CN116926517A - Corrosion-resistant temperature-resistant impact-resistant composite layer based on tin layer, aluminum substrate corrosion-resistant temperature-resistant impact-resistant treatment method and aluminum terminal - Google Patents
Corrosion-resistant temperature-resistant impact-resistant composite layer based on tin layer, aluminum substrate corrosion-resistant temperature-resistant impact-resistant treatment method and aluminum terminal Download PDFInfo
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- CN116926517A CN116926517A CN202310934996.2A CN202310934996A CN116926517A CN 116926517 A CN116926517 A CN 116926517A CN 202310934996 A CN202310934996 A CN 202310934996A CN 116926517 A CN116926517 A CN 116926517A
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- temperature
- impact
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- 230000007797 corrosion Effects 0.000 title claims abstract description 225
- 238000005260 corrosion Methods 0.000 title claims abstract description 225
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 156
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000002131 composite material Substances 0.000 title claims abstract description 120
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000000758 substrate Substances 0.000 title claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 142
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 140
- 229910052802 copper Inorganic materials 0.000 claims abstract description 140
- 239000003513 alkali Substances 0.000 claims abstract description 62
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims abstract description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 54
- 239000007921 spray Substances 0.000 claims abstract description 41
- 238000007747 plating Methods 0.000 claims description 108
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 72
- 238000009713 electroplating Methods 0.000 claims description 72
- 229910052725 zinc Inorganic materials 0.000 claims description 72
- 239000011701 zinc Substances 0.000 claims description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 44
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 238000005498 polishing Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- 230000007704 transition Effects 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 13
- 239000000571 coke Substances 0.000 claims description 11
- 230000003746 surface roughness Effects 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims description 3
- 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 claims description 3
- 238000004080 punching Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 36
- 230000008569 process Effects 0.000 description 27
- 238000000576 coating method Methods 0.000 description 25
- 238000012360 testing method Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 17
- 238000000151 deposition Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000009863 impact test Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000149 penetrating effect Effects 0.000 description 7
- 238000003466 welding Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000006056 electrooxidation reaction Methods 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- -1 hydrogen ions Chemical class 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940081974 saccharin Drugs 0.000 description 2
- 235000019204 saccharin Nutrition 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical group [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005542 laser surface treatment Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a tin layer-based corrosion-resistant and temperature-resistant impact composite layer, an aluminum substrate corrosion-resistant and temperature-resistant impact treatment method and an aluminum terminal. The corrosion-resistant and temperature-resistant impact-resistant composite layer based on the tin layer comprises: an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer; wherein: the thickness of the alkali copper layer is 1-10 mu m, the thickness of the pyrocopper layer is 2-18 mu m, the thickness of the nickel sulfamate layer is 3-28 mu m, and the thickness of the tin layer is 3-30 mu m. The corrosion-resistant treatment method of the aluminum substrate comprises the step of arranging the corrosion-resistant and temperature-resistant impact-resistant composite layer on the surface of the aluminum substrate. The surface of the corrosion-resistant aluminum terminal is provided with the corrosion-resistant temperature impact-resistant composite layer. The composite layer has excellent performance and good corrosion resistance after being subjected to temperature cycle impact; after the temperature cycle impact, the 240H salt spray corrosion resistance requirement can be met.
Description
Technical Field
The invention relates to a tin layer-based corrosion-resistant and temperature-resistant impact composite layer, an aluminum substrate corrosion-resistant and temperature-resistant impact treatment method and an aluminum terminal, and belongs to the technical field of corrosion resistance.
Background
At present, the processes of electroplating, chemical plating, spraying, laser surface treatment and the like can play a role in protecting a matrix by coating a film layer on the surface of aluminum and aluminum alloy, but the effect of salt spray resistance experiments is not ideal, the common aluminum workpiece can be corroded only after the salt spray time is maintained for 48 hours, and the service life of the aluminum workpiece in the assembly is greatly limited. At the same time, the expansion coefficient of the metal aluminum is very large and is 23.21 multiplied by 10 -6 and/K, stress is necessarily generated on the surface film layer in the process of temperature impact, and the film layer is torn. In the subsequent salt spray test, the damaged film layer has a greatly reduced protective effect, so that the salt spray of the aluminum workpiece after temperature impact can not reach 12 hours.
The current electroplating manufacturer develops less aluminum electroplating technology, and only carries out the next electroplating by plating nickel after secondary zinc precipitation, the plating scheme is different in selection and general in effect, and the aluminum workpiece electroplating requirement of high corrosion resistance after temperature impact is difficult to solve, and particularly the aluminum workpiece used in the fields of military industry, aerospace, automobiles and the like and in the severe environment with rapid temperature change can not meet the use requirement.
At present, terminals or workpieces applied to assemblies such as connectors, car bodies, controllers and battery packs in the market are subjected to temperature impact test, the temperature is kept at minus 40 ℃ for 30min, the temperature is kept at 140 ℃ for 30min in 30s, the problems of contact resistance overrun, poor appearance, pressure resistance overrun and the like are avoided after the test is performed for 100 times in a circulating way, the terminals tested by the temperature impact test are seemingly good, but cracks appear in the microcosmic and the aluminum terminals are more serious.
However, the prior art is not concerned about the corrosion resistance after the temperature impact cycle, and the coating is damaged at this time, so that the corrosion resistance of the coating is lost, and the service performance of a terminal, a workpiece and the like is greatly influenced; serious consequences can occur if the corrosion resistance of the terminal or workpiece after being subjected to temperature shock cycles does not meet the practical use requirements.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the corrosion-resistant and temperature-resistant impact composite layer which has excellent salt spray corrosion resistance, particularly corrosion resistance after temperature impact and can be used for corrosion-resistant and temperature-resistant impact treatment of an aluminum substrate.
To achieve the above object, the present invention provides a corrosion-resistant and temperature-resistant composite layer, which includes: an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer;
wherein: the thickness of the alkali copper layer is 1-10 mu m, the thickness of the pyrocopper layer is 2-18 mu m, the thickness of the nickel sulfamate layer is 0.5-28 mu m, and the thickness of the tin layer is 3-30 mu m.
In the above corrosion-resistant and temperature-resistant composite layer, preferably, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer, and the tin layer are sequentially disposed.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, the thickness of the alkali copper layer is preferably 1 to 6 μm, more preferably 2 to 4 μm.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, the thickness of the pyrocopper layer is preferably 5 to 15 μm, more preferably 8 to 10 μm.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, the nickel sulfamate layer preferably has a thickness of 0.5 to 18 μm, more preferably 6 to 9 μm. In some cases, the thickness of the nickel sulfamate layer may be controlled to be 3-28 μm, preferably 4-15 μm.
In the above-mentioned corrosion-resistant temperature impact-resistant composite layer, according to the difference of the requirements of the applicable position for corrosion resistance, the tin layer may have different thicknesses, for example, in the contact area or welding area of the male and female aluminum terminals, the contact area between these areas and the environment is smaller, belonging to the semi-exposed area, the requirements for corrosion resistance are lower, and a thinner tin layer may be provided, preferably, the thickness of the tin layer (thin tin layer) is 3-10 μm, more preferably 3-6 μm; in the completely exposed area where the contact area of the aluminum terminal with the environment is large, the requirement for corrosion resistance is high, and a thick tin layer is required, preferably, the thickness of the tin layer (thick tin layer) is 10-25 μm, and more preferably, 14-18 μm.
