CN112779576B - Neodymium-iron-boron magnet composite coating and preparation method thereof - Google Patents
Neodymium-iron-boron magnet composite coating and preparation method thereof Download PDFInfo
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- CN112779576B CN112779576B CN202011567211.5A CN202011567211A CN112779576B CN 112779576 B CN112779576 B CN 112779576B CN 202011567211 A CN202011567211 A CN 202011567211A CN 112779576 B CN112779576 B CN 112779576B
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- nickel
- plating layer
- zinc
- tin
- plating
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 79
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 193
- 238000007747 plating Methods 0.000 claims abstract description 185
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 95
- OQDDOQFECBFUPY-UHFFFAOYSA-N [Ni].[Sn].[Zn] Chemical group [Ni].[Sn].[Zn] OQDDOQFECBFUPY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910002058 ternary alloy Inorganic materials 0.000 claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 31
- 239000011701 zinc Substances 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 230000007797 corrosion Effects 0.000 claims abstract description 24
- 238000005260 corrosion Methods 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims description 171
- 238000005406 washing Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 230000004913 activation Effects 0.000 claims description 30
- 238000004070 electrodeposition Methods 0.000 claims description 25
- 239000011229 interlayer Substances 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 16
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 15
- 239000000080 wetting agent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 13
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 13
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 12
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 12
- 238000005238 degreasing Methods 0.000 claims description 11
- 239000011135 tin Substances 0.000 claims description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000011686 zinc sulphate Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 150000003840 hydrochlorides Chemical class 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- -1 sulfonimides Chemical class 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 239000006172 buffering agent Substances 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910020953 Sn-Ni-Zn Inorganic materials 0.000 claims description 2
- 229910009051 Sn—Ni—Zn Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 238000007772 electroless plating Methods 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229960001922 sodium perborate Drugs 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 235000015895 biscuits Nutrition 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 229940124530 sulfonamide Drugs 0.000 claims 1
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- 150000003871 sulfonates Chemical class 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 53
- 239000000243 solution Substances 0.000 description 42
- 238000001994 activation Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 11
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 9
- WRYPDLONHOXTBL-UHFFFAOYSA-N [Ni].[Ni].[Zn].[Sn] Chemical compound [Ni].[Ni].[Zn].[Sn] WRYPDLONHOXTBL-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- OPXJEFFTWKGCMW-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Ni].[Cu] OPXJEFFTWKGCMW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 6
- 229910000990 Ni alloy Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- IQXLITYPMOJFDQ-UHFFFAOYSA-N [Ni].[Cu].[Ni].[Zn] Chemical compound [Ni].[Cu].[Ni].[Zn] IQXLITYPMOJFDQ-UHFFFAOYSA-N 0.000 description 2
- SCLVRDWIOFTWNM-UHFFFAOYSA-N [Zn].[Ni].[Zn] Chemical compound [Zn].[Ni].[Zn] SCLVRDWIOFTWNM-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002368 cardiac glycoside Substances 0.000 description 1
- 229940097217 cardiac glycoside Drugs 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- LPMXVESGRSUGHW-HBYQJFLCSA-N ouabain Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@@H]1C[C@@]2(O)CC[C@H]3[C@@]4(O)CC[C@H](C=5COC(=O)C=5)[C@@]4(C)C[C@@H](O)[C@@H]3[C@@]2(CO)[C@H](O)C1 LPMXVESGRSUGHW-HBYQJFLCSA-N 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229930002534 steroid glycoside Natural products 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- 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
Abstract
The invention discloses a composite coating of a neodymium iron boron magnet and a preparation method thereof. The composite coating at least comprises two coatings: the plating layer comprises a first plating layer and a second plating layer, wherein the first plating layer is a plating layer containing at least one metal of nickel, copper and zinc, and the second plating layer is a tin-nickel-zinc ternary alloy plating layer. The composite coating for the neodymium iron boron magnet provided by the invention can further improve the corrosion resistance and the humidity resistance of a neodymium iron boron magnet product, the binding force between the coating and the surface of the magnet and between the coating and the coating is excellent, and the coating hardly influences the magnetic property of the magnet. The whole preparation process has the advantages of simple operation, convenient maintenance, strong environmental protection, high production efficiency and the like. The composite plating layer has good corrosion resistance (SST can reach more than 300 h), and the damp-heat resistance can reach more than 3000 h.
Description
Technical Field
The invention belongs to the technical field of neodymium iron boron magnet corrosion prevention, and particularly relates to a neodymium iron boron magnet composite coating and a preparation method thereof.
Background
Based on the advantages of the neodymium iron boron, the neodymium iron boron is widely applied to industries such as information technology, automobiles, motors, wind power, hybrid electric vehicles and the like. The neodymium-iron-boron magnet is a product of powder metallurgy, because the electrode potentials of various neodymium-rich phases, boron-rich phases and main phases of the neodymium-iron-boron magnet are different, electrochemical corrosion is easily caused, neodymium is one of elements with high chemical activity, corrosion is easily caused, and poor corrosion resistance of the outer surface is one of the key defects of the neodymium-iron-boron magnet. Therefore, before application, the neodymium-iron-boron magnet must be surface-treated to prevent corrosion.
The surface treatment method of the general neodymium iron boron magnet comprises phosphorization, electrodeposition, electrophoresis, spraying, physical vapor deposition and the like. Conventional electrodeposition coatings include nickel, nickel-copper-nickel, zinc-nickel alloy-copper-nickel, and the like.
The nickel plating layer has high porosity, so the corrosion resistance can be improved only by increasing the thickness of the plating layer, but the thickness of the nickel plating layer is too thick, which not only influences the magnetic performance, but also highlights corner effect, and seriously influences the product assembly.
