CN117248212A - 一种钕铁硼双镀层表面防护方法 - Google Patents
一种钕铁硼双镀层表面防护方法 Download PDFInfo
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 75
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000007747 plating Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000009713 electroplating Methods 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 238000005554 pickling Methods 0.000 claims abstract description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 11
- 239000002344 surface layer Substances 0.000 claims abstract description 8
- 230000007547 defect Effects 0.000 claims abstract description 7
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005498 polishing Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000005238 degreasing Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002161 passivation Methods 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- -1 neodymium-iron-boron rare earth Chemical class 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
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Abstract
本发明公开了一种钕铁硼双镀层表面防护方法,将钕铁硼部件进行表面物理缺陷机械处理、表面除油处理之后,在酸洗液中进行超声处理;然后通过物理法气相沉积或磁控溅射法在钕铁硼部件表面沉积铜层,其中部分铜原子扩散进入钕铁硼表层并分布在晶界中;在钕铁硼部件表面沉积铜层上电镀镍层。本发明一方面通过沉积铜层优化边界显微结构,另一方面优先选用双镀层代替三层镀层结构,减少镀层产生的磁屏蔽;实现了既不影响表面结合力,同时将很大程度上降低其磁性能的损耗甚至不产生磁性能的损耗的高耐蚀性的新型表面防护。
Description
技术领域
本发明属于钕铁硼表面防护技术领域,涉及一种钕铁硼双镀层表面防护方法。
背景技术
钕铁硼稀土永磁材料广泛应用于各类电机中。但是,钕铁硼的多相结构以及各相之间的化学特性差异特点,使得钕铁硼稀土永磁材料表现出固有的耐蚀性不足。如果发生腐蚀后,磁体内部主相晶粒之间的结合介质消失,将造成主相晶粒的脱落,严重时还会造成磁体的粉化失效。因此,钕铁硼稀土永磁材料腐蚀防护技术的发展很大程度上制约其应用。
目前提高钕铁硼材料耐蚀性一方面是从提高材料自身耐蚀性,另一反面对材料表面进行涂层防护;而其表面涂层防护得益于其易于操作、成本可控、工艺相对简单以及批量生产不受限制,成为研究的热点。
