するネオジム鉄ホウ素磁石を得た。酸化物層の厚さは3μmであった。
Example 3
Using polishing, 50 sintered neodymium iron boron magnet materials (length 55 mm, width 21.4 mm, height 1.8 mm) were chamfered and polished. The surface of the neodymium iron boron magnet material was degreased using an alkaline degreasing agent. After degreasing, the neodymium iron boron magnet material was washed with water and pickled with a 3 wt% nitric acid solution to remove surface oxides. Finally, ultrasonic cleaning and washing with water were repeated twice to obtain neodymium iron-boron magnets.
Neodymium iron boron magnets were impregnated in isopropanol for 20 minutes and then removed and blow dried to give a preform. Arrange the preforms neatly on a copper net, turn on the tunnel heating furnace, heat to a temperature of 420 ° C, open the nitrogen valve, control the nitrogen gas flow rate in the furnace to 45 L / min, and preform after 1 minute. A copper net containing copper was placed in the feed port of the belt, sent from the belt into a tunnel heating furnace, and heated for 40 minutes to obtain a neodymium iron-boron magnet having an oxide layer on the surface. The thickness of the oxide layer was 3 μm.
実施例4
研磨加工を採用して50枚の焼結ネオジム鉄ホウ素磁石素材(長さ55mm、幅さ21.4mm、高さ1.8mm)を面取り研磨した。アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面を脱脂した。脱脂した後のネオジム鉄ホウ素磁石素材を水洗い、そして3wt%硝酸溶液によって酸洗し、表面の酸化物を除去した。最後に超音波洗浄および水洗することを2回繰り返して、ネオジム鉄ホウ素磁石を得た。
ネオジム鉄ホウ素磁石をイソプロパノールに20分間含浸し、そして取り出してブロー乾燥し、プリフォームを得た。前記プリフォームを銅網の上に整然と並べ、トンネル加熱炉をオンにして温度450℃に加熱し、窒素バルブを開き、炉内の窒素ガス流量を55L/minに制御し、1分間後にプリフォーム入り銅網をベルトのフィード口に置き、ベルトからトンネル加熱炉内に送り、35min加熱して表面が酸化物層を有するネオジム鉄ホウ素磁石を得た。酸化物層の厚さは3.5μmであった。
Example 4
Using polishing, 50 sintered neodymium iron boron magnet materials (length 55 mm, width 21.4 mm, height 1.8 mm) were chamfered and polished. The surface of the neodymium iron boron magnet material was degreased using an alkaline degreasing agent. After degreasing, the neodymium iron boron magnet material was washed with water and pickled with a 3 wt% nitric acid solution to remove surface oxides. Finally, ultrasonic cleaning and washing with water were repeated twice to obtain neodymium iron-boron magnets.
Neodymium iron boron magnets were impregnated in isopropanol for 20 minutes and then removed and blow dried to give a preform. Arrange the preforms neatly on a copper net, turn on the tunnel heating furnace, heat to a temperature of 450 ° C, open the nitrogen valve, control the nitrogen gas flow rate in the furnace to 55 L / min, and preform after 1 minute. A copper net was placed in the feed port of the belt, sent from the belt into a tunnel heating furnace, and heated for 35 minutes to obtain a neodymium iron-boron magnet having an oxide layer on the surface. The thickness of the oxide layer was 3.5 μm.
比較例1
研磨加工を採用して50枚の焼結ネオジム鉄ホウ素磁石素材(長さ55mm、幅さ21.4mm、高さ1.8mm)を面取り研磨した。アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面を脱脂した。脱脂した後のネオジム鉄ホウ素磁石素材を水洗い、そして3wt%硝酸溶液によって酸洗し、表面の酸化物を除去した。最後に超音波洗浄および水洗することを2回繰り返して、ネオジム鉄ホウ素磁石を得た。
前記ネオジム鉄ホウ素磁石を銅網の上に整然と並べ、トンネル加熱炉をオンにして温度380℃に加熱し、窒素バルブを開き、炉内の窒素ガス流量を50L/minに制御し、1分間後にプリフォーム入り銅網をベルトのフィード口に置き、ベルトからトンネル加熱炉内に送り、25min加熱して表面に酸化物層を有するネオジム鉄ホウ素磁石を得た。酸化物層の厚さは0.8μmであった。
Comparative example 1
Using polishing, 50 sintered neodymium iron boron magnet materials (length 55 mm, width 21.4 mm, height 1.8 mm) were chamfered and polished. The surface of the neodymium iron boron magnet material was degreased using an alkaline degreasing agent. After degreasing, the neodymium iron boron magnet material was washed with water and pickled with a 3 wt% nitric acid solution to remove surface oxides. Finally, ultrasonic cleaning and washing with water were repeated twice to obtain neodymium iron-boron magnets.