Double-layer nickel plating, generally semi-bright nickel is a columnar structure, bright nickel is a layered structure, so the corrosion resistance of the double-layer nickel is better than that of single-layer nickel, but the problem of low corrosion resistance caused by high porosity of the nickel cannot be avoided.
The corrosion resistance of the product is improved due to the addition of copper with better compactness in the nickel-copper-nickel coating structure, but the improvement is limited, and the requirement of high corrosion resistance can not be met for the product with higher corrosion resistance requirement.
The zinc-nickel alloy in the zinc-nickel alloy-copper-nickel coating structure replaces semi-bright nickel in the nickel-copper-nickel coating structure, the influence on the magnetic property can be reduced, the bonding force with a substrate is far better than that of nickel and the substrate, but the zinc-nickel alloy is difficult to clean and easy to bring impurities to a copper plating solution, and the zinc is more active than the copper, so that Zn is generated in the copper plating solution2+Impurities affect the plating performance of copper, are complex to produce and maintain, and bring troubles to stable production.
In patent document CN 103326005a, a tin-nickel-zinc ternary alloy soft porous material applied to a negative electrode of a lithium ion battery and a preparation method thereof are disclosed, in which a tin-nickel-zinc ternary alloy is obtained on the surface of a soft porous conductive material, and then a relatively active metal is selectively corroded by corrosion, so as to obtain the porous material. However, the method cannot be directly applied to magnetic materials such as neodymium iron boron and the like, and iron and even neodymium in the neodymium iron boron magnet can be corroded in the process of selectively corroding the active metal, so that the structure of the magnet is damaged, and the corrosion resistance of the magnet is influenced. And the porous structure obtained by corroding the coating is extremely favorable for the storage capacity and the service life of the lithium ion battery, but for the neodymium iron boron magnet, the corrosion resistance of the magnet can be influenced, the integrity of the coating can be damaged, and the service life of the magnet can be influenced.
Patent document CN 102276245a discloses a nickel-zinc soft magnetic ferrite material and a preparation method thereof, wherein the main formula comprises iron oxide Fe in molar parts2O345-50 mol% of zinc oxide (ZnO), 26-32 mol% of zinc oxide (ZnO), 17-21 mol% of nickel protoxide (NiO) and 4-8 mol% of copper oxide (CuO); meanwhile, in the main formula, 0.2-0.5 wt% of auxiliary material A and 0.1-0.2 wt% of auxiliary material B are added according to the weight percentage, wherein the auxiliary material A is Bi2O3、SiO2、Ta2O5One or two of the auxiliary materials B is TiO2、V2O5、Nb2O5One or more of them. The obtained nickel-zinc soft magnetic ferrite material has the characteristics of high frequency, high magnetic conductivity, high Bs and high TC.
Patent document CN107502929A discloses electroplating tin-nickel-zinc ternary alloy on the surface of stainless steel material, the obtained coating has bright and flat surface, good binding property with stainless steel matrix, small internal stress of coating, and good binding property with its outer continuous film layer, cardiac glycoside and aluminum isopropoxide synergistic effect can improve the anti-tarnishing ability of the film layer, polysilazane modified resin and filler etc. combined effect, so that the scratch resistance of the surface is significantly improved, and the application range of stainless steel shelf can be enlarged.
Disclosure of Invention
The invention provides a composite coating of a neodymium iron boron magnet, which at least comprises a tin-nickel-zinc ternary alloy coating.
According to the embodiment of the invention, the composite coating is a tin-nickel-zinc ternary alloy coating. For example, the number of layers of the tin-nickel-zinc ternary alloy coating may be one, two or more. Illustratively, the composite coating is a tin-nickel-zinc ternary alloy coating with one layer. For example, the thickness of the single layer tin-nickel-zinc ternary alloy coating is 2-25 μm, such as 4-20 μm, illustratively 2 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 45 μm, 20 μm.
According to an embodiment of the invention, the composite coating comprises at least two coatings: the plating layer comprises a first plating layer and a second plating layer, wherein the first plating layer is a plating layer containing at least one metal of nickel, copper and zinc, and the second plating layer is a tin-nickel-zinc ternary alloy plating layer.
According to an embodiment of the invention, the first coating layer is at least one layer of an alloy coating of at least two metals of nickel, copper and zinc, or at least one layer of a single metal coating of nickel, copper or zinc, preferably at least one layer of a single metal coating of nickel, copper or zinc, or at least one layer of an alloy coating of nickel and copper; further preferred is at least one layer of a single metal plating of nickel or at least one layer of an alloy plating of nickel and copper.
According to an embodiment of the invention, the thickness of the first plating layer is 2-20 μm, preferably 4-10 μm, exemplarily 2 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 45 μm, 20 μm. If the first plating layer is too thin, the corrosion resistance of the magnet is not good, and if the first plating layer is too thick, the corner effect is large.
According to an embodiment of the invention, the thickness of the second plating layer is 2-25 μm, preferably 4-10 μm, exemplarily 2 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm.
According to the embodiment of the invention, in the tin-nickel-zinc ternary alloy, the zinc content is 5-70 wt%, the nickel content is 10-35 wt% and the tin content is 15-70 wt% in percentage by mass. For example, the zinc content is 30 to 65 wt%, the nickel content is 12 to 30 wt%, and the tin content is 20 to 50 wt% in mass%. Illustratively, in the tin-nickel-zinc ternary alloy, the zinc content is 55.97 wt%, the nickel content is 16.38 wt%, and the tin content is 27.65 wt% in percentage by mass.