In the above corrosion-resistant and temperature-resistant composite layer, preferably, the corrosion-resistant and temperature-resistant composite layer further includes a transition layer, and the transition layer is disposed on a side of the alkaline copper layer, which is not in contact with the pyrocopper layer. The transition layer is arranged between the alkali copper layer and the base material needing corrosion resistance treatment, and can be realized by adopting a proper surface treatment mode as transition.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, preferably, the transition layer includes a zinc layer, or a combination of a zinc layer and a secondary zinc precipitation layer; the zinc layer (or zinc layer, secondary zinc layer), alkali copper layer, pyrocopper layer and tin layer are arranged in sequence. The zinc layer and the secondary zinc layer are used as transition of the subsequent electroplated layer, so that the adhesive force of the zinc layer and the secondary zinc layer can be ensured. According to a specific embodiment of the invention, the combination of the zinc layer and the secondary zinc layer comprises a mode of superposing the zinc layer and the secondary zinc layer (superposing the zinc layer on top of each other and covering the zinc layer by the secondary zinc layer); and a manner in which the zinc layer and the secondary zinc layer are located in different regions of the same layer, and in this manner, both may have a portion superimposed on each other. The transition layer of the invention is not limited to a zinc layer and a secondary zinc layer, and can be made of other metal or alloy materials, so long as the adhesion of the multifunctional composite layer can be improved, for example, the transition layer can be formed on the surface of the aluminum terminal through surface treatment processes such as spraying, vacuum plating and the like.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, the zinc layer preferably has a thickness of 0.1 to 10 μm, more preferably 0.5 to 1 μm.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, the thickness of the secondary zinc-deposited layer is preferably 0.1 to 10 μm, more preferably 1.5 to 2.5 μm.
In the above corrosion-resistant and temperature-resistant composite layer, preferably, the zinc layer, the secondary zinc-precipitation layer, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer, and the tin layer are respectively electroplated layers.
In the above-described corrosion-resistant and temperature-resistant composite layer, preferably, the corrosion-resistant and temperature-resistant composite layer further includes an electroless copper layer (or electroless copper plating layer).
In the above corrosion-resistant and temperature-resistant composite layer, preferably, the chemical copper layer is disposed on the surface of the alkaline copper layer or the surface of the pyrocopper layer, that is, the chemical copper layer may have the following arrangement modes: (1) The surface of one side of the alkali copper layer, which is not contacted with the copper layer, is provided with a copper layer; (2) disposed between the alkaline copper layer and the pyrocopper layer; (3) The copper-base layer is arranged on the surface of one side of the copper-base layer, which is not contacted with the copper-base layer.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, the thickness of the chemical copper layer is preferably 3 to 25 μm, more preferably 5 to 15 μm.
In the above-described corrosion-resistant temperature-resistant impact composite layer, preferably, the corrosion-resistant temperature-resistant impact composite layer further includes an acid copper layer.
In the above corrosion-resistant and temperature-resistant composite layer, preferably, the acid copper layer is disposed on the surface of the alkali copper layer or the surface of the pyrocopper layer, that is, the chemical copper layer may have the following arrangement modes: (1) The surface of one side of the alkali copper layer, which is not contacted with the copper layer, is provided with a copper layer; (2) disposed between the alkaline copper layer and the pyrocopper layer; (3) The copper-base layer is arranged on the surface of one side of the copper-base layer, which is not contacted with the copper-base layer.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, the thickness of the acid copper layer is preferably 1 to 20 μm, more preferably 3 to 10 μm.
In the above-described corrosion-resistant temperature-resistant impact composite layer, preferably, the corrosion-resistant temperature-resistant impact composite layer further includes a watt nickel layer.
In the above corrosion-resistant and temperature-resistant composite layer, preferably, the watt nickel layer is disposed on the surface of the nickel sulfamate layer, that is, the watt nickel layer may have the following arrangement modes: (1) The nickel sulfamate layer is arranged between the nickel sulfamate layer and the copper coke layer; (2) Is arranged between the nickel sulfamate layer and the silver layer.
In the above-described corrosion-resistant and temperature-resistant composite layer, the thickness of the watt nickel layer is preferably 1 to 20 μm, more preferably 3 to 9 μm.
In the above-mentioned corrosion-resistant and temperature-resistant composite layer, preferably, the corrosion-resistant and temperature-resistant composite layer may include both the chemical copper layer and the acid copper layer, and, for specific positions of both of them, may be disposed at any one or two of three positions of a side surface of the alkali copper layer which is not in contact with the pyrocopper layer, a side surface of the alkali copper layer which is between the alkali copper layer and the pyrocopper layer, and a side surface of the pyrocopper layer which is not in contact with the alkali copper layer, and when both of them select the same position, the order of each other may be arbitrary, for example, when both of the chemical copper layer and the acid copper layer are located between the alkali copper layer and the pyrocopper layer, the order of the alkali copper layer, the chemical copper layer, the acid copper layer, and the pyrocopper layer may be either the order of the alkali copper layer, the acid copper layer, the chemical copper layer and the pyrocopper layer. On the basis, the nickel layer can be simultaneously arranged.
Because of the difference in expansion coefficient between the aluminum base material (e.g., aluminum terminal, work) and the plating film layer, and the difference in expansion coefficient between the plating film layer and the plating film layer, the expansion coefficient of the aluminum base material is generally 23.21×10 when the temperature impact test is performed -6 In the temperature impact test, the thermal expansion volume of the aluminum substrate is larger than that of the electroplated film, and the volume difference between the aluminum substrate and the electroplated film causes great tensile stress between the workpiece and the electroplated film. The stress causes the electroplated film to be torn or even destroyed, and when the salt spray test is carried out on the workpiece with the torn surface film, chloride ions in the salt spray liquid easily pass through and contact with the aluminum substrate, so that the electrochemical corrosion of the aluminum substrate is caused.
The alkali copper layer, the pyrocopper layer and the tin layer of the corrosion-resistant and temperature-resistant composite layer provided by the invention have similar expansion coefficients with aluminum (copper is 17 multiplied by 10) -6 K, tin 26.7X10 -6 And (K), the tensile stress generated by volume expansion in temperature impact is greatly reduced, and meanwhile, the tin layer adopts a high-ductility and high-toughness nickel sulfamate layer, so that the nickel sulfamate layer is not torn after bearing the tensile stress, the original compactness is still maintained, and a workpiece can be effectively protected in a salt spray test to avoid corrosion. The tin layer is used as a plating layer of the outermost layer in the composite layer, so that salt fog liquid can be effectively prevented from penetrating through the plating layer to corrode the substrate.
The invention also provides a preparation method of the corrosion-resistant temperature-resistant impact-resistant composite layer, which comprises the following steps: and forming an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer on the surface of the base material in sequence in an electroplating mode.
In the above method for preparing a corrosion-resistant and temperature-resistant composite layer, preferably, the alkaline copper layer uses an electroplating solution containing cuprous cyanide based on the total volume of the electroplating solution: 40-50g/L, total sodium cyanide: 40-60g/L, free sodium cyanide: 8-14g/L, potassium sodium tartrate: 30-45g/L, sodium hydroxide: 1-3g/L, additive (one or more than two of polyethylene glycol, fatty amine polyoxyethylene ether (AEO) and OP series octyl phenol polyoxyethylene ether, etc.): 3-5mL/L. The remainder of the plating solution is water.
In the above method for preparing the corrosion-resistant and temperature-resistant composite layer, preferably, the temperature of the alkaline copper layer is 40-50 ℃, and the area ratio of anode to cathode is 1:1-2 (preferably 1:1.5) and a current density of 0.7-1.2A/dm 2 The electroplating time is 5-15min.
In the above method for preparing a corrosion-resistant and temperature-resistant composite layer, preferably, the plating solution used for the pyrocopper layer contains copper pyrophosphate, based on the total volume of the plating solution: 50-70g/L, potassium pyrophosphate: 300-450g/L, ammonium citrate: 15-30g/L, ammonia water: 2-5mL/L. The remainder of the plating solution is water.
In the method for preparing the corrosion-resistant and temperature-resistant composite layer, preferably, the temperature of the electroplated copper coke layer is 40-50 ℃ and the current density is 0.7-1.2A/dm 2 The area ratio of the cathode to the anode is 1:1-2 (preferably 1:1.5), and the electroplating time is 50-90min (preferably 70 min).