当前烧结钕铁硼表面的涂层防护主要是通过电镀、化学镀、有机涂覆以及物理气相沉积等方法实现。其中电镀Ni基合金由于耐高温、抗氧化、耐蚀和装饰性能优良,抗压、抗弯、抗冲击力等力学性能好而被广泛应用。但是电镀过程容易产生杂质元素的带入、施镀过程不断有H2产生;并且镍镀层具有铁磁性,对磁体会产生磁屏蔽作用,已有数据显示,上述因素将会带来5%以上磁性能的降低。
发明内容
本发明解决的技术问题在于提供一种钕铁硼双镀层表面防护方法,减少镍镀层产生的磁屏蔽,降低其磁性能的损耗甚至不产生磁性能的损耗。
本发明是通过以下技术方案来实现:
一种钕铁硼双镀层表面防护方法,其特征在于,包括以下操作:
1)将钕铁硼部件进行表面物理缺陷机械处理、表面除油处理之后,在酸洗液中进行超声处理;
所述的酸洗液中至少包括柠檬酸、氨水和尿素;酸洗后钕铁硼部件表面区域的晶界相裸露,并形成钝化膜;
2)通过物理法气相沉积或磁控溅射法在钕铁硼部件表面沉积铜层,铜层厚度为4~6μm;其中部分铜原子扩散进入钕铁硼表层并分布在晶界中;
3)在钕铁硼部件的沉积铜层上电镀镍层,镍层厚度3.5~15.5μm。
所述表面物理缺陷机械处理是进行研磨抛光处理,研磨后钕铁硼部件棱边半径R小于0.5mm;
所述表面除油处理是将钕铁硼部件置入无磷去除油污溶液中超声清洗180~300s。
所述研磨抛光是利用振动光饰机进行研磨抛光,在振动光饰机中加入棕刚玉磨石和硅酸钠添加液,然后放入钕铁硼部件抛光研磨;
所述硅酸钠添加液,是按质量百分比在硅酸钠中添加0.1~0.4%的三乙醇胺、0.2~0.8%的硼酸和0.01~0.05%的乙二胺四乙酸。
以质量分数计,取15%~25%的氢氧化钠、30%~35%的碳酸钠、4%~5%的五水偏硅酸钠、3%~15%的十二烷基硫酸钠、20%~25%的烷基取代二元羧酸盐、2%~3%的异构脂肪醇烷氧基化物,以及0.5%~1.0%的层状结晶二硅酸钠;用水充分溶解制成无磷去除油污溶液;
超声清洗时,超声波功率1500~2000W、超声频率35~40KHz。
以质量分数计,所述的酸洗液包括6%~10%的柠檬酸、3%~5%的硝酸钠、0.2%~0.4%的氨水和1.5%~3.5%的尿素;
清洗方式超声辅助清洗,清洗温度控制在20~30℃之间,清洗时间控制在60~180s。
所述沉积铜层的磁控溅射操作包括:
1)安装铜靶材后开机启动空气压缩机、水冷机、稳压电源,打开氩气并调整好压力;
2)预热,抽真空;真空度达到5*10~3Pa开启加热器,加热至100~200℃后,真空度达到5*10~4Pa开启电离真空计;
3)通氩气,氩气纯度99.995%,氩气流量50~200sccm;调节真空度至1Pa~3Pa,执行铜层沉积;
4)沉积完成后,取出试样。
所述电镀镍层包括以下操作:
1)预沉积层表面活化处理:
将钕铁硼部件浸入体积浓度3%~10%的稀硫酸中,在室温下搅拌30~60s;
2)电镀镍层
取出钕铁硼部件置入电镀液中作为阴极进行电镀,电镀液中包括200g/L~350g/L的硫酸镍、30g/L~55g/L的氯化镍、5g/L~20g/L的硫酸镁、5g/L~15g/L的氯化钠、35g/L~60g/L的硼酸和2g/L~5g/L的氨水,其pH为3.8~5.0;
阳极为纯度>99.9%的高纯度镍球,电镀的电流密度为0.3~0.8A/dm2、温度为45℃~55℃、电镀时间为3600s~7200s;
3)清洗
电镀完成后采用蒸馏水或去离子水多次漂洗,再经45℃~55℃热水清洗,然后20~60℃热风吹干。
与现有技术相比,本发明具有以下有益的技术效果:
本发明提供的钕铁硼双镀层表面防护方法,先通过物理法气相沉积或磁控溅射法沉积铜层优化钕铁硼边界显微结构,然后再进行表面电镀镍;一方面铜铜原子很容易扩散进入钕铁硼表层并分布在晶界中,原子不但能够促进磁体表层的致密性,在保证了沉积层和基体的结合力的同时阻止了烧结钕铁硼磁体的进一步腐蚀;另一方面铜原子主要分布在晶界中一定程度上改善了晶界相微观结构,可促进烧结钕铁硼磁体磁性能的提升;而且本发明在铜沉积层上电镀镍金属,避免了钕铁硼基体直接与镍镀液中的氯离子接触、腐蚀,避免电镀过程钕铁硼基体直接接触带入的杂质元素。