According to an exemplary aspect of the invention, the composite coating comprises two coatings: the first plating layer is a nickel layer with the thickness of 10 mu m, and the second plating layer is a tin-nickel-zinc ternary alloy plating layer with the thickness of 10 mu m;
or the first plating layer is a nickel layer with the thickness of 4 mu m, and the second plating layer is a tin-nickel-zinc ternary alloy plating layer with the thickness of 4 mu m;
or the first plating layer is a nickel layer with the thickness of 2 mu m, and the second plating layer is a tin-nickel-zinc ternary alloy plating layer with the thickness of 2 mu m;
or the first plating layer is a nickel layer with the thickness of 20 mu m, and the second plating layer is a tin-nickel-zinc ternary alloy plating layer with the thickness of 25 mu m;
or the first plating layer contains a nickel layer with the thickness of 5 mu m and a copper layer with the thickness of 5 mu m, and the second plating layer is a tin-nickel-zinc ternary alloy plating layer with the thickness of 10 mu m.
According to an exemplary embodiment of the present invention, the composite coating is a tin-nickel-zinc ternary alloy coating with a thickness of 20 μm.
The invention also provides a neodymium iron boron magnet containing the composite coating. Preferably, the first plating layer is in contact with the neodymium iron boron magnet, and the second plating layer is in contact with the first plating layer.
The invention also provides a preparation method of the composite coating of the neodymium iron boron magnet, which comprises the following steps: preparing a first coating on the surface of the neodymium iron boron magnet, and preparing a second coating on the surface of the first coating;
the first and second plating layers have the meaning as described above.
According to the embodiment of the invention, the surface of the neodymium iron boron magnet is also subjected to pretreatment before the first plating layer is prepared on the surface of the neodymium iron boron magnet. For example, the pretreatment includes degreasing, derusting and/or activating the surface of the iron boron magnet, and after each process of degreasing, derusting and activating is completed, the neodymium iron boron magnet needs to be washed by water.
According to an embodiment of the present invention, the degreasing treatment may be performed on the surface of the ferroboron magnet using a degreasing liquid. For example, the degreasing fluid is non-foaming and non-phosphorus normal-temperature degreasing fluid. For another example, the time for the degreasing treatment is 60-200s, and preferably 100-150 s.
According to the embodiment of the invention, the rust removal can be performed by treating the surface of the degreased ferroboron magnet by using dilute nitric acid. For example, the dilute nitric acid has a concentration of 1 to 10% by volume, preferably 1 to 6% by volume. For example, the time of the rust removing treatment is 10 to 300s, preferably 30 to 200 s.
According to an embodiment of the present invention, the first and/or second coating layer may be prepared by methods known in the art, such as electrodeposition, electroless plating or PVD (physical vapor deposition) and the like, preferably electrodeposition.
Preferably, Dk (cathode current density) is in the range of 0.5-1.5A/dm for the electrodeposition preparation of the first coating layer2。
According to an embodiment of the present invention, the plating solution of the first plating layer is a plating solution containing at least one metal element of nickel, copper, and zinc, and preferably a nickel plating solution and a copper plating solution.
According to the embodiment of the invention, the plating solution of the first plating layer contains main salt, an activating agent and at least one of a conductive agent, a buffering agent, a cylinder opening agent, a leveling agent and a wetting agent which optionally contains or does not contain the main salt and the activating agent.
Wherein the main salt can be selected from at least one of sulfates of nickel, copper and zinc or hydrated sulfates thereof, such as NiSO4·6H2O。
Preferably, the content of the main salt in the plating solution of the first plating layer is 180-400g/L, such as 320g/L, 350g/L, 380g/L and 400 g/L.
Wherein the activator may be selected from chlorides, such as at least one of the hydrochlorides of sodium, potassium, nickel, copper and zinc or their hydrated hydrochlorides, for example NiCl2·6H2And O. Preferably, the activator is contained in the plating solution of the first plating layer in an amount of 0.1 to 80g/L, for example, 40 to 70g/L, and illustratively 50g/L and 60 g/L.
Wherein the conductive agent may be selected from at least one of sulfuric acid, sulfate, and hydrated sulfate, such as NaSO4. For example, the concentration of the conductive agent in the plating solution of the first plating layer is 15 to 45 g/L.
Wherein the buffer may be selected from H3BO3. Preferably, in the plating solution of the first plating layer, the content of the buffer is 30-60g/L,for example, 40-50g/L, with 45g/L being exemplary.
Wherein, the cylinder opener can be selected from one, two or more of sulfamide, sulfimide, formaldehyde, polysulfide organic sulfonate and the like. Preferably, the content of the cylinder opener in the plating solution of the first plating layer is 2-9ml/L, such as 3ml/L, 4ml/L, 5ml/L, 6ml/L, 7ml/L, and 8 ml/L.
Wherein, the filling agent can be one or two selected from sodium perborate, 1, 4-butynediol, ethylene thiourea and the like. Preferably, the content of the leveling agent in the plating solution of the first plating layer is 0.1-1.5ml/L, for example, 0.5-1.0 ml/L.
Wherein, the wetting agent may be selected from one, two or more of sodium dodecylbenzene sulfonate, sodium dodecylsulfate, OP emulsifier, and the like. Preferably, the content of the wetting agent in the plating solution of the first plating layer is 0.5-5ml/L, such as 1-4ml/L, and is exemplarily 2ml/L and 3 ml/L.
Preferably, the plating solution of the first plating layer comprises the following components: 400g/L of main salt 300, 30-80g/L of activating agent, 30-60g/L of buffering agent, 2-9ml/L of cylinder opener agent, 0.1-1.5ml/L of filling agent and 0.5-5ml/L of wetting agent.
According to an embodiment of the invention, the pH of the bath of the first coating is 3.5-5.0, such as 3.5, 4.0, 4.5, 5.0.
Illustratively, the plating solution includes the following components: main salt NiSO4·6H2O300-2·6H2O30-80 g/L, buffer H3BO330-60g/L, 2-9ml/L of a jar opener, 0.1-1.5ml/L of a flatting agent and 0.5-5ml/L of a wetting agent. Preferably, the pH value of the plating solution is 3.5-5.0.