In the above method for preparing a corrosion-resistant and temperature-resistant composite layer, preferably, the plating solution used for the nickel sulfamate layer contains nickel sulfamate, based on the total volume of the plating solution: 300-500g/L, nickel chloride: 10-25g/L, boric acid: 30-40g/L sulfamic acid: 100-150g/L, additive (one or more of pyridine derivatives, propynyl derivatives, saccharin and the like): 5-10ml/L. The remainder of the plating solution is water.
In the method for preparing the corrosion-resistant and temperature-resistant composite layer, preferably, the temperature of the nickel sulfamate layer is 50-60 ℃ and the nickel sulfamate layer is electroplatedThe flow density is 0.8-1.2A/dm 2 The area ratio of the cathode to the anode is 1:1-2 (preferably 1:1.5), and the electroplating time is 1-80min (preferably 40-60min, preferably 50 min).
In the above method for preparing a corrosion-resistant and temperature-resistant composite layer, preferably, the plating solution used for the tin layer contains stannous sulfate based on the total volume of the plating solution: 10-50g/L, sulfuric acid: 60-190ml/L, gelatin: 1-10g/L, formaldehyde: 5-10ml/L, benzalacetone: 5-30g/L. The remainder of the plating solution is water.
In the above method for producing a corrosion-resistant and temperature-resistant composite layer, preferably, the temperature of the electroplated tin layer is 10-40 ℃, the cathode-anode area ratio is 1:1-2 (preferably 1:1.5), and the current density is 0.5-2A/dm 2 (preferably 0.7-1.2A/dm) 2 ) The electroplating time is 15-120min (preferably 60 min).
The tin layer can be a fog tin layer or a bright tin layer, and can obtain good corrosion resistance, and the specific electroplating preparation process can be determined according to the needs.
In the preparation method of the corrosion-resistant and temperature-resistant composite layer, preferably, the alkaline copper plating layer, the coke copper plating layer, the tin plating layer and the like can be electroplated by adopting a pulse electroplating process, and can be promoted on the basis of the original compactness, so that the electroplated layer is more compact, fewer in pores and stronger in salt spray resistance.
In the above-described method for producing a corrosion-resistant composite layer, preferably, when a chemical copper layer, an acid copper layer, a watt nickel layer are contained, these layers can be obtained in a corresponding manner at an appropriate timing.
In the method for preparing the corrosion-resistant and temperature-resistant composite layer, preferably, the zinc layer and the secondary zinc layer can be prepared by adopting a conventional electroplating method.
In the preparation method of the corrosion-resistant and temperature-resistant composite layer, other working procedures such as acid activation treatment before each working procedure, pure water washing cleaning before each working procedure and the like can be added in the electroplating process step to ensure the electroplating binding force.
The invention also provides a corrosion-resistant and temperature-resistant impact treatment method for the aluminum substrate, which comprises the step of arranging the corrosion-resistant and temperature-resistant impact composite layer on the surface of the aluminum substrate. The aluminum substrate of the present invention includes pure aluminum substrates and aluminum alloy substrates.
In the above-described corrosion-resistant and temperature-resistant impact treatment method for an aluminum substrate, preferably, the corrosion resistance means salt spray corrosion resistance.
In the above method for corrosion-resistant and temperature-resistant impact treatment of an aluminum substrate, preferably, the temperature impact resistance means resistance to a temperature cycle impact, that is, resistance to a cold-hot alternating cycle impact.
In the above method for corrosion-resistant and temperature-resistant impact treatment of an aluminum substrate, the surface roughness of the aluminum substrate is preferably less than Ra 3.6, more preferably less than Ra 0.8.
The invention also provides a corrosion-resistant and temperature-resistant aluminum terminal, wherein a part or all of the area of the surface of the corrosion-resistant and temperature-resistant aluminum terminal is provided with the corrosion-resistant and temperature-resistant composite layer.
In the above-described corrosion-resistant and temperature-resistant aluminum terminal, the corrosion-resistant and temperature-resistant composite layer may cover the entire surface of the aluminum terminal, or may cover only a surface area requiring corrosion-resistant and temperature-resistant treatment.
The invention also provides a preparation method of the corrosion-resistant and temperature-resistant aluminum terminal, which comprises the following steps:
rolling and polishing the front surface of the aluminum terminal;
punching the side surface of the aluminum terminal;
and forming a zinc layer, a secondary zinc deposition layer, an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer on the front surface and the side surface of the treated aluminum terminal in sequence through electroplating, so that the corrosion-resistant and temperature-resistant aluminum terminal is achieved.
In the above-described method for producing an aluminum terminal resistant to corrosion and temperature impact, the rolling treatment, polishing treatment, stamping treatment, and the like may be performed only on the region where corrosion and temperature impact resistance are required, and are not necessarily limited to the entire region of the surface of the aluminum terminal. The method is favorable for welding by adopting a local area treatment mode, and can be matched with various connection processes such as friction welding, friction stir welding, ultrasonic welding, molecular diffusion welding, resistance welding and the like, so that the corrosion-resistant terminal with high reliability and various connection processes is obtained.
In the method for preparing the corrosion-resistant and temperature-resistant aluminum terminal, preferably, the terminal material is rolled, so that the compactness of the terminal surface can be enhanced, and the corrosion resistance and temperature-resistant impact resistance of the subsequent electroplating treatment can be enhanced.
In the method for manufacturing the corrosion-resistant and temperature-resistant aluminum terminal, preferably, the polishing treatment is performed on the terminal material, so that the finish of the terminal surface can be enhanced, and the corrosion resistance and temperature-resistant impact resistance of the subsequent electroplating treatment can be enhanced. The polishing treatment may be performed by chemical polishing, mechanical polishing, or the like.
In the above-described method for producing an aluminum terminal resistant to corrosion and temperature impact, it is preferable that the front surface roughness of the aluminum terminal subjected to the rolling treatment and the polishing treatment is less than Ra 3.6, more preferably less than Ra 0.8.
In the above-described method for producing an aluminum terminal resistant to corrosion and temperature impact, it is preferable that the rolled aluminum terminal has a side roughness of less than Ra 3.6 (more preferably less than Ra 0.8) and a bright band of more than 50% (more preferably more than 98%).
In the above method for manufacturing an aluminum terminal resistant to corrosion and temperature impact, when a transition layer is provided, it is preferable that the transition layer is formed on the front and side surfaces of the treated aluminum terminal before the alkali copper layer is formed by electroplating.
According to the technical scheme, from the practical application point of view (the terminal is more easily corroded after the temperature is suddenly changed in practical application and corrosion is present at any time), the corrosion resistance of the aluminum terminal after temperature impact cycle is optimized, namely the salt spray corrosion resistance of the aluminum terminal after temperature impact cycle is improved, the aluminum terminal can still have better corrosion resistance after being subjected to the temperature cycle impact cycle of 30 minutes to 140 ℃ for 30 minutes at 100 times, the full-exposure area of a thick tin layer is adopted, the salt spray time can reach 240H, the salt spray resistance of 60 hours can be realized by adopting the semi-exposure area of a thin tin layer, and the aluminum terminal still has longer mechanical life in a severe environment with high temperature sudden change and high corrosiveness.
Drawings
Fig. 1 is a schematic view showing an exemplary overall structure of an aluminum terminal according to the present invention.
Fig. 2 is a schematic diagram of an exemplary electroplating process for an aluminum terminal according to the present invention.
Fig. 3 is a profile view of the side of an aluminum terminal obtained by ordinary stamping and precision stamping.
Fig. 4 is an SEM image of a conventional aluminum plate and a rolled aluminum plate.
Fig. 5 is a graph of sample morphology before and after a temperature impact test.
Fig. 6 is a surface SEM image and a side cross-sectional metallographic image of a conventional plating layer (nickel plating) before and after temperature impact.
Fig. 7 is a side cross-sectional metallographic image of a conventional plating (nickel plating) and the plating of example 1 of the present invention after temperature impact.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The invention provides an aluminum terminal with a plating film layer, which comprises an aluminum terminal material and a plating film layer, wherein the aluminum terminal material is provided with a terminal surface and a terminal side surface; the plating film layer (corrosion-resistant and temperature-resistant composite layer) includes: zinc layer, secondary zinc layer, alkali copper layer, pyrocopper layer, nickel sulfamate layer, and tin layer. An exemplary overall structure of an aluminum terminal with a corrosion-resistant and temperature-resistant composite layer is shown in fig. 1, wherein a zinc layer 2, an alkali copper layer 3, a pyrocopper layer 4, a nickel sulfamate layer 5 and a tin layer 6 are sequentially arranged on the surface of an aluminum substrate 1; if necessary, a secondary zinc precipitation layer can be further arranged between the zinc layer 2 and the alkaline copper layer 3.
An exemplary electroplating process for an aluminum terminal is shown in fig. 2: the electroplating process comprises the following steps: ultrasonic degreasing, alkaline washing, acid washing, chemical zinc precipitation, chemical zinc removal, secondary zinc precipitation, activation, alkaline copper electroplating, coke copper electroplating, nickel sulfamate electroplating, tin electroplating, post-treatment, pure water washing and drying; wherein, the step of secondary zinc precipitation can be selected according to the requirement.
Terminal corrosion principle: common corrosion of metallic materials is oxidation corrosion and electrochemical corrosion.
The principle of oxidation corrosion is that the metal is oxidized in the air, and the metal with stronger activity is more easily oxidized and corroded, and the following two methods are generally adopted to avoid corrosion: 1. the surface treatment is carried out, and a film is coated on the surface of the metal in a surface treatment mode, so that the effect of isolating air is achieved, and the metal is prevented from reacting due to contact with the air; 2. conversion of oxidation corrosion to electrochemical corrosion by cathodic protection of the workpiece in a manner that corrodes another metal, namely a sacrificial anode: the metal with strong reducibility is used as a protection electrode and is connected with the protected metal to form a primary battery, the metal with strong reducibility is used as a negative electrode to be consumed by oxidation reaction, and the protected metal is used as a positive electrode to avoid corrosion.
The electrochemical corrosion principle is that the metal reacts with the primary cell in the ocean atmospheric environment, the metal, impurities, water and sodium chloride plasma salt form the primary cell, which generates oxidation reaction on the anode (metal) to dissolve the anode (namely the metal is corroded), and the reduction reaction is generated on the cathode to transfer electrons and discharge. The corrosion time and process are very long, a salt spray test method is generally used for verifying the corrosion resistance of the metal material, namely, a salt spray test is a simulation experiment for simulating the corrosion resistance of the metal material in ocean atmosphere or humid air, and the environment test for checking the corrosion resistance of the product or the metal material is performed by using the artificial simulated salt spray environment condition created by salt spray test equipment. Electrochemical corrosion under salt mist generally prevents the salt mist liquid from contacting metal materials by means of surface treatment of a covering film layer, however, chloride ions in the salt mist environment have very strong penetrating capacity and can penetrate into a substrate from pores of the metal surface film layer, so that corrosion occurs. The invention designs the terminal material and the electroplating film layer, so that the electroplating film layer of the terminal can effectively prevent chloride ions from penetrating, and the corrosion resistance of the aluminum terminal is greatly improved.
Corrosion principle after terminal temperature impact test: the expansion coefficient of the aluminum workpiece is 23.21 multiplied by 10 when the temperature impact test is carried out due to the difference of the expansion coefficients of the workpiece and the plating film and the difference of the expansion coefficients of the plating film and the plating film -6 The thermal expansion volume of the aluminum workpiece is far greater than that of the electroplated film, and the volume difference between the aluminum workpiece and the electroplated film causes great tensile stress between the workpiece and the electroplated film. The stress causes the electroplated film layer to be torn or even destroyed, and when the salt spray test is carried out on the workpiece with the torn surface film layer, chloride ions in the salt spray liquid medicine easily pass through the workpiece to contact with the aluminum workpiece base material, so that the electrochemical corrosion of the workpiece is caused.
The invention is designed from the selection of the plating film layer, and uses the plating film layer (copper 17 multiplied by 10) of copper, tin and the like with the expansion coefficient similar to that of aluminum -6 K, tin 26.7X10 -6 And (K), the tensile stress generated by volume expansion in temperature impact is greatly reduced, and meanwhile, the tin layer adopts a high-ductility and high-toughness nickel sulfamate layer, so that the nickel sulfamate layer is not torn after bearing the tensile stress, the original compactness is still maintained, and a workpiece can be effectively protected in a salt spray test to avoid corrosion. The tin layer is used as a plating layer of the outermost layer in the composite layer, so that salt fog liquid can be effectively prevented from penetrating through the plating layer to corrode the substrate.
The surface density of the aluminum material is increased by applying pressure through mechanical means in the rolling treatment, so that the porosity of the surface of the aluminum terminal material is reduced, the compactness of the aluminum terminal material is improved, the preparation is made for the covering of the next electroplating film layer, the fewer the pores of the material are, the fewer the pores of the electroplating film layer are, and the protection is higher. SEM images of conventional aluminum plates and rolled aluminum plates are shown in fig. 3. In fig. 3, a graph a shows a conventional aluminum plate, and b graph b shows a rolled aluminum plate. As can be seen from fig. 3: through the roll-in treatment, the roughness of aluminum plate surface reduces, and the roughness obtains promoting by a wide margin.
The polishing treatment is performed in a magnetic polishing mode, specifically, a magnetic field is generated by electrifying, the magnetic field drives the stainless steel needle to move, and in the moving process, the stainless steel needle rubs the surface of the terminal material, so that the mechanical polishing effect is achieved, and the smoothness and the flatness of the surface of the terminal material are improved.
Polishing treatment, precise stamping process and the like are used for improving the smoothness and flatness of the front surface and the side surface of the terminal material.
The flatness and the smoothness of the terminal material are improved, so that the electroplating process is greatly beneficial to the electroplating film layer, and more electroplating film layers can be accumulated at the position where the electrons of the workpiece are enriched in the electroplating process due to the influence of current, so that the thickness of the electroplating film layer on the surface of the terminal is different, and even a large number of pits appear, so that chloride ions in salt mist are collected and penetrated. When the flatness of the terminal material is insufficient, due to the principle of point discharge, the more the conductor surface is bent, the more charges are accumulated at the place with smaller relative surface area, and a large number of electrons are accumulated on the uneven bulge on the material surface, so that the bulge position on the surface of the electroplated workpiece is more convex, and the concave position is more concave, thus small holes are formed, salt fog liquid medicine is easily accumulated, chloride ions are easily penetrated, and corrosion is caused. After the terminal material is treated by the process provided by the invention, the terminal material can effectively cover the electroplating film layer, and the corrosion resistance of the terminal material is effectively improved.
Electroplating alkali copper: the alkaline copper is cyanide copper plating, the complexing ability of cyanide in water is extremely strong, the cathode polarization of electroplating can be greatly increased, copper ions are deposited together after a large amount of cathode is accumulated, and the compactness of a plating film layer is improved; the plating layer electroplated by the cyanide system is compact and quick and efficient in reaction, and a compact and flat copper layer can be covered on the surface of the zinc layer; and copper has relatively inactive chemical property and low electroplating internal stress, is an excellent intermediate plating layer, and is easy to electroplate a subsequent metal plating layer.
The plating parameters were as follows: cuprous cyanide: 40-50g/L, total sodium cyanide: 40-60g/L, free sodium cyanide: 8-14g/L, potassium sodium tartrate: 30-45g/L, sodium hydroxide: 1-3g/L of additive: 3-5mL/L, temperature: 40-50 ℃, and the area ratio of the cathode to the anode: 1:1.5, current density: 0.7-1.2A/dm 2 Electroplating time: 5-15min, coating thickness: preferably 1-6 μm.
In order to enhance the compactness of the coating, the invention carries out process optimization: generally, to meet the requirement of electroplating efficiency, the method is faster in production, and the current density of the alkaline copper electroplated in an electroplating plant is 4-10A/dm 2 Far above the present invention. The density of the plating layer is directly affected by the current density, the cathode polarization can be weakened due to high current density, meanwhile, the overpotential of precipitation of hydrogen ions in the solution is easier to reach, the occurrence of hydrogen evolution side reaction during electroplating is caused, and the precipitated hydrogen can leave pores in the plating layer, so that the compactness of the plating layer is reduced. The alkaline copper plating process used in the invention reduces the current density and increases the concentration of the main salt cuprous cyanide and the free sodium cyanide at the same time, thereby obtaining the alkaline copper plating layer with excellent plating efficiency and compactness.
Electroplating the coke copper: the electroplated copper pyrophosphate layer is electroplated copper pyrophosphate, the complexing ability of the pyrophosphate in water is stronger than that of cyanide, and the cathode polarization effect in a pyrophosphate system is also stronger. Because of [ Cu (P) 2 O 7 ) 2 ] 6- The more negative charge is, the more the cathode process is affected, and at the same time [ Cu (P) 2 O 7 ) 2 ] 6- Is difficult to discharge and needs to be hydrolyzed into [ CuP ] 2 O 7 ] 2- Can discharge to deposit copper layer, [ CuP ] 2 O 7 ] 2- Is slower and so again increases the cathodic polarization. The coke copper electroplating film layer is more compact, has fewer pores, can effectively prevent chloride ions from penetrating in salt spray experiments, and enhances the corrosion resistance and the temperature impact resistance of the workpiece.
The plating parameters were as follows: copper pyrophosphate: 50-70g/L, potassium pyrophosphate: 300-450g/L, ammonium citrate: 15-30g/L, ammonia water: 2-5mL/L, current density 0.7-1.2A/dm 2 The temperature is 40-50 ℃, and the area ratio of the cathode to the anode is: 1:1.5, electroplating time is 50-90min, and electroplating thickness is as follows: preferably 5-15 μm. Also, in order to improve the compactness of the plating layer, the process used by the invention is optimized, and the current density is reduced.
The chemical copper layer is formed by orderly depositing copper ions on the base material in a chemical reaction self-catalytic plating mode, and good binding force can be obtained by adding the chemical copper layer between the layers, so that the chemical copper layer is a good intermediate plating layer, and the binding force of the whole plating layer can be enhanced. Meanwhile, the preparation process of the chemical copper layer is simple chemical reaction, and the thickness and the porosity of the plating layer cannot be influenced by current distribution, so that the thickness of the chemical copper layer is more uniform, the porosity is lower, and the corrosion resistance of the whole plating layer can be enhanced by adding the chemical copper layer.
Electroless copper plating parameters were as follows: composition of electroless plating solution: copper sulfate: 5-20g/L, sodium hypophosphite: 20-50g/L, sodium citrate: 5-30g/L, nickel sulfate: 0.1-5g/L, potassium ferrocyanide: 0.5-7mg/L, boric acid: 15-50g/L; the temperature is 60-90 ℃, the pH is 7.8-10.2, the electroplating time is 40-100min, and the general plating speed is 1 mu m/6min, namely: 6min-1 μm, namely 24min-4 μm,48min-8 μm; the plating thickness can be controlled by controlling parameters of electroless copper plating as needed.
The acid copper layer (namely acid copper plating layer) is copper sulfate plating, has good binding force with other plating layers and the like, can be used as an excellent intermediate plating layer, and is stable in copper sulfate plating solution adopted in the preparation of the acid copper layer, low in cost, and the acid copper is added between or on two sides of the alkali copper layer and the pyrocopper layer, so that the brightness and corrosion resistance of the whole plating layer can be enhanced.
The parameters for electroplating acid copper are as follows: composition of the plating solution: copper sulfate pentahydrate: 160-250g/L, sulfuric acid: 25-50mL/L, chloride ion: 40-120ppm of additive (one or more than two of sodium polydithio-dipropyl sulfonate, 2-mercaptobenzimidazole, 1, 2-ethylene thiourea and polyamine compound): 4-15mL/L, current density 0.8-2.0A/dm 2 The temperature is 20-30 ℃, and the area ratio of the cathode to the anode is 1:1.5, electroplating time is 20-80min, and the plating thickness is controlled by controlling electroplating parameters according to the requirement.
The watt nickel layer (namely the watt nickel coating and the bright nickel coating) is a nickel sulfate electroplated layer, has good binding force with other coatings and the like, can be used as an excellent intermediate coating, increases the watt nickel between or on two sides of an alkali copper layer and a coke copper layer, can generate potential difference in a corrosion environment, can be used as an anode to be corroded first, protects other coatings, and enhances the brightness and corrosion resistance of the whole coating.
The parameters of the electroplated watt nickel layer are as follows: composition of the plating solution: nickel sulfate hexahydrate: 250-350g/L, nickel chloride hexahydrate: 60-95g/L boric acid: 40-60g/L, additive (sodium dodecyl sulfate, saccharin, and butyl)One or a mixture of two or more of the acetylene glycol ethoxy ethers): 6-12mL/L; pH is 3-5, current density is 0.8-2.0A/dm 2 The temperature is 50-60 ℃, and the area ratio of the cathode to the anode is 1:1.5, electroplating time is 30-70min, and the plating thickness is controlled by controlling electroplating parameters according to the requirement.
Electroplating nickel sulfamate: nickel sulfamate is used as main salt, nickel chloride is used as depolarizer of anode, nickel layer electroplated under the liquid medicine system has good ductility, and compared with other electroplated nickel layers, the film layer electroplated by nickel sulfamate has higher toughness and lower internal stress, can bear tensile stress generated by temperature impact without being torn, still maintains original compactness, and can effectively protect workpieces from corrosion in salt spray tests.
The plating parameters were as follows: nickel sulfamate: 300-500g/L, nickel chloride: 10-25g/L, boric acid: 30-40g/L sulfamic acid: 100-150g/L, additive: 5-10ml/L; current density: 0.8-1.2A/dm 2 Temperature: 50-60 ℃, cathode-anode area ratio: 1:1.5, electroplating time: 1-80min; the plating thickness can be controlled by controlling parameters of electroless copper plating as needed. Also, in order to improve the compactness of the plating layer, the process used by the invention is optimized, and the current density is reduced.
Electroplating tin: compared with the silver electroplating, the compactness of the electroplated tin is better, the texture of the tin electroplating film layer is soft, the tight connection with other workpieces can be realized, and the electrical performance is better. And meanwhile, the cost of tin is far lower than that of silver, so that the tin is a good choice of corrosion-resistant aluminum terminals.
The plating parameters were as follows: electroplating solution composition: stannous sulfate: 10-50g/L, sulfuric acid: 60-190ml/L, gelatin: 1-10g/L, formaldehyde: 5-10ml/L, benzalacetone: 5-30g/L; temperature: 10-40 ℃, and the area ratio of the cathode to the anode: 1:1.5, current density: 0.7-1.2A/dm 2 Electroplating time: 15-120min, and the plating thickness is controlled by controlling the plating parameters according to the requirement.
After the impact test, when the thick tin layer is adopted, the salt fog resistance of the aluminum terminal provided by the invention can still reach 240H, and the corrosion resistance requirement of the full-exposed area of the aluminum terminal is met; when a thin tin layer is adopted, salt mist resistance can be realized for 48 hours, and the corrosion resistance requirement of a semi-exposed area of an aluminum terminal is met; meanwhile, the ductility of the alkaline copper, the pyrocopper and the tin layer is also excellent, and the alkaline copper, the pyrocopper and the tin layer can effectively bear tensile stress (on one hand, the tensile stress can be reduced, and on the other hand, the applied tensile stress can be borne) without breakage in a temperature impact cycle.
The nickel sulfamate layer adopted by the invention has good ductility and toughness, can easily bear stress caused by volume change, can not be damaged under the microcosmic plating layer, can continuously keep good compactness, and has better protection effect.
The invention can bring the following technical effects by mutually matching the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer, the tin layer and the like:
1. in the temperature cycle, the increase of the temperature can lead to the release of internal stress of the electroplated layers, so that the bonding force between the electroplated layers is invalid, the alkaline copper layer is used as the lowest layer, the bonding force is good, the bonding force of the terminal in the temperature impact can be ensured, and the problems of foaming peeling and the like can not occur. Meanwhile, the nickel sulfamate is also a low-stress nickel plating seed, has lower internal stress, is matched with an alkali copper layer and the like, and can effectively increase the plating binding force of the terminal.
2. Enhancing the salt fog effect: because the surface state of the base material has great influence on the electroplated layer and can not directly electroplate a very compact plated layer on the porous surface of the aluminum material, the invention adopts a scheme of gradually improving the compactness, the compactness of the zinc layer is lower than that of alkali copper, the compactness of the alkali copper is slightly lower than that of pyrocopper, and the compactness of the three layers is gradually improved, so that the compactness of the final pyrocopper layer is optimal, therefore, the invention preferably adopts 1-6 mu m alkali copper and 5-15 mu m pyrocopper for combination, and can effectively improve the corrosion resistance of a workpiece.
When the alkali copper layer is thicker, the rough plating layer is easy to appear, so the invention selects plating of 1-10 mu m (preferably 1-6 mu m), and the binding force and compactness can meet the requirement under the thickness of the plating layer. The thickness of the copper-coke layer is selected to be 2-18 μm, and the thicker the plating layer is, the more the pores of the copper-coke layer can be covered, but in consideration of the influence of the plating time, 5-15 μm is preferable. The nickel sulfamate layer is too thick, which still causes an increase in internal stress and a decrease in ductility, so that the selection of 4 to 15 μm is preferable in consideration of the combination.
The corrosion-resistant composite layer provided by the invention comprises the following components: the electroplating film layers such as the alkali copper layer, the coke copper layer and the tin layer have stronger compactness, can effectively prevent chloride ions from penetrating in a salt spray test, and the interaction of the metal/alloy layers is mutually overlapped, so that the pores existing in the original single plating layer are covered by other electroplating film layers, and even if the chloride ions penetrate one electroplating film layer in the salt spray test, other compact plating layers can effectively prevent the chloride ions from penetrating further, thereby greatly improving the corrosion resistance of the aluminum substrate. By adding a zinc layer, a secondary zinc deposition layer, a chemical copper layer, an acid copper layer, a watt nickel layer and the like, the corrosion resistance can be further improved.
Example 1
The present embodiment provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, wherein:
the front surface of the aluminum terminal material is subjected to rolling and polishing treatment, the roughness is smaller than Ra 0.8, the side surface is processed by a precision stamping process, the bright band is larger than 98%, and the roughness is smaller than Ra 0.8; the first figure in fig. 4 is a side picture of a normal press, and the second figure is a side picture of a precision press, as can be seen from fig. 4: the rough bands on the side surfaces of the aluminum terminals obtained by common stamping are relatively high, while the side surfaces of the aluminum terminals obtained by precise stamping are basically bright bands, and the proportion is more than 98%. The condition of the bright band is determined by projector detection and the duty cycle of the bright band is determined by calculating the length or area. The roughness before and after polishing of the front surface of the aluminum terminal material was 0.315 μm and 0.282 μm, respectively, and it can be seen that the surface roughness can be greatly reduced and the finish can be improved by polishing, wherein the sampling cut-off wavelength λc=0.8mm×5 of the filter in the roughness test.
The composite corrosion-resistant temperature impact-resistant layer comprises a zinc layer, a secondary zinc-depositing layer, an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer which are arranged in the full-exposure area on the surface of the aluminum terminal material, wherein the thicknesses of the zinc layer, the secondary zinc-depositing layer, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer and the tin layer are respectively 0.5 mu m, 2 mu m, 10 mu m, 8 mu m and 15 mu m. After the composite corrosion-resistant layer is formed, the roughness of the surface of the aluminum terminal is also improved and reduced to 0.196 μm.
Example 2
The present embodiment provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, wherein:
the front surface of the aluminum terminal material is subjected to rolling and polishing treatment, the roughness is smaller than Ra 0.8, the side surface is processed by a precision stamping process, the bright band is larger than 98%, and the roughness is smaller than Ra 0.8;
the composite corrosion-resistant temperature impact-resistant layer comprises a zinc layer, a secondary zinc-depositing layer, an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer which are arranged in the full-exposure area on the surface of the aluminum terminal material, wherein the thicknesses of the zinc layer, the secondary zinc-depositing layer, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer and the tin layer are respectively 0.5 mu m, 2 mu m, 15 mu m, 10 mu m and 20 mu m.
Example 3
The present embodiment provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, wherein:
the front surface of the aluminum terminal material is subjected to rolling and polishing treatment, the roughness is smaller than Ra 0.8, the side surface is processed by a precision stamping process, the bright band is larger than 98%, and the roughness is smaller than Ra 0.8;
the composite corrosion-resistant temperature impact-resistant layer comprises a zinc layer, a secondary zinc-depositing layer, an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer which are arranged in a semi-exposed area on the surface of the aluminum terminal material, wherein the thicknesses of the zinc layer, the secondary zinc-depositing layer, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer and the tin layer are respectively 0.5 mu m, 2 mu m, 1 mu m and 3 mu m.
Example 4
The present embodiment provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, wherein:
The front surface of the aluminum terminal material is subjected to rolling and polishing treatment, the roughness is smaller than Ra 0.8, the side surface is processed by a precision stamping process, the bright band is larger than 98%, and the roughness is smaller than Ra 0.8;
the composite corrosion-resistant temperature impact-resistant layer comprises a zinc layer, a secondary zinc-depositing layer, an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer which are arranged in a semi-exposed area on the surface of the aluminum terminal material, wherein the thicknesses of the zinc layer, the secondary zinc-depositing layer, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer and the tin layer are respectively 0.5 mu m, 2 mu m, 3 mu m, 5 mu m and 7 mu m.
Example 5
The present embodiment provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, wherein:
the front surface of the aluminum terminal material is subjected to rolling and polishing treatment, the roughness is smaller than Ra 0.8, the side surface is processed by a precision stamping process, the bright band is larger than 98%, and the roughness is smaller than Ra 0.8;
the composite corrosion-resistant temperature impact-resistant layer comprises a zinc layer, a secondary zinc-depositing layer, an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer which are arranged in a semi-exposed area on the surface of the aluminum terminal material, wherein the thicknesses of the zinc layer, the secondary zinc-depositing layer, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer and the tin layer are respectively 0.5 mu m, 2 mu m, 3 mu m, 5 mu m, 18 mu m and 7 mu m.
Example 6
The present embodiment provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, wherein:
the front surface of the aluminum terminal material is subjected to rolling and polishing treatment, the roughness is smaller than Ra 0.8, the side surface is processed by a precision stamping process, the bright band is larger than 98%, and the roughness is smaller than Ra 0.8;
The composite corrosion-resistant temperature impact-resistant layer comprises a zinc layer, a secondary zinc-depositing layer, an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer which are arranged in the full-exposure area on the surface of the aluminum terminal material, wherein the thicknesses of the zinc layer, the secondary zinc-depositing layer, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer and the tin layer are respectively 0.5 mu m, 2 mu m, 3 mu m, 5 mu m and 29 mu m.
Comparative example 1
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant composite layer only comprises a zinc layer, a secondary zinc precipitation layer and an alkali copper layer, and the thickness of the composite layer is 0.5 mu m, 2 mu m and 35 mu m.
The thickness of each comparative example was kept as compared with example 1, and the total thickness of each layer was unchanged.
Comparative example 2
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant composite layer only comprises a zinc layer, a secondary zinc-precipitation layer and a pyrocopper layer, and the thickness of the composite layer is 0.5 mu m, 2 mu m and 35 mu m.