本发明提供的钕铁硼双镀层表面防护方法,通过沉积铜层-表层镀镍的双镀层,代替底层镀镍-镀铜-表层镀镍的三层电镀镀层结构,减少镍镀层产生的磁屏蔽;实现了既不影响表面结合力,同时将很大程度上降低其磁性能的损耗,甚至不产生磁性能的损耗的高耐蚀性的新型表面防护。
附图说明
图1为边界优化前的钕铁硼基体示意图;
图2为边界优化后钕铁硼基体示意图。
具体实施方式
下面结合实施例对本发明做进一步详细描述,所述是对本发明的解释而不是限定。
一种钕铁硼双镀层表面防护方法,其特征在于,包括以下操作:
1)将钕铁硼部件进行表面物理缺陷机械处理、表面除油处理之后,在酸洗液中进行超声处理;
所述的酸洗液中至少包括柠檬酸、氨水和尿素;酸洗后钕铁硼部件表面区域的晶界相裸露,并形成钝化膜;
2)通过物理法气相沉积或磁控溅射法在钕铁硼部件表面沉积铜层,铜层厚度为4~6μm;其中部分铜原子扩散进入钕铁硼表层并分布在晶界中;
3)在钕铁硼部件沉积铜层上电镀镍层,镍层厚度3.5~15.5μm。
下面给出具体的实施例。
一种钕铁硼双镀层表面防护方法,包括以下操作:
步骤一:钕铁硼部件预处理
11)表面机械处理
首先处理钕铁硼部件机械加工后的表面物理缺陷;优先选用振动光饰机进行研磨抛光,加入棕刚玉磨石和硅酸钠添加液(按其质量百分比添加0.4%三乙醇胺、0.8%硼酸、0.05%乙二胺四乙酸),放入钕铁硼部件抛光研磨,研磨后零件棱边半径R小于0.5mm为宜。
12)表面除油处理
采用低碱性、强乳化力、油污分散能力强的无磷去除油污溶液:
以质量分数计,取氢氧化钠15%~25%、碳酸钠30%~35%、五水偏硅酸钠4%~5%、十二烷基硫酸钠(K12)3%~15%、烷基取代二元羧酸盐(DG)20%~25%、异构脂肪醇烷氧基化物(EH)2%~3%以及0.5%~1.0%层状结晶二硅酸钠;用水充分溶解制成无磷去除油污溶液;
具体的,取氢氧化钠20%、碳酸钠35%、五水偏硅酸钠4%、十二烷基硫酸钠(K12)12%、烷基取代二元羧酸盐(DG)25%、异构脂肪醇烷氧基化物(EH)3%,层状结晶二硅酸钠1.0%;用水充分溶解制成无磷去除油污溶液;
将无磷去除油污溶液倒入超声波清洗机(内槽尺寸800mm*640mm*350mm),放入钕铁硼部件,超声波功率:2000W、超声频率:40KHz;超声清洗180S~300s。
13)酸洗
质量分数计,酸洗溶液中包括柠檬酸6%~10%、硝酸钠3%~5%、氨水0.2%~0.4%、尿素1.5%~3.5%;清洗方式采用超声辅助清洗;清洗温度控制在20~30℃之间,清洗时间控制在60S~180S。
本发明选用酸性较弱的有机酸体系减少酸洗过程对基体损伤;有机酸清洗体系在利用H+离子与碱性的金属氧化物发生作用的条件下,同时在柠檬酸溶液中加入氨水,通过柠檬酸的络合作用生成溶解度很高的柠檬酸亚铁铵和柠檬酸高铁铵复盐而达到提高去除氧化铁的效应,也可防止溶度积很小的Fe(OH)3沉淀产生;进一步的通过添加硝酸盐,协同柠檬酸作用,加速表面污染物的溶解,从而有效的提高清洗效果。
优选的,在柠檬酸铵溶液中加入0.1%的尿素,实现新清洗面的快速钝化;钝化后,试样表面金属氧化物、金属氢氧化物以及少量的金属单质和结晶水组成钝化膜,有效的改善钕铁硼富钕相在溶液中腐蚀导致外表面变得疏松的现象,其耐蚀性大大的提高。
步骤二:物理法气相沉积或磁控溅射法沉积铜层
以磁控溅射为例进行说明,镀膜设备可由真空室、旋转系统、机架、无油真空系统、冷却系统、气动系统、电气系统等部份组成。
具体的,选用的磁控溅射镀膜机,真空室尺寸大于φ1000mm*1200mm,膜厚不均匀性≤5%,极限真空度≤5.0*10~4Pa,真空室保压:系统停泵关机12小时后真空度≤5Pa;电源:直流1000W(1台)、射频:600W;偏压:0~200V负偏压,连续可调;加热温度:室温~350℃可调,自动控温,控温精度优于1%;气体流量控制:Ar~1000sccm;O2~100sccm;N2~100sccm,精度优于1%,气体压强控制范围:10Pa~1×10~5Pa;