According to an embodiment of the present invention, interlayer activation and water washing are required before the second plating layer is prepared on top of the first plating layer.
According to an embodiment of the present invention, the activation in the pretreatment and the interlayer activation may be performed using an activation solution. Preferably, the activating solution contains 1-5% of acid by mass concentration, 0.5-1.5g/L of corrosion inhibitor and 0.5-1.5g/L of surfactant; preferably, the acid is citric acid, the corrosion inhibitor is thiourea, and the surfactant is sodium dodecyl benzene sulfonate. Illustratively, the activating solution contains 3.5% by mass of citric acid, 1g/L of thiourea and 1g/L of sodium dodecyl benzene sulfonate.
Preferably, the time of the activation treatment in the pretreatment and the time of the interlayer activation treatment are the same or different, for example, 5 to 15 seconds each.
According to the embodiment of the invention, the tin-nickel-zinc ternary alloy plating solution used for the second plating layer comprises the following components: the conductive tin sulfate comprises tin sulfate or sulfate hydrate thereof, nickel sulfate or sulfate hydrate thereof, zinc sulfate or sulfate hydrate thereof, a complexing agent, a conductive salt and a wetting agent.
Wherein the sulfate of tin may be SnSO4. Preferably, in the tin-nickel-zinc ternary alloy plating solution, the content of tin sulfate or sulfate hydrate thereof is 8-12g/L, such as 8g/L, 9g/L, 10g/L, 11g/L and 12 g/L.
Wherein the sulfate hydrate of nickel may be NiSO4·6H2And O. Preferably, in the tin-nickel-zinc ternary alloy plating solution, the content of the sulfate of nickel or the sulfate hydrate thereof is 10-20g/L, such as 10g/L, 12g/L, 14g/L, 15g/L, 18g/L and 20 g/L.
Wherein the sulfate hydrate of zinc may be ZnSO4·7H2And O. Preferably, in the tin-nickel-zinc ternary alloy plating solution, the content of the sulfate of nickel or the sulfate hydrate thereof is 40-80g/L, such as 40g/L, 50g/L, 60g/L, 70g/L and 80 g/L.
Wherein the complexing agent may be selected from C6H5Na3O7·2H2O and C4H6O6One or two of (tartaric acid). Preferably, the content of the complexing agent in the tin-nickel-zinc ternary alloy plating solution is 90-150g/L, preferably 100-140g/L, and exemplarily 100g/L, 110g/L, 120g/L, 125g/L, 130g/L and 140 g/L.
Wherein the conductive salt can be selected from KCl and/or Na2SO4. Preferably, in the tin-nickel-zinc ternary alloy plating solution, conductive saltThe content of (b) is 5 to 10g/L, for example, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10 g/L.
Wherein the wetting agent is selected from one, two or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and OP emulsifier. Preferably, the content of the wetting agent in the tin-nickel-zinc ternary alloy plating solution is 0.5-2g/L, such as 1g/L, 1.5g/L and 2 g/L.
According to an embodiment of the invention, the pH of the tin-nickel-zinc ternary alloy plating solution is 6.5 to 7.5, for example 6.5, 6.6, 6.8, 7.0, 7.2, 7.5.
Preferably, the tin-nickel-zinc ternary alloy plating solution contains the following components: SnSO4 8-12g/L，NiSO4·6H2O 10-20g/L，ZnSO4·7H240-80g/L of O, 90-150g/L of complexing agent, 5-10g/L of conductive salt and 0.5-2g/L of wetting agent.
According to an embodiment of the invention, the Dk ranges from 0.4 to 2.0A/dm when the second coating is prepared by electrodeposition2。
According to an embodiment of the invention, the water wash is at least one rinse or ultrasonic water wash.
According to an embodiment of the invention, the preparation method further comprises: and after the second coating is prepared, washing and drying the neodymium iron boron magnet.
The invention also provides a preparation method of the neodymium iron boron magnet containing the composite coating, which comprises the preparation method of the composite coating.
The invention has the beneficial effects that:
the composite coating for the neodymium iron boron magnet provided by the invention can further improve the corrosion resistance and the humidity resistance of a neodymium iron boron magnet product, the binding force between the coating and the surface of the magnet and between the coating and the coating is excellent, and the coating hardly influences the magnetic property of the magnet. The whole preparation process has the advantages of simple operation, convenient maintenance, strong environmental protection, high production efficiency and the like.
The obtained composite plating layer has good corrosion resistance, the SST can reach more than 300h, and the damp-heat resistance can reach more than 3000 h.
Drawings
Fig. 1 is a surface electron microscope photograph of the nickel-tin-nickel-zinc composite plating layer prepared in example 1.
FIG. 2 is the surface energy spectrum of the ternary alloy of Sn-Ni-Zn in the composite coating of example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The following examples and comparative examples all use a 20mm × 10mm × 4mm square neodymium iron boron product, the electrodeposition is performed in a barrel plating manner, and the pretreatment process of the neodymium iron boron product before electrodeposition is as follows:
step one, degreasing: degreasing the neodymium iron boron product by adopting a non-foaming and non-phosphorus normal-temperature degreasing liquid for 120 s;
step two, washing twice with water;
thirdly, rust removal: carrying out rust removal treatment on the degreased product by using dilute nitric acid with the volume concentration of 5%, wherein the treatment time is 40 s;
fourthly, after rust removal, carrying out ultrasonic water washing-water washing on the product;
fifthly, activation: after the fourth step is finished, activating the derusted neodymium iron boron product by using an activating solution, wherein the activating solution consists of 3.5 wt% of citric acid, 1g/L of thiourea and 1g/L of sodium dodecyl benzene sulfonate, and the activating time is 12 s;
and sixthly, washing twice to obtain the pretreated neodymium iron boron product.
The thickness of the plating layers in the following examples and comparative examples refers to the thickness of the center point of the composite plating layer.
Wherein, the SST experimental test conditions are as follows: and at the temperature of 35 ℃, the concentration of the NaCl aqueous solution is 50g/L +/-5 g/L, the pH value is between 6.5 and 7.2, salt mist is deposited on the composite plating neodymium iron boron product to be detected in a spraying mode, and the time in the table 1 is the time when the plating layer begins to rust.
The testing condition of the damp-heat experiment is that the composite coating neodymium iron boron product is placed in a closed environment with the temperature of 85 ℃ and the humidity of 85% RH, and the corrosion condition of the coating is observed. The wet heat result time in table 1 is the time when the coating starts to rust.
Example 1
Preparing a composite coating on the surface of the pretreated neodymium iron boron product, wherein the preparation process comprises the following steps:
step one, electrodepositing nickel on the surface of the pretreated neodymium iron boron product: the nickel plating solution comprises NiSO4·6H2O 350g/L，NiCl2·6H2O 50g/L，H3BO345g/L, 5ml/L of sulfamide, 1ml/L of 1, 4-butynediol and 2ml/L of sodium dodecyl sulfate;
dk (cathode current density) is in the range of 1.0-1.2A/dm2；
Secondly, washing the neodymium iron boron product with the nickel layer plated on the surface twice after the nickel plating;
thirdly, interlayer activation: after the second step of water washing is finished, carrying out interlayer activation on the nickel-plated neodymium iron boron product, wherein the interlayer activation is the same as the activation process in the pretreatment;
step four, after the step three is finished, washing the product twice;
fifthly, electrodepositing the ternary alloy of tin, nickel and zinc: the composition of the plating solution is SnSO4 8g/L，NiSO4·6H2O 13g/L，ZnSO4·7H2O 70g/L，C6H5Na3O7·2H2O 125g/L，C4H6O626g/L, KCl 9g/L and sodium dodecyl sulfate 1 g/L;
dk (cathode current density) is in the range of 1.0-1.2A/dm2；
Sixthly, after the fifth step is finished, washing the neodymium iron boron product with the tin-nickel-zinc ternary alloy layer plated on the nickel layer twice;
seventhly, drying;
and step eight, drying to obtain the neodymium iron boron product with the nickel-tin-nickel-zinc composite coating.
Examples 1 to 1
Through the preparation process in the embodiment 1, the total thickness of the obtained nickel-tin-nickel-zinc composite plating layer is 20 μm, wherein the thickness of the nickel layer is 10 μm, and the thickness of the tin-nickel-zinc ternary alloy layer is 10 μm. Wherein the current densities of the nickel layer and the tin-nickel-zinc layer are both 1.0-1.2A/dm2The electrodeposition time of the nickel layer is 60min, and the electrodeposition time of the tin-nickel-zinc layer is 55 min.
As shown in figure 1, the surface of the nickel-tin-nickel-zinc composite coating is flat and compact.
As shown in fig. 2, in the tin-nickel-zinc ternary alloy layer, the content of Ni element was 16.38 wt%, the content of Zn element was 55.97 wt%, and the content of Sn element was 27.65 wt%.
Examples 1 to 2
Through the preparation process in the embodiment 1, the total thickness of the obtained nickel-tin-nickel-zinc composite plating layer is 8 μm, wherein the thickness of the nickel layer is 4 μm, and the thickness of the tin-nickel-zinc ternary alloy layer is 4 μm. Wherein the current densities of the nickel layer and the tin-nickel-zinc layer are both 1.0-1.2A/dm2The electrodeposition time of the nickel layer is 25min, and the electrodeposition time of the tin-nickel-zinc layer is 20 min.
Examples 1 to 3
Through the preparation process in the embodiment 1, the total thickness of the obtained nickel-tin-nickel-zinc composite plating layer is 4 μm, wherein the thickness of the nickel layer is 2 μm, and the thickness of the tin-nickel-zinc ternary alloy layer is 2 μm. Wherein the current densities of the nickel layer and the tin-nickel-zinc layer are both 1.0-1.2A/dm2The electrodeposition time of the nickel layer is 10min, and the electrodeposition time of the tin-nickel-zinc layer is 10 min.
Examples 1 to 4
Through the preparation process in the embodiment 1, the total thickness of the obtained nickel-tin-nickel-zinc composite plating layer is 45 μm, wherein the thickness of the nickel layer is 20 μm, and the thickness of the tin-nickel-zinc ternary alloy layer is 25 μm. Wherein the current densities of the nickel layer and the tin-nickel-zinc layer are both 1.0-1.2A/dm2The electrodeposition time of the nickel layer is 120min, and the electrodeposition time of the tin-nickel-zinc layer is 135 min.
Comparative example 1
The total thickness of the nickel-tin-nickel-zinc plating layer obtained by the process treatment in the embodiment 1 is 3 μm, wherein the thickness of the nickel layer is 1.5 μm, and the thickness of the tin-nickel-zinc ternary alloy is 1.5 μm. Wherein the current densities of the nickel layer and the tin-nickel-zinc layer are both 1.0-1.2A/dm2The electrodeposition time of the nickel layer is 9min, and the electrodeposition time of the tin-nickel-zinc layer is 8 min.
Example 2
Preparing a composite coating on the surface of the pretreated neodymium iron boron product, wherein the preparation process comprises the following steps:
step one, electrodepositing nickel on the surface of the pretreated neodymium iron boron product: the composition of the nickel plating solution is NiSO4·6H2O 350g/L，NiCl2·6H2O 50g/L，H3BO345g/L, 5ml/L of sulfamide, 1ml/L of 1, 4-butynediol and 2ml/L of sodium dodecyl sulfate;
dk (cathode current density) is in the range of 1.0-1.2A/dm2；
Secondly, washing the neodymium iron boron product with the nickel layer plated on the surface twice after the nickel plating;
thirdly, interlayer activation: after the second step of water washing is finished, carrying out interlayer activation on the nickel-plated neodymium iron boron product, wherein the interlayer activation is the same as the activation process in the pretreatment;
step four, after the step three is finished, washing the product twice;
fifthly, electrodepositing copper by adopting a conventional method, wherein the main salt is CuSO4·5H2O。
Dk (cathode current density) is in the range of 1.2-1.5A/dm2；
Sixthly, after the fifth step is finished, washing the neodymium iron boron product sequentially plated with the nickel layer and the copper layer twice;
seventhly, interlayer activation: after the sixth step of water washing is finished, interlayer activation is carried out on the nickel-plated neodymium iron boron product, and the activation process in the pretreatment is the same as that in the step of water washing;
eighthly, washing twice after interlayer activation;
and ninthly, electrodepositing the tin-nickel-zinc ternary alloy: the plating solution consists ofSnSO4 8g/L，NiSO4·6H2O 13g/L，ZnSO4·7H2O 70g/L，C6H5Na3O7·2H2O 125g/L，C4H6O626g/L, KCl 9g/L and sodium dodecyl sulfate 1 g/L;
dk (cathode current density) is in the range of 1.2-1.5A/dm2；
Step ten, after the step ninth, washing the neodymium iron boron product sequentially plated with the ternary alloy layers of the nickel layer, the copper layer and the tin-nickel-zinc layer twice;
step eleven, drying;
and step eleven, drying to obtain the neodymium iron boron product with the nickel-copper-tin-nickel-zinc composite coating.
The composite plated nd-fe-b products obtained in examples 1-1 to 1-4, example 2 and comparative example 1 were subjected to corrosion resistance and wet heat resistance tests, and the test results are shown in table 1.
TABLE 1
The results in table 1 show that the corner effect and the salt spray resistance and damp-heat resistance of the different coating thicknesses in examples 1-1 to 1-4 and comparative example 1 are different, and the thinner the coating is, the worse the salt spray resistance and damp-heat resistance is, and the thicker the coating is, the larger the corner effect is. The combination of properties is better than the products of examples 1-1 and 2.
The results in Table 1 show that the edge effect, the salt spray resistance and the damp-heat resistance are equivalent to each other under the same film thickness in the case of the comparison between the example 1-1 and the example 2.
Example 3
Preparing a composite coating on the surface of the pretreated neodymium iron boron product, wherein the preparation process comprises the following steps:
step one, electrodepositing a tin-nickel-zinc ternary alloy on the surface of the pretreated neodymium iron boron product: the composition of the plating solution is SnSO4 8g/L，NiSO4·6H2O 13g/L，ZnSO4·7H2O 70g/L，C6H5Na3O7·2H2O 125g/L，C4H6O626g/L, KCl 9g/L and sodium dodecyl sulfate 1 g/L;
dk (cathode current density) is in the range of 1.0-1.2A/dm2The electrodeposition time was 110 min.
Step two, after the step five is finished, washing the product with the tin-nickel-zinc ternary alloy layer plated on the neodymium iron boron twice;
thirdly, drying;
and fourthly, drying to obtain the neodymium iron boron product with the tin-nickel-zinc composite coating, wherein the thickness of the coating is 20 microns.
Comparative example 2
Plating a nickel layer on the surface of the pretreated neodymium iron boron product, wherein the treatment process is as follows:
step one, electrodepositing nickel on the surface of the pretreated neodymium iron boron product: the nickel plating solution consists of NiSO4·6H2O 350g/L，NiCl2·6H2O 50g/L，H3BO345g/L, 5ml/L of sulfamide, 1ml/L of 1, 4-butynediol and 2ml/L of sodium dodecyl sulfate;
dk (cathode current density) is in the range of 1.0-1.2A/dm2；
Secondly, washing the neodymium iron boron product with the nickel layer plated on the surface twice after the nickel plating;
thirdly, drying;
and fourthly, drying to obtain the neodymium iron boron product with the surface plated with the nickel layer, wherein the thickness of the plating layer is 20 microns.
Comparative example 3
Plating a nickel-nickel layer on the surface of the pretreated neodymium iron boron product, and the process is as follows:
step one, electrodepositing nickel on the surface of the pretreated neodymium iron boron product: the nickel plating solution consists of NiSO4·6H2O 350g/L，NiCl2·6H2O 50g/L，H3BO345g/L, 5ml/L of sulfamide, 1ml/L of 1, 4-butynediol and 2ml/L of sodium dodecyl sulfate;
dk (cathode current density) is in the range of 1.0-1.2A/dm2；
Secondly, washing the neodymium iron boron product with the nickel layer plated on the surface twice after the nickel plating;
thirdly, carrying out secondary nickel electrodeposition, and carrying out the same operation as the first step;
fourthly, after the secondary nickel plating is finished, washing the neodymium iron boron product with the nickel-nickel layer plated on the surface twice;
fifthly, drying;
and sixthly, drying to obtain the neodymium iron boron product with the surface plated with the nickel-nickel layer, wherein the total thickness of the plating layer is 20 mu m.
Comparative example 4
Plating a nickel-copper-nickel layer on the surface of the pretreated neodymium iron boron product, and the process is as follows:
step one, electrodepositing nickel on the surface of the pretreated neodymium iron boron product: the nickel plating solution consists of NiSO4·6H2O 350g/L，NiCl2·6H2O 50g/L，H3BO345g/L, 5ml/L of sulfamide, 1ml/L of 1, 4-butynediol and 2ml/L of sodium dodecyl sulfate;
dk (cathode current density) is in the range of 1.0-1.2A/dm2；
Secondly, washing the neodymium iron boron product with the nickel layer plated on the surface twice after the nickel plating;
thirdly, after the second step of water washing is finished, carrying out interlayer activation on the nickel-plated neodymium iron boron product, wherein the interlayer activation is the same as the activation process in the pretreatment;
step four, after the step three is finished, washing the product twice;
fifthly, electrodepositing copper: the composition of the copper plating solution was the same as in example 2;
sixthly, washing the product plated with the nickel-copper layer twice;
seventhly, performing interlayer activation on the product plated with the nickel-copper layer after washing, wherein the activation treatment is the same as the third step;
eighthly, washing the product twice after the seventh step;
and step nine, electrodepositing nickel again: the operation is the same as the first step;
step ten, after the nickel plating is finished, washing the neodymium iron boron product with the surface plated with nickel-copper-nickel twice;
step eleven, drying;
and step eleven, drying to obtain the neodymium iron boron product with the surface plated with nickel-copper-nickel, wherein the total thickness of the plating layer is 20 microns.
Comparative example 5
Plating a zinc-nickel-copper-nickel layer on the surface of the pretreated neodymium iron boron product, wherein the process is as follows:
firstly, performing conventional electrodeposition of zinc on the surface of the pretreated neodymium iron boron product, wherein the main salt is ZnSO4·7H2O。
Dk (cathode current density) is in the range of 1.2-1.5A/dm2；
Secondly, washing the neodymium iron boron product with the zinc layer plated on the surface twice after the zinc plating is finished;
thirdly, emitting light;
fourthly, washing the product twice after finishing the light extraction;
fifthly, electrodepositing zinc-nickel alloy on the neodymium iron boron product with the surface plated with the zinc layer, wherein the zinc-nickel alloy plating solution is alkaline and consists of zinc2+Nickel, nickel2+Sodium hydroxide, complexing agent and additive;
dk (cathode current density) is in the range of 3.5-4.0A/dm2；
Sixthly, washing the neodymium iron boron product with zinc-zinc nickel plated on the surface twice after the zinc-nickel plating is finished;
seventhly, interlayer activation: after the sixth step of washing, carrying out interlayer activation on the zinc-nickel-neodymium-iron-boron product, wherein the interlayer activation is the same as the activation process in the pretreatment;
eighthly, washing the product twice after the seventh step;
step nine, electrodepositing copper on the neodymium iron boron product with the surface plated with the zinc-zinc nickel layer, wherein the operation of copper plating is the same as the fifth step in the embodiment 2;
step ten, after the copper plating is finished, washing the zinc-nickel-copper plated neodymium iron boron product twice;
step ten, interlayer activation: after the tenth step of water washing is finished, carrying out interlayer activation on the zinc-nickel-copper plated neodymium iron boron product, wherein the interlayer activation is the same as the activation process in the pretreatment;
a twelfth step of washing the product twice after the seventh step;
step ten, electrodepositing nickel on the zinc-nickel-copper plated neodymium iron boron product, wherein the operation of nickel plating is the same as the first step in the embodiment 1;
fourteenth, washing the product twice after the thirteenth step;
fifteenth, drying;
sixthly, drying to obtain the neodymium iron boron product with the surface plated with the zinc-nickel-copper-nickel layer, wherein the total thickness of the plating layer is 20 microns.
TABLE 2
Wherein the thickness of the plating layer is the total thickness; the binding force is the shearing force tested by a mechanical testing machine, and the binding force between the coating and the substrate and between the coating layers meets the requirements.
The results in Table 2 show that the corrosion resistance of example 1-1 is better than that of example 3, the salt spray resistance and the wet heat resistance of the plating layers of examples 1-1 and 3 are obviously better than those of each comparative example, and the influence on the magnetic flux is smaller than that of the comparative example.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (46)
1. The neodymium iron boron magnet containing the composite coating is characterized in that the composite coating at least comprises a tin-nickel-zinc ternary alloy coating;
in the tin-nickel-zinc ternary alloy, the zinc content is 5-70 wt%, the nickel content is 10-35 wt%, and the tin content is 15-70 wt%;
the thickness of the tin-nickel-zinc ternary alloy coating is 10-25 mu m;
when the composite coating is a tin-nickel-zinc ternary alloy coating with one layer, the tin-nickel-zinc ternary alloy coating is prepared by electrodeposition;
when the composite coating comprises at least two coatings: when the alloy is a first plating layer and a second plating layer, the first plating layer is a plating layer containing at least one metal of nickel, copper and zinc, and the second plating layer is the ternary alloy plating of tin, nickel and zinc; the first plating layer is in contact with the neodymium iron boron magnet, and the second plating layer is in contact with the first plating layer; the second plating layer is prepared by electrodeposition.
2. The ndfeb magnet according to claim 1, wherein the first plating layer is an alloy plating of at least two of nickel, copper and zinc, or a single metal plating of at least one of nickel, copper or zinc.
3. The ndfeb magnet according to claim 1 or 2, wherein the first plating layer has a thickness of 2-20 μ ι η.
4. The method for preparing a neodymium-iron-boron magnet containing a composite coating according to any one of claims 1 to 3, characterized by comprising the following steps: preparing a first plating layer on the surface of the neodymium iron boron magnet, and preparing a second plating layer on the surface of the first plating layer.
5. The preparation method of claim 4, wherein the surface of the NdFeB magnet is pretreated before the first plating layer is prepared on the surface of the NdFeB magnet.
6. A method of producing as claimed in claim 5, wherein the pre-treatment includes degreasing, derusting and/or activating the surface of a ferroboron magnet.
7. The method according to claim 4 or 5, wherein the first plating layer is produced by electrodeposition, electroless plating, or a PVD method.
8. The method according to claim 7, wherein the Dk is in the range of 0.5 to 1.5A/dm when the first plating layer is formed by electrodeposition2。
9. The method of claim 7, wherein the Dk ranges from 0.4 to 2.0A/dm when the second plating layer is electrodeposited2。
10. The production method according to claim 4, wherein the plating solution of the first plating layer is a plating solution containing at least one metal element of nickel, copper, and zinc.
11. The production method according to claim 10, wherein the plating solution of the first plating layer is a nickel plating solution or a nickel-plated copper alloy solution.
12. The method according to claim 10, wherein the plating solution of the first plating layer contains a main salt, an activator, and optionally at least one of a conductive agent, a buffer, a leveling agent, and a wetting agent.
13. The method of claim 12, wherein the main salt is selected from at least one of sulfates of nickel, copper, and zinc or hydrated sulfates thereof.
14. The preparation method according to claim 12 or 13, wherein the plating solution of the first plating layer contains 180-400g/L of the main salt.
15. The method of claim 12, wherein the activator is selected from the group consisting of chlorides: at least one of the hydrochlorides of sodium, potassium, nickel, copper and zinc or their hydrated hydrochlorides.
16. The production method according to claim 12 or 15, wherein the activator is contained in an amount of 0.1 to 80g/L in the plating solution of the first plating layer.
17. The production method according to claim 12, wherein the conductive agent is at least one selected from sulfuric acid, hydrochloride, and hydrochloride hydrate.
18. The production method according to claim 12 or 17, wherein a concentration of the conductive agent in the plating solution of the first plating layer is 15 to 45 g/L.
19. The method of claim 12, wherein the buffering agent is selected from the group consisting of H3BO3。
20. The production method according to claim 12 or 19, wherein the content of the buffer in the plating solution of the first plating layer is 30 to 60 g/L.
21. The method according to claim 12, wherein the biscuit release agent is one or more selected from the group consisting of sulfonamides, sulfonimides, formaldehydes, and polysulfide organic sulfonates.
22. The production method according to claim 12 or 21, wherein the content of the cylinder opener in the plating solution of the first plating layer is 2 to 9 ml/L.
23. The method of claim 12, wherein the leveling agent is selected from one or two of sodium perborate, 1, 4-butynediol, and ethylene thiourea.
24. The production method according to claim 12 or 23, wherein the content of the leveling agent in the plating solution of the first plating layer is 0.1 to 1.5 ml/L.
25. The method according to claim 12, wherein the wetting agent is one or more selected from the group consisting of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate and OP emulsifier.
26. The production method according to claim 12 or 25, wherein the content of the wetting agent in the plating solution of the first plating layer is 0.5 to 5 ml/L.
27. The production method according to claim 10, wherein the plating solution of the first plating layer has a pH of 3.5 to 5.0.
28. The production method according to claim 6, wherein interlayer activation and water washing are required before the second plating layer is produced on the first plating layer.
29. The production method according to claim 28, wherein the activation in the pretreatment and the interlayer activation are performed using an activation solution.
30. The method according to claim 29, wherein the activating solution contains 1-5% by mass of an acid, 0.5-1.5g/L of a corrosion inhibitor, and 0.5-1.5g/L of a surfactant.
31. The method of claim 30, wherein the acid is citric acid, the corrosion inhibitor is thiourea, and the surfactant is sodium dodecylbenzenesulfonate.
32. The preparation method according to claim 4, wherein the ternary alloy plating solution of tin, nickel and zinc used for the second plating layer comprises the following components: the conductive tin sulfate comprises tin sulfate or sulfate hydrate thereof, nickel sulfate or sulfate hydrate thereof, zinc sulfate or sulfate hydrate thereof, a complexing agent, a conductive salt and a wetting agent.
33. The method of claim 32, wherein the tin sulfate is SnSO4。
34. The production method according to claim 32, wherein the content of sulfate of tin or sulfate hydrate thereof in the tin-nickel-zinc ternary alloy plating solution is 8 to 12 g/L.
35. The method of claim 32, wherein the sulfate hydrate of nickel is NiSO4·6H2O。
36. The preparation method according to claim 32, wherein the content of the sulfate of nickel or the sulfate hydrate thereof in the tin-nickel-zinc ternary alloy plating solution is 10 to 20 g/L.
37. A process according to claim 32, wherein the sulfate hydrate of zinc is ZnSO4·7H2O。
38. The preparation method according to claim 32, wherein the content of zinc sulfate or sulfate hydrate thereof in the tin-nickel-zinc ternary alloy plating solution is 40 to 80 g/L.
39. The method of claim 32, wherein the complexing agent is selected from the group consisting of C6H5Na3O7·2H2O and C4H6O6One or two of them.
40. The preparation method according to claim 32 or 39, wherein the content of the complexing agent in the ternary Sn-Ni-Zn alloy plating solution is 90-150 g/L.
41. The method of claim 32, wherein the conductive salt is selected from KCl and/or Na2SO4。
42. The preparation method according to claim 32 or 41, wherein the content of the conductive salt in the ternary tin-nickel-zinc alloy plating solution is 5-10 g/L.
43. The method according to claim 32, wherein the wetting agent is one or more selected from the group consisting of sodium dodecylbenzenesulfonate, sodium dodecylsulfate and OP emulsifier.
44. The method according to claim 32 or 43, wherein the content of the wetting agent in the ternary tin-nickel-zinc alloy plating solution is 0.5-2 g/L.
45. The method of claim 32, wherein the tin-nickel-zinc ternary alloy plating solution has a pH of 6.5 to 7.5.
46. The method of manufacturing according to claim 4, further comprising: and after the second coating is prepared, washing and drying the neodymium iron boron magnet.
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