CN113215628A - Electroplating solution and application thereof - Google Patents
Electroplating solution and application thereof Download PDFInfo
- Publication number
- CN113215628A CN113215628A CN202110490015.0A CN202110490015A CN113215628A CN 113215628 A CN113215628 A CN 113215628A CN 202110490015 A CN202110490015 A CN 202110490015A CN 113215628 A CN113215628 A CN 113215628A
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- Prior art keywords
- plastic
- solution
- electroplating
- deionized water
- weight
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- Granted
Links
- 238000009713 electroplating Methods 0.000 title claims abstract description 115
- 229920003023 plastic Polymers 0.000 claims abstract description 178
- 239000004033 plastic Substances 0.000 claims abstract description 178
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000002156 mixing Methods 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000008139 complexing agent Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 239000003381 stabilizer Substances 0.000 claims abstract description 31
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 16
- 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 claims abstract description 15
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 15
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 171
- 239000008367 deionised water Substances 0.000 claims description 82
- 229910021641 deionized water Inorganic materials 0.000 claims description 82
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 70
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 66
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 229920001661 Chitosan Polymers 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000004140 cleaning Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 230000003213 activating effect Effects 0.000 claims description 33
- 238000006386 neutralization reaction Methods 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 30
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 30
- 229920002873 Polyethylenimine Polymers 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 230000008961 swelling Effects 0.000 claims description 28
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 25
- 235000006408 oxalic acid Nutrition 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 22
- 230000001235 sensitizing effect Effects 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000002791 soaking Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- -1 sulfhydryl compound Chemical class 0.000 claims description 14
- GWTZZUPJEUZZLU-UHFFFAOYSA-N 5,5-diethylimidazolidine-2,4-dione Chemical compound CCC1(CC)NC(=O)NC1=O GWTZZUPJEUZZLU-UHFFFAOYSA-N 0.000 claims description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 13
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 12
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims description 12
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229940015043 glyoxal Drugs 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 12
- 239000001119 stannous chloride Substances 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 206010070834 Sensitisation Diseases 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000001103 potassium chloride Substances 0.000 claims description 11
- 235000011164 potassium chloride Nutrition 0.000 claims description 11
- 238000007781 pre-processing Methods 0.000 claims description 11
- 230000008313 sensitization Effects 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims description 2
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003585 thioureas Chemical class 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- OKFGMSNMXNMZKQ-UHFFFAOYSA-N [Ni].[Cu].[Cu].[Zn] Chemical compound [Ni].[Cu].[Cu].[Zn] OKFGMSNMXNMZKQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005057 refrigeration Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001431 copper ion Inorganic materials 0.000 abstract description 9
- 230000010287 polarization Effects 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 206010042674 Swelling Diseases 0.000 description 26
- 239000010410 layer Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007788 roughening Methods 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical compound SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses an electroplating solution and application thereof, wherein the electroplating solution is prepared by mixing 1-3 wt% of copper sulfate, 1.5-5 wt% of sodium hypophosphite, 1-3 wt% of complexing agent, 0.1-1 wt% of accelerator, 0.1-1 wt% of stabilizer and the balance of water. The complexing agent, the stabilizing agent and the accelerator are added into the electroplating solution, so that the precipitation speed of copper ions in the electroplating process is effectively controlled, the occurrence of polarization phenomenon is reduced, and the uniformity and the stability of a plating layer are improved. The electroplating solution is used for electroplating the surface of the plastic, so that the wear resistance, the corrosion resistance and the binding force between the metal coating and the plastic are effectively improved.
Description
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to electroplating solution and application thereof.