射频磁控溅射主要步骤包括抽真空、抽空加热、洗靶、离子清洗、成膜、冷却、出炉和清洁。
21)将要施镀的样品置于旋转架上,并将旋转架安装至真空室架座;将要进行溅射的铜靶材安装到阴极靶材座;开机启动空气压缩机、水冷机、稳压电源,打开氩气并调整好压力,并开旋转架,设定旋转速度位5~30转/分钟;
22)预热,抽真空;真空度达到5*10~3Pa开启加热器(100~200℃),加热完成后,真空度达到5*10~4Pa开启电离真空计;
23)通氩气,氩气纯度99.995%,氩气流量50~200sccm;调节主阀使得真空度至1Pa~3Pa;
24)打开射频溅射电源开始工作,起辉并调节射频功率20W~160W;打开直流溅射电源开关;工件架应有旋转装置,其旋转速度应连续可调;工件架加0~200V负偏压,连续可调(精度1V);按设定的工艺参数进行溅射镀膜至要求厚度;工作压强自动控制范围:10Pa~1×10~1Pa,工作压强自动控制精度为1%;
25)沉积完成后,取出钕铁硼部件。
本发明将铜原子沉积在钕铁硼基体上,形成致密的铜层,优化钕铁硼边界显微结构(参见图1、图2所示的边界优化前、后的对比图)。通过调节溅射设备的工作电压、放电电流,得到良好结合力的铜沉积层;随沉积时间的变化,得到铜层膜厚达到5μm左右;且沉积过程不受零件形状的限制。同时,由于钕铁硼基体清洗处理后表面区域的晶界相裸露,一部分铜原子很容易扩散进入钕铁硼表层;铜原子不但能够促进磁体表层的致密性,保证了沉积层和基体的结合力,而且铜原子主要分布在晶界中改善了晶界相微观结构,可促进磁性能的提升。
步骤三:电镀镍层
31)预沉积层表面活化处理
选用3%~10%体积浓度的稀硫酸,将钕铁硼部件浸入其中,在室温下轻微搅拌30s~60s。
32)电镀镍层
电镀溶液中包括:硫酸镍、氯化钠、氯化镍、硼酸、硫酸镁、氨水和水组成。其中硫酸镍(200g/L~350g/L)、氯化镍(30g/L~55g/L)、硫酸镁(5g/L~20g/L)、氯化钠(5g/L~15g/L)、硼酸(35g/L~60g/L)、氨水(2g/L~5g/L);选用电流密度(0.3~0.8A/dm2);选用PH=3.8~5.0;选用温度:(45℃~55℃);选用电镀时间:3600s~7200s。
电镀选用STP~100A/12V.R高频电源,输入AC220V/1PH,输出100A/12V。配套整流电源多时段时间继电器,一路总工作时间控制,其它1~5路按工艺顺序开启关闭,同时能够通过电位器数值的改变控制不同时段的电流输出。阳极选用高纯度镍球(纯度>99.9%)。
3)清洗
电镀完成后采用蒸馏水或去离子水清洗试样。多次漂洗后再经两次热水洗,然后热风吹干。
本发明在铜沉积层上电镀镍金属,避免了钕铁硼基体直接与镍镀液中的氯离子接触后容易被氯离子腐蚀,由此导致电镀完成后钕铁硼零件的磁性能下降较多;避免电镀过程钕铁硼基体直接接触带入的杂质元素。
下面给出本发明的一些检测数据来进行说明本发明双镀层与底层镀镍-镀铜-表层镀镍的三层电镀镀层的磁性能的损耗。
磁性能或磁性能损耗对比之一
磁性能或磁性能损耗对比之二
磁性能或磁性能损耗对比之三
由此可见,本发明的双镀层降低了钕铁硼部件磁性能的损耗。
下面给出本发明制作的双镀层与底层镀镍-镀铜-表层镀镍的的耐蚀性比较:
项目 | 双层镀层结构 | 三层镀层结构 |
自腐蚀电流密度 | 1.8*10~7A/cm2 | 5.3*10~6A/cm2 |
48小时耐盐雾结果 | 试样完好 | 试样完好 |
96小时耐盐雾结果 | 试样完好 | 试样完好 |
120小时耐盐雾结果 | 试样完好 | 试样开始出现锈点 |
168小时耐盐雾结果 | 试样开始出现锈点 | / |
结果比较 | 较好 | 一般 |
由此,可见本发明实现了既不影响表面结合力,同时将很大程度上降低其磁性能的损耗,甚至不产生磁性能的损耗的高耐蚀性的新型表面防护。
以上给出的实施例是实现本发明较优的例子,本发明不限于上述实施例。本领域的技术人员根据本发明技术方案的技术特征所做出的任何非本质的添加、替换,均属于本发明的保护范围。
Claims (7)
1.一种钕铁硼双镀层表面防护方法,其特征在于,包括以下操作:
1)将钕铁硼部件进行表面物理缺陷机械处理、表面除油处理之后,在酸洗液中进行超声处理;
所述的酸洗液中至少包括柠檬酸、氨水和尿素;酸洗后钕铁硼部件表面区域的晶界相裸露,并形成钝化膜;
2)通过物理法气相沉积或磁控溅射法在钕铁硼部件表面沉积铜层,铜层厚度为4~6μm;其中部分铜原子扩散进入钕铁硼表层并分布在晶界中;
3)在钕铁硼部件的沉积铜层上电镀镍层,镍层厚度3.5~15.5μm。
2.如权利要求1所述的钕铁硼双镀层表面防护方法,其特征在于,所述表面物理缺陷机械处理是进行研磨抛光处理,研磨后钕铁硼部件棱边半径R小于0.5mm;
所述表面除油处理是将钕铁硼部件置入无磷去除油污溶液中超声清洗180~300s。
3.如权利要求2所述的钕铁硼双镀层表面防护方法,其特征在于,所述研磨抛光是利用振动光饰机进行研磨抛光,在振动光饰机中加入棕刚玉磨石和硅酸钠添加液,然后放入钕铁硼部件抛光研磨;
所述硅酸钠添加液,是按质量百分比在硅酸钠中添加0.1~0.4%的三乙醇胺、0.2~0.8%的硼酸和0.01~0.05%的乙二胺四乙酸。
4.如权利要求2所述的钕铁硼双镀层表面防护方法,其特征在于,以质量分数计,取15%~25%的氢氧化钠、30%~35%的碳酸钠、4%~5%的五水偏硅酸钠、3%~15%的十二烷基硫酸钠、20%~25%的烷基取代二元羧酸盐、2%~3%的异构脂肪醇烷氧基化物,以及0.5%~1.0%的层状结晶二硅酸钠;用水充分溶解制成无磷去除油污溶液;
超声清洗时,超声波功率1500~2000W、超声频率35~40KHz。
5.如权利要求1所述的钕铁硼双镀层表面防护方法,其特征在于,以质量分数计,所述的酸洗液包括6%~10%的柠檬酸、3%~5%的硝酸钠、0.2%~0.4%的氨水和1.5%~3.5%的尿素;
清洗方式超声辅助清洗,清洗温度控制在20~30℃之间,清洗时间控制在60~180s。
6.如权利要求1所述的钕铁硼双镀层表面防护方法,其特征在于,所述沉积铜层的磁控溅射操作包括:
1)安装铜靶材后开机启动空气压缩机、水冷机、稳压电源,打开氩气并调整好压力;
2)预热,抽真空;真空度达到5*10~3Pa开启加热器,加热至100~200℃后,真空度达到5*10~4Pa开启电离真空计;
3)通氩气,氩气纯度99.995%,氩气流量50~200sccm;调节真空度至1Pa~3Pa,执行铜层沉积;
4)沉积完成后,取出试样。
7.如权利要求1所述的钕铁硼双镀层表面防护方法,其特征在于,所述电镀镍层包括以下操作:
1)预沉积层表面活化处理:
将钕铁硼部件浸入体积浓度3%~10%的稀硫酸中,在室温下搅拌30~60s;
2)电镀镍层
取出钕铁硼部件置入电镀液中作为阴极进行电镀,电镀液中包括200g/L~350g/L的硫酸镍、30g/L~55g/L的氯化镍、5g/L~20g/L的硫酸镁、5g/L~15g/L的氯化钠、35g/L~60g/L的硼酸和2g/L~5g/L的氨水,其pH为3.8~5.0;
阳极为纯度>99.9%的高纯度镍球,电镀的电流密度为0.3~0.8A/dm2、温度为45℃~55℃、电镀时间为3600s~7200s;
3)清洗
电镀完成后采用蒸馏水或去离子水多次漂洗,再经45℃~55℃热水清洗,然后20~60℃热风吹干。
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