The neodymium iron boron magnets are neatly arranged on a copper net, the tunnel heating furnace is turned on and heated to a temperature of 380 ° C, the nitrogen valve is opened, the nitrogen gas flow rate in the furnace is controlled to 50 L / min, and after 1 minute. A copper net containing preform was placed in the feed port of the belt, sent from the belt into a tunnel heating furnace, and heated for 25 minutes to obtain a neodymium iron boron magnet having an oxide layer on the surface. The thickness of the oxide layer was 0.8 μm.
比較例2
研磨加工を採用して50枚の焼結ネオジム鉄ホウ素磁石素材(長さ55mm、幅さ21.4mm、高さ1.8mm)を面取り研磨した。アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面を脱脂した。脱脂した後のネオジム鉄ホウ素磁石素材を水洗い、そして3wt%硝酸溶液によって酸洗し、表面の酸化物を除去した。最後に超音波洗浄および水洗することを2回繰り返して、ネオジム鉄ホウ素磁石を得た。
ネオジム鉄ホウ素磁石をイソプロパノールに20分間含浸し、そして取り出してブロー乾燥し、プリフォームを得た。前記プリフォームを銅網の上に整然と並べ、トンネル加熱炉をオンにして温度350℃に加熱し、窒素バルブを開き、炉内の窒素ガス流量を40L/minに制御し、1分間後にプリフォーム入り銅網をベルトのフィード口に置き、ベルトからトンネル加熱炉内に送り、20min加熱して表面が酸化物層を有するネオジム鉄ホウ素磁石を得た。酸化物層の厚さは0.5μmであった。
Comparative example 2
Using polishing, 50 sintered neodymium iron boron magnet materials (length 55 mm, width 21.4 mm, height 1.8 mm) were chamfered and polished. The surface of the neodymium iron boron magnet material was degreased using an alkaline degreasing agent. After degreasing, the neodymium iron boron magnet material was washed with water and pickled with a 3 wt% nitric acid solution to remove surface oxides. Finally, ultrasonic cleaning and washing with water were repeated twice to obtain neodymium iron-boron magnets.
Neodymium iron boron magnets were impregnated in isopropanol for 20 minutes and then removed and blow dried to give a preform. Arrange the preforms neatly on a copper net, turn on the tunnel heating furnace, heat to a temperature of 350 ° C, open the nitrogen valve, control the nitrogen gas flow rate in the furnace to 40 L / min, and preform after 1 minute. A copper net was placed in the feed port of the belt, sent from the belt into a tunnel heating furnace, and heated for 20 minutes to obtain a neodymium iron-boron magnet having an oxide layer on the surface. The thickness of the oxide layer was 0.5 μm.
比較例3
研磨加工を採用して50枚の焼結ネオジム鉄ホウ素磁石素材(長さ55mm、幅さ21.4mm、高さ1.8mm)を面取り研磨した。アルカリ性脱脂剤を用いてネオジム鉄ホウ素磁石素材表面を脱脂した。脱脂した後のネオジム鉄ホウ素磁石素材を水洗い、そして3wt%硝酸溶液によって酸洗し、表面の酸化物を除去した。最後に超音波洗浄および水洗することを2回繰り返して、ネオジム鉄ホウ素磁石を得た。
ネオジム鉄ホウ素磁石をイソプロパノールに20分間含浸し、そして取り出してブロー乾燥し、プリフォームを得た。前記プリフォームを銅網の上に整然と並べ、トンネル加熱炉をオンにして温度500℃に加熱し、窒素バルブを開き、炉内の窒素ガス流量を50L/minに制御し、1分間後にプリフォーム入り銅網をベルトのフィード口に置き、ベルトからトンネル加熱炉内に送り、25min加熱して表面が酸化物層を有するネオジム鉄ホウ素磁石を得た。酸化物層の厚さは0.7μmであった。
Comparative example 3
Using polishing, 50 sintered neodymium iron boron magnet materials (length 55 mm, width 21.4 mm, height 1.8 mm) were chamfered and polished. The surface of the neodymium iron boron magnet material was degreased using an alkaline degreasing agent. After degreasing, the neodymium iron boron magnet material was washed with water and pickled with a 3 wt% nitric acid solution to remove surface oxides. Finally, ultrasonic cleaning and washing with water were repeated twice to obtain neodymium iron-boron magnets.
Neodymium iron boron magnets were impregnated in isopropanol for 20 minutes and then removed and blow dried to give a preform. Arrange the preforms neatly on a copper net, turn on the tunnel heating furnace, heat to a temperature of 500 ° C, open the nitrogen valve, control the nitrogen gas flow rate in the furnace to 50 L / min, and preform after 1 minute. A copper net was placed in the feed port of the belt, sent from the belt into a tunnel heating furnace, and heated for 25 min to obtain a neodymium iron-boron magnet having an oxide layer on the surface. The thickness of the oxide layer was 0.7 μm.
表1から分かるように、本発明に係るネオジム鉄ホウ素磁石は耐食性が著しく改善した。実施例1および比較例1からわかるように、イソプロピルアルコールを含浸しなかったネオジム鉄ホウ素磁石(比較例1)は、熱処理後の耐食性が劣っていた。イソプロピルアルコールを含浸したネオジム鉄ホウ素磁石(実施例1)は、熱処理後の耐食性が著しく向上された。 As can be seen from Table 1, the neodymium iron-boron magnet according to the present invention has significantly improved corrosion resistance. As can be seen from Example 1 and Comparative Example 1, the neodymium iron boron magnet (Comparative Example 1) not impregnated with isopropyl alcohol was inferior in corrosion resistance after heat treatment. The neodymium iron boron magnet impregnated with isopropyl alcohol (Example 1) had significantly improved corrosion resistance after heat treatment.
熱処理条件を調整することにより、ネオジム鉄ホウ素磁石の耐食性をさらに向上させることができる。実施例1~3によれば、熱処理温度を適度に高くし、熱処理時間を長くすることにより、酸化層の厚さを厚くしてネオジム鉄ホウ素磁石の耐食性を向上させた。実施例4と実施例3との比較から分かるように、熱処理温度を上げるには、過剰な酸化を避けるために窒素ガス流量をその分増加させる必要があり、さもないと耐食性が低下する。 By adjusting the heat treatment conditions, the corrosion resistance of the neodymium iron-boron magnet can be further improved. According to Examples 1 to 3, the heat treatment temperature was appropriately raised and the heat treatment time was lengthened to increase the thickness of the oxide layer and improve the corrosion resistance of the neodymium iron-boron magnet. As can be seen from the comparison between Example 4 and Example 3, in order to raise the heat treatment temperature, it is necessary to increase the nitrogen gas flow rate by that amount in order to avoid excessive oxidation, or the corrosion resistance is lowered.
実施例1と比較例2~3との比較からわかるように、熱処理温度が低すぎる場合も高すぎる場合もネオジム鉄ホウ素磁石の耐食性の改善には不利である。
本発明は上記実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者が思いつく任意の変形、改良、置換などを本発明の範囲に含まれるものとする。
As can be seen from the comparison between Example 1 and Comparative Examples 2 and 3, it is disadvantageous to improve the corrosion resistance of the neodymium iron-boron magnet when the heat treatment temperature is too low or too high.
The present invention is not limited to the above-described embodiment, and any modifications, improvements, substitutions, etc. that can be conceived by those skilled in the art are included in the scope of the present invention without departing from the spirit of the present invention.
Claims (10)
(そのうち、RはC2~C15の炭化水素基から選ばれたものであり、nは1~3の自然数である。) Use of a hydroxyl group compound for improving the corrosion resistance of a neodymium iron boron magnet, wherein the hydroxyl group compound has a structure represented by the formula (I).
(Of these, R is selected from the hydrocarbon groups of C2 to C15, and n is a natural number of 1 to 3.)
(そのうち、RはC2~C15の炭化水素基から選ばれたものであり、nは1~3の自然数である。) A method for surface treatment of a neodymium iron boron magnet, which comprises a step of forming a hydroxyl group compound layer on the surface of the neodymium iron boron magnet to obtain a preform, and the hydroxyl compound has a structure represented by the formula (I). ..
(Of these, R is selected from the hydrocarbon groups of C2 to C15, and n is a natural number of 1 to 3.)
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CN116285578A (en) * | 2023-03-24 | 2023-06-23 | 合肥工业大学 | Preparation method of NdFeB surface modified hexagonal boron nitride reinforced epoxy composite coating |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019214920A1 (en) * | 2018-05-08 | 2019-11-14 | Abiomed Europe Gmbh | Corrosion-resistant permanent magnet and intravascular blood pump comprising the magnet |
JP2020503083A (en) * | 2016-11-02 | 2020-01-30 | アビオメド オイローパ ゲーエムベーハー | Intravascular blood pump with corrosion-resistant permanent magnet |
CN111073467A (en) * | 2019-12-20 | 2020-04-28 | 浙江中杭新材料科技有限公司 | Corrosion-resistant composite protective layer material for neodymium iron boron |
CN111073466A (en) * | 2019-12-20 | 2020-04-28 | 浙江中杭新材料科技有限公司 | Preparation method of low-cost high-corrosion-resistance neodymium iron boron |
CN111974655A (en) * | 2020-08-27 | 2020-11-24 | 宁波美固力磁电有限公司 | Preparation method of neodymium iron boron magnet with corrosion resistance |
WO2022134662A1 (en) * | 2020-12-22 | 2022-06-30 | 天津三环乐喜新材料有限公司 | Sintered neodymium-iron-boron magnet and anti-corrosion treatment method therefor |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102324814B (en) * | 2011-08-26 | 2013-08-28 | 邓上云 | Preparation process of neodymium-iron-boron /ferrite composite magnet body for permanent magnet alternating current synchronous motor |
CN102877058B (en) * | 2012-10-31 | 2018-07-24 | 四川职业技术学院 | A method of being used for neodymium iron boron magnetic body surface antirust treatment |
CN105839045A (en) * | 2016-04-17 | 2016-08-10 | 北京工业大学 | Method for improving anticorrosion performance of sintered neodymium-iron-boron magnet |
CN111020659A (en) * | 2019-12-07 | 2020-04-17 | 爱科科技有限公司 | Method for reducing porosity of coating on surface of neodymium iron boron permanent magnet material |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020503083A (en) * | 2016-11-02 | 2020-01-30 | アビオメド オイローパ ゲーエムベーハー | Intravascular blood pump with corrosion-resistant permanent magnet |
WO2019214920A1 (en) * | 2018-05-08 | 2019-11-14 | Abiomed Europe Gmbh | Corrosion-resistant permanent magnet and intravascular blood pump comprising the magnet |
CN111073467A (en) * | 2019-12-20 | 2020-04-28 | 浙江中杭新材料科技有限公司 | Corrosion-resistant composite protective layer material for neodymium iron boron |
CN111073466A (en) * | 2019-12-20 | 2020-04-28 | 浙江中杭新材料科技有限公司 | Preparation method of low-cost high-corrosion-resistance neodymium iron boron |
CN111974655A (en) * | 2020-08-27 | 2020-11-24 | 宁波美固力磁电有限公司 | Preparation method of neodymium iron boron magnet with corrosion resistance |
WO2022134662A1 (en) * | 2020-12-22 | 2022-06-30 | 天津三环乐喜新材料有限公司 | Sintered neodymium-iron-boron magnet and anti-corrosion treatment method therefor |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116285578A (en) * | 2023-03-24 | 2023-06-23 | 合肥工业大学 | Preparation method of NdFeB surface modified hexagonal boron nitride reinforced epoxy composite coating |
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