Comparative example 3
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant composite layer only comprises a zinc layer, a secondary zinc precipitation layer and a nickel sulfamate layer, and the thickness of the composite layer is 0.5 mu m, 2 mu m and 35 mu m.
Comparative example 4
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant composite layer only comprises a zinc layer, a secondary zinc-precipitation layer and a tin layer, and the thickness of the composite layer is 0.5 mu m, 2 mu m and 35 mu m.
Comparative example 5
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant impact-resistant composite layer omits an alkali copper layer, and only comprises a zinc layer, a secondary zinc precipitation layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer, wherein the thickness of the alkali copper layer is 0.5 mu m, 2 mu m, 12 mu m, 8 mu m and 15 mu m.
Comparative example 6
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant impact-resistant composite layer omits a pyrocopper layer, and only comprises a zinc layer, a secondary zinc precipitation layer, an alkali copper layer, a nickel sulfamate layer and a tin layer, wherein the thickness of the pyrocopper layer is 0.5 mu m, 2 mu m, 12 mu m, 8 mu m and 15 mu m.
Comparative example 7
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant impact-resistant composite layer omits a nickel sulfamate layer, and only comprises a zinc layer, a secondary zinc precipitation layer, an alkali copper layer, a pyrocopper layer and a tin layer, wherein the thickness of the nickel sulfamate layer is 0.5 mu m, 2 mu m, 10 mu m and 23 mu m.
Comparative example 8
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the corrosion-resistant and temperature-resistant impact-resistant composite layer omits a tin layer, and only comprises a zinc layer, a secondary zinc deposition layer, an alkali copper layer, a pyrocopper layer and a nickel sulfamate layer, wherein the thickness of the tin layer is 0.5 mu m, 2 mu m, 10 mu m and 23 mu m.
Comparative example 9
This comparative example provides a wire cut aluminum: the plating was the same as in example 1, and was not subjected to precision press and polishing treatment.
Comparative example 10
This comparative example provides an aluminum terminal having a corrosion-resistant and temperature-resistant composite layer, which differs from example 1 in that: the plating was the same as in example 1, without the roll treatment.
Comparative examples 11 to 14
These comparative examples each provide an aluminum terminal with a corrosion resistant composite layer, which differs from example 3 in that: the coating thickness was different from that of example 3, and is shown in Table 1.
Comparative example 15
This comparative example provides an aluminum terminal with a corrosion resistant composite layer, which differs from example 1 in that: the coating thickness was different from that of example 1, and is shown in Table 1.
Comparative example 16
This comparative example provides an aluminum terminal with a transition layer and a conventional electroless nickel layer on the surface.
The results of the salt spray corrosion resistance test after the temperature impact cycle test of the aluminum terminal of the example and the comparative example and the wire cut aluminum material of the comparative example are shown in table 1.
TABLE 1
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The temperature impact experiment is according to national standard: GB/T2423.22-2012, specifically: the sample is firstly kept at the temperature of minus 40 ℃ for 30min, then is transferred to 140 ℃ for 30min in 30s, and is kept at the temperature of minus 40 ℃ for 30min and is kept at the temperature of 140 ℃ for 30min for 100 times, and then salt spray corrosion resistance experiment is carried out according to national standard GB/T2423.17-2008. And (5) qualification standard: the coating has no corrosion, no surface pitting, peeling, bubbling and the like, and no speckles and color change.
Test results:
the following properties are compared with conventional plated terminals: 1. SEM after temperature cycling (see its coating breakage); 2. salt fog after temperature cycling (see its corrosion resistance). The test results are shown in FIG. 5, wherein the graph a in FIG. 5 shows the conventional coating after 100 times of temperature impact, the graph b shows the coating of the invention example 1 after 100 times of temperature impact, the graph c shows the conventional coating without temperature impact, and the graph d shows the coating of the invention example 1 without temperature impact.
As can be seen from fig. 5: the corrosion resistance of the aluminum terminal after temperature impact is reduced more, and corrosion points are obviously more than those of a sample piece which does not do temperature impact; the conventional plating (only tinning) has poorer corrosion resistance than the plating of the invention, and has more serious corrosion no matter whether the temperature impact experiment is carried out or not.
Comparative example 16 is a electroless nickel plating 3 μm thick on the transition layer. After temperature cycling, the sample showed corrosion in salt spray resistance experiment 12H.
After the corrosion-resistant and temperature-resistant impact composite layer is subjected to 100 times of temperature impact, salt spray corrosion resistance test is carried out, and the test shows that: the corrosion-resistant and temperature-resistant composite layer can still not generate corrosion in a 240H salt spray test, and a good state is maintained.
Fig. 6 is a surface SEM image and a side cross-sectional metallographic image of a conventional plating layer (nickel plating) before and after temperature impact.
As can be seen from fig. 6: obvious cracks can be seen in the conventional nickel coating after temperature impact under SEM, and after section metallographic test, obvious cracks on the side surface can be observed, which shows that the temperature impact has great influence on the coating, so that the coating is invalid and the protection of the terminal is lost.
Fig. 7 is a side cross-sectional metallographic image of a conventional plating layer (nickel plating) after temperature impact and a plating layer of example 1 of the present invention, wherein the left drawing is the conventional plating layer and the right drawing is the plating layer of example 1 of the present invention.
As can be seen from fig. 7: the coating of the embodiment 1 of the invention can effectively bear temperature impact without generating cracks, has good extensibility in the environment of rapid temperature change, and maintains the integrity of the coating.
And (3) binding force test: the aluminum terminal obtained in example 1 of the present invention was baked at 220℃for 30 minutes and then quenched in water without adhesion defects such as peeling and foaming.
The salt spray corrosion resistance of the aluminum terminal provided by the embodiment 3 of the present invention with the corrosion-resistant and temperature-resistant composite layer in the semi-exposed area can reach 48H, although the corrosion-resistant time is inferior to that of the embodiment 1, the test is performed in the condition of being completely exposed to the salt spray environment, but in the actual use process of the aluminum terminal, the area is not completely exposed to the environment, therefore, the corrosion-resistant time obtained by the test of the embodiment 3 is lower than that of the embodiment 1, the service life of the aluminum terminal is not affected, and the corrosion-resistant and temperature-resistant composite layer still can exert good corrosion-resistant effect, namely, if the corrosion-resistant and temperature-resistant composite layer in the embodiment 3 is arranged in the semi-exposed area of the aluminum terminal of the embodiment 1, the service life of the corrosion-resistant and temperature-resistant composite layer in the semi-exposed area is not lower than that of the corrosion-resistant and temperature-resistant composite layer in the exposed area, and the corrosion resistance of the whole aluminum terminal is ensured.
Based on the method, different corrosion-resistant and temperature-resistant impact composite layers can be arranged at different positions of the aluminum terminal according to regional characteristics (whether the aluminum terminal is exposed to the environment or not, the corrosion resistance is required to be high or low), the use requirement and the like, so that the cost can be reduced under the condition of ensuring the corrosion resistance and the service life.
Experiment of influence of surface roughness and bright band on corrosion resistance:
example 7, comparative example 9 and comparative examples 17 to 19 formed the same corrosion-resistant layer (i.e., the corrosion-resistant layer in example 1) on the surface of the terminal (including wire cut material) having different surface roughness (surface roughness before the corrosion-resistant layer was prepared), different bright band duty ratio, and salt spray resistance test (performed according to national standard GB/T2423.17-2008) was performed to evaluate the effect of the surface roughness, bright band duty ratio on the salt spray corrosion resistance performance, the qualification standard: the coating has no corrosion, no surface pitting, peeling, bubbling and the like, and no speckles and color change. The experimental results are shown in table 2.
TABLE 2
From the experimental data given in table 2 for example 7, comparative example 17, comparative example 18, it can be seen that: under the condition that other conditions are the same, the smaller the surface roughness of the surface of the base material is, the longer the salt spray resistance time of the aluminum terminal with the corrosion-resistant composite layer on the surface is, and the better the salt spray corrosion resistance is;
from the experimental data given in table 2 for example 7, comparative example 19, comparative example 9, it can be seen that: under the conditions of the same other conditions and the similar surface roughness, the higher the bright band ratio of the surface of the base material, the longer the salt spray resistance time of the aluminum terminal with the corrosion-resistant composite layer on the surface, and the better the salt spray corrosion resistance.
The technical scheme of the invention has the following advantages:
1. the cost is low, and the process is simple; 2. the composite layer has excellent performance and can still have good corrosion resistance after being subjected to temperature cycle impact; after temperature cycle impact, the requirement of 240H on salt spray corrosion resistance can be met when a thicker tin layer is adopted, the requirement of 48H on salt spray corrosion resistance can be met when a thinner tin layer is adopted, different conditions can be met, and different corrosion resistance requirements can be met; 3. the adhesive force of each layer is excellent; 4. the aluminum terminal surface is provided with a corrosion-resistant and temperature-resistant composite layer, but the conductivity is still very good.
Claims (16)
1. A tin layer-based corrosion-resistant temperature impact-resistant composite layer comprising: an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer;
wherein: the thickness of the alkali copper layer is 1-10 mu m, the thickness of the pyrocopper layer is 2-18 mu m, the thickness of the nickel sulfamate layer is 0.5-28 mu m, and the thickness of the tin layer is 3-30 mu m;
preferably, the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer and the tin layer are sequentially arranged.
2. The corrosion-resistant and temperature-resistant composite layer according to claim 1, wherein the alkali copper layer has a thickness of 1-6 μm.
3. The corrosion-resistant and temperature-resistant composite layer according to claim 1, wherein the thickness of the pyrocopper layer is 5-15 μm.
4. The corrosion-resistant and temperature-resistant composite layer according to claim 1, wherein the nickel sulfamate layer has a thickness of 0.5-18 μm.
5. The corrosion-resistant and temperature-resistant composite layer according to claim 1, wherein the tin layer has a thickness of 3-10 μm or 10-25 μm.
6. The corrosion-resistant temperature impact-resistant composite layer according to claim 1, further comprising a transition layer provided on a side of the alkali copper layer not in contact with the pyrocopper layer;
preferably, the transition layer is a zinc layer, or a zinc layer and a secondary zinc precipitation layer;
preferably, the zinc layer has a thickness of 0.1 to 10.0 μm, more preferably 0.5 to 1 μm;
preferably, the thickness of the secondary zinc layer is 0.1-10 μm, more preferably 1.5-2.5 μm.
7. The corrosion-resistant and temperature-resistant composite layer according to any one of claims 1 to 6, wherein the alkali copper layer, the pyrocopper layer, the nickel sulfamate layer, and the tin layer are respectively electroplated layers.
8. The corrosion-resistant temperature impact-resistant composite layer according to any one of claims 1 to 7, further comprising a chemical copper layer provided on a surface of the alkaline copper layer or a surface of the pyrocopper layer;
Preferably, the thickness of the electroless copper layer is 3-25 μm, more preferably 5-15 μm.
9. The corrosion-resistant temperature impact-resistant composite layer according to any one of claims 1 to 8, further comprising a copper acid layer provided on a surface of the alkali copper layer or a surface of the pyrocopper layer;
preferably, the thickness of the acid copper layer is 1 to 20 μm, more preferably 3 to 10 μm.
10. The corrosion-resistant temperature impact-resistant composite layer according to any one of claims 1-9, wherein the corrosion-resistant temperature impact-resistant composite layer further comprises a wattage nickel layer provided on a surface of the nickel sulfamate layer;
preferably, the thickness of the watt nickel layer is 1-20 μm, more preferably 3-9 μm.
11. The method for preparing the tin layer-based corrosion-resistant and temperature-resistant composite layer according to any one of claims 1 to 10, comprising the steps of:
sequentially forming an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer on the surface of the base material in an electroplating manner;
preferably, the alkaline copper layer uses a plating solution containing cuprous cyanide based on the total volume of the plating solution: 40-50g/L, total sodium cyanide: 40-60g/L, free sodium cyanide: 8-14g/L, potassium sodium tartrate: 30-45g/L, sodium hydroxide: 1-3g/L of additive: 3-5mL/L; the temperature of the alkaline copper layer is 40-50 ℃, and the area ratio of anode to cathode is 1:1-2 (preferably 1:1.5) and a current density of 0.7-1.2A/dm 2 Electroplating for 5-15min;
preferably, the plating solution used for the pyrocopper layer contains copper pyrophosphate, based on the total volume of the plating solution: 50-70g/L, potassium pyrophosphate: 300-450g/L, ammonium citrate: 15-30g/L, ammonia water: 2-5mL/L; the temperature of the electroplated copper coke layer is 40-50 ℃ and the current density is 0.7-1.2A/dm 2 The area ratio of the cathode to the anode is 1:1-2 (preferably 1:1.5), and the electroplating time is 50-90min (preferably 70 min);
preferably, the plating solution used for the nickel sulfamate layer contains nickel sulfamate, based on the total volume of the plating solution: 300-500g/L, nickel chloride: 10-25g/L, boric acid: 30-40g/L sulfamic acid: 100-150g/L, additive: 5-10ml/L; the temperature of the electroplated nickel sulfamate layer is 50-60 ℃ and the current density is 0.8-1.2A/dm 2 The area ratio of the cathode to the anode is 1:1-2 (preferably 1:1.5), and the electroplating time is 1-80min (preferably 40-60min, preferably 50 min);
preferably, the plating solution used for the tin layer contains stannous sulfate based on the total volume of the plating solution: 10-50g/L, sulfuric acid: 60-190ml/L, gelatin: 1-10g/L, formaldehyde: 5-10ml/L, benzalacetone: 5-30g/L; the temperature of the electroplated tin layer is 10-40deg.C, the area ratio of cathode to anode is 1:1-2 (preferably 1:1.5), and the current density is 0.5-2A/dm 2 (preferably 0.7-1.2A/dm) 2 ) The electroplating time is 15-120min (preferably 60 min).
12. An aluminum substrate corrosion-resistant and temperature-resistant impact treatment method comprising the step of arranging the tin layer-based corrosion-resistant and temperature-resistant impact composite layer according to any one of claims 1 to 10 on the surface of an aluminum substrate.
13. The method of claim 12, wherein the corrosion resistance is salt spray corrosion resistance and the temperature shock resistance is temperature cycle shock resistance.
14. The method according to claim 12, wherein the surface of the aluminum substrate has a roughness of less than Ra 3.6, preferably less than Ra 0.8.
15. A corrosion-resistant and temperature-resistant aluminum terminal, wherein a part or all of the area of the surface of the corrosion-resistant and temperature-resistant aluminum terminal is provided with the tin-layer-based corrosion-resistant and temperature-resistant composite layer as claimed in any one of claims 1 to 10.
16. The method for preparing the corrosion-resistant and temperature-resistant aluminum terminal of claim 15, comprising the steps of:
the front surface of the aluminum terminal is subjected to a rolling treatment and a polishing treatment, preferably, the front surface roughness of the aluminum terminal subjected to the rolling treatment and the polishing treatment is less than Ra 3.6, more preferably less than Ra 0.8;
the side surface of the aluminum terminal is subjected to punching treatment, preferably, the side surface roughness of the aluminum terminal subjected to rolling treatment is less than Ra 3.6 (more preferably less than Ra 0.8), and the bright band is more than 50% (more preferably more than 98%);
Forming an alkali copper layer, a pyrocopper layer, a nickel sulfamate layer and a tin layer on the front surface and the side surface of the treated aluminum terminal in sequence through electroplating to achieve the corrosion-resistant and temperature-resistant aluminum terminal;
preferably, the transition layers are formed on the front and side surfaces of the treated aluminum terminal prior to the formation of the alkaline copper layer by electroplating.
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