Background
Electroplating is a metal electrodeposition method for reducing metal ions in electroplating solution and depositing the metal ions on the surface of a material under direct current, and compared with surface treatment methods such as a vapor deposition mode and a coating, the method has the characteristics of uniform coating, moderate thickness, high speed and the like. The good electroplating solution can increase the stability and the oxidation resistance of the solution, improve the quality of a plating layer and enlarge the cathode current density range of metal. The plastic product has the advantages of easy processing, light weight, chemical stability and the like, and is widely applied to aspects of agriculture, industry, building, packaging and the like, but in some applications, the heat resistance, wear resistance and corrosion resistance of the plastic are still to be improved. The surface metallization of the plastic is an effective means, so that the advantages of the plastic, such as high rigidity, low density, high strength and easiness in processing, can be ensured, and the conductivity, wear resistance, magnetic conductivity, appearance and the like of the plastic can be improved. Generally, plastic is difficult to be completely soaked due to chemical inertness and hydrophobicity, so that the plastic is difficult to deposit on the surface of the plastic with metals such as silver, copper and the like, and a metal coating and the plastic are poor in adhesion, so that the phenomena of falling, bubbling and even plating leakage are easy to occur. Therefore, it is important to provide a plating solution and a method for plating a plastic surface that can solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides electroplating solution and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the first aspect of the invention provides a preparation method of electroplating solution, which comprises the steps of mixing 1-3 wt% of copper sulfate, 1.5-5 wt% of sodium hypophosphite, 1-3 wt% of complexing agent, 0.1-1 wt% of accelerator, 0.1-1 wt% of stabilizer and the balance of water, and then adjusting the pH value to 10-13 by using 1-4mol/L of sodium hydroxide.
The accelerator is any one of guanidine, glycine, benzotriazole, mercaptopyridine and mercaptopyrimidine; preferably, the accelerator is glycine.
The stabilizer is any one of 5, 5-diethyl hydantoin, thiourea derivatives, persulfate or thiosulfate; preferably, the stabilizer is 5,5 diethylhydantoin.
The complexing agent is chitosan or sulfhydryl chitosan.
The electroplating solution in the invention takes copper sulfate as a plating layer metal solution, sodium hypophosphite as a non-toxic and harmless reducing agent, a complexing agent for complexing copper ions, the speed of the electroplating process is effectively controlled, and a stabilizer for stabilizing the stability of the electroplating solution enables the electroplating solution to be uniform and stable, thereby improving the performance of the plating layer.
In the conventional electroless copper plating process, since the chemical equilibrium and the reduction potential value according to the chemical equilibrium are also changed by the polarization phenomenon generated at the time of deposition by the reduction reaction of copper ions, overvoltage is generated, and the mass transfer of copper ions is slow in the solution interior, and concentration polarization or a combination of both types of polarization phenomena occurs if the concentration deviation of the interface is increased. As a result, the rate of copper precipitation becomes very slow or even ceases, causing the coating to slow or cease to occur, ultimately resulting in non-uniformity and instability of the coating. Therefore, it is required to minimize the polarization phenomenon, which requires a proper control of the copper precipitation rate, an inhibition of electron movement or mass transfer by the addition of an accelerator or a copper complex ion salt, and a significant decrease in the concentration of free copper ions present in the plating solution after the addition of a complexing agent, which can effectively control the rapid-acting of the plating layer, and the kind and concentration of the complexing agent have a great influence on the copper precipitation rate.
Although chitosan has stronger complexing and adsorbing capacity, good mechanical property, high fixing efficiency and stable chemical property, the adhesion and the complexing property are further enhanced after the chitosan molecules are connected with sulfydryl, the chitosan can be effectively adsorbed on the surface of an electrode, and the sulfydryl chitosan has the characteristics of good stability and longer service life. The sulfhydryl group is easy to oxidize to form a disulfide bond, thereby forming a network structure and having obvious adsorption effect. The introduction of sulfhydryl groups imparts new biological properties to chitosan: when the content of sulfydryl is increased, the contact time between the mucous membrane and the thiolated chitosan is prolonged, and when the pH value is increased, the activity of sulfydryl is enhanced, and a plurality of disulfide bonds are formed inside the thiolated chitosan molecules.
According to the invention, the sulfydryl chitosan is obtained by reacting chitosan with sulfydryl polyethyleneimine or N-acetyl-L-cysteine, has a network structure, ensures the stability of plating solution, and can form a copper plating layer with hardness and flexibility required by the plating layer; in addition, a higher plating layer formation speed can be provided, and even if the number of times of use of the plating solution is increased, the utilization rate of the substance is improved, and the plating layer has excellent corrosion resistance and wear resistance.
Preferably, the complexing agent is sulfhydryl chitosan; the preparation method of the mercapto chitosan comprises the following steps:
mixing 0.5-3 parts by weight of chitosan, 0.5-1.5 parts by weight of N-hydroxysuccinimide and 50-100 parts by weight of water, stirring at the room temperature of 500rpm for 1-5min under 300-2 ℃, adding 1-6 parts by weight of sulfhydryl compound, adjusting the pH value of the reaction solution to 4-6 by using 0.5-2mol/L NaOH, reacting for 1-3h under the stirring at the temperature of 800rpm under 500-50 ℃, adding 50-80 parts by weight of absolute ethyl alcohol, standing for 1-3h, performing suction filtration, washing for 2-5 times by using the absolute ethyl alcohol, performing vacuum drying at the temperature of 40-70 ℃ for 6-12h, and refrigerating and storing at the temperature of 0-8 ℃ to obtain the sulfhydryl chitosan.
The sulfhydryl compound is sulfhydrylation polyethyleneimine and/or N-acetyl-L-cysteine; preferably, the mercapto compound is a mercapto polyethyleneimine and N-acetyl-L-cysteine in a mass ratio of 1: (1-5) in the presence of a catalyst.
The preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 0.5-2 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 1-4 parts by weight of methyl thioglycolate for mixing, stirring at 50-70 ℃ and 300-500rpm for 6-10h to obtain a mixed solution A, carrying out reduced pressure concentration at the vacuum degree of 0.06-0.09MPa and the temperature of 40-60 ℃ until 1/5-1/3 of the mixed solution A, adding 2-10 parts by weight of deionized water for dissolving, adding 2-8 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at the vacuum degree of 0.05-0.1MPa and the temperature of 40-60 ℃ until 1/5-1/3 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine.
An electroplating solution is prepared by adopting the method.
In a second aspect, the present invention provides the use of the above-mentioned electroplating solution for electroplating plastic surfaces.
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the surface of the plastic for 5-10min at room temperature by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1 (1-2); cleaning with 40-60 deg.C sodium carbonate water solution with pH of 7-8.5 for 3-10min, ultrasonic cleaning with acetic acid with pH of 5-6.5 at room temperature for 1-3min, and cleaning with 30-50 deg.C water for 2-5min to obtain pretreated plastic;
s2, coarsening: soaking the pretreated plastic in swelling solution at 30-50 deg.C for 5-15min, and then in microetching solution at 50-65 deg.C, and treating at ultrasonic frequency of 20-40kHz and ultrasonic power of 120-;
s3, neutralization: immersing the microetching plastic into a neutralization solution, stirring for 5-15min at 50-70 ℃ and 200-500rpm, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, 15-50 wt% of sulfuric acid and 1-5 wt% of oxalic acid are taken out and washed for 2-5min by deionized water;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 20-40min at 30-50 ℃, wherein the sensitizing solution is prepared by mixing 0.01-0.1 wt% of palladium chloride, 1-5 wt% of stannous chloride, 30-40 wt% of hydrochloric acid with the concentration of 20-40ml/L, 10-25 wt% of potassium chloride and the balance of deionized water;
s5, activation: placing the sensitized plastic in an activating solution, and activating at the room temperature and at the speed of 300-500rpm for 3-10min, wherein the activating solution is formed by mixing 1-5 wt% of silver nitrate, 0.5-2 wt% of ammonia water, 2-10 wt% of glyoxal, 0.5-3 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 20-30 ℃, and the current density is 0.5-2.0A/dm2Electroplating for 20-50 min;
s7, finished product: drying the electroplated plastic at 50-70 deg.C for 1-3h, and cooling to room temperature to obtain the plastic surface metal coating. The thickness of the metal plating layer is 0.2-10 μm.
The plastic is any one of polycarbonate plastic, ABS plastic and polyimide plastic.
The plastic surface shows obvious chemical inertness and hydrophobicity, is difficult to be completely soaked with aqueous solution, is difficult to form chemically bonded active functional groups with metals such as silver, copper, nickel and the like, and is difficult to induce the deposition of the metals. According to the invention, a specific swelling solution is firstly adopted for treatment in the roughening preparation process of the metal coating, so that on one hand, a swelling agent penetrates through the surface of the polymer to form a porous channel capable of penetrating into the polymer, thus the contact surface area between the substrate and the microetching agent is increased, and the oxidation-reduction reaction rate in the microetching process is increased; on the other hand, hydrophilic polar groups such as-COOH, -OH, -CHO and the like are formed on the surface of the plastic after the swelling treatment, so that reaction points on the surface of the substrate are fully exposed, and the two factors can obviously enhance the bonding strength between the substrate and the chemical plating layer.
The swelling solution is prepared by mixing 10-25 wt% of 5-carboxyl benzotriazole, 20-40 wt% of N-methyl pyrrolidone, 10-20 wt% of potassium hydroxide, 5-15 wt% of N, N-dimethylformamide and the balance of deionized water.
The micro-scaleThe etching solution comprises 20-30 wt% of phosphoric acid, 50-65 wt% of sulfuric acid and 3-8 wt% of MnO20.01 to 0.05 weight percent of hexadecyl trimethyl ammonium bromide, 0.1 to 1 weight percent of sodium tripolyphosphate and the balance of deionized water.
The invention has the beneficial effects that: the complexing agent, the stabilizing agent and the accelerator are added into the electroplating solution, so that the precipitation speed of copper ions in the electroplating process is effectively controlled, the occurrence of polarization phenomenon is reduced, and the uniformity and the stability of a plating layer are improved. The plastic surface electroplating method provided by the invention can effectively improve the wear resistance and the corrosion resistance, the bonding property between the metal coating and the plastic is strong, and the service life is prolonged.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
in the examples, the polycarbonate plastics are purchased from Yongde metallocene science and technology Limited of Shenzhen.
Examples cetyltrimethylammonium bromide, CAS: 57-09-0.
Examples sodium tripolyphosphate, CAS: 7758-29-4.
Examples oxalic acid, CAS: 144-62-7.
Examples palladium chloride, CAS: 7647-10-1.
Examples stannous chloride, CAS: 7772-99-8.
Examples glyoxal, CAS: 107-22-2.
Examples triethanolamine, CAS: 102-71-6.
Example 1, 2-cyclohexanediaminetetraacetic acid, CAS: 13291-61-7.
Copper sulfate, CAS: 7758-98-7.
Examples sodium hypophosphite, CAS: 7681-53-0.
MnO in examples2，CAS：1313-13-9。
Example 5,5 diethylhydantoin, CAS: 5455-34-5.
Example 4-mercaptopyridine, CAS: 4556-23-4.
Examples sodium persulfate, CAS: 7775-27-1.
Example 5-Carboxybenzotriazole, CAS: 23814-12-2.
Examples N-methylpyrrolidone, CAS: 872-50-4.
Examples N, N-dimethylformamide, CAS: 68-12-2.
In the examples, chitosan was purchased from wuhan woxuan science ltd, CAS: 9012-76-4, and the content of active substances is as follows: 99%, molecular weight: 3000 g/mol.
Examples N-hydroxysuccinimide, CAS: 6066-82-6.
Examples N-acetyl-L-cysteine, CAS: 616-91-1.
In the examples, polyethyleneimine is available from pharmaceutical chemicals, Inc. of Wuhan La Na white, CAS: 26658-46-8, molecular weight: 10000 g/mol.
Examples ethyl thioglycolate, CAS: 623-51-8.
Example 1
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: putting the pretreated plastic into microetching liquid with the ultrasonic power of 160W and the ultrasonic frequency of 25kHz at 55 ℃ for treating for 20min to obtain microetching plastic; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, washing with deionized water for 3 times;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid with the concentration of 30ml/L, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is 4-mercaptopyridine; the stabilizer is sodium persulfate; the complexing agent is chitosan.
Example 2
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling liquid is 20wt% 5-carboxyl benzotriazole, 30 wt% N-methyl pyrrolidone, 15 wt% potassium hydroxide, 10 wt% N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, washing with deionized water for 3 times;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid with the concentration of 30ml/L, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is 4-mercaptopyridine; the stabilizer is sodium persulfate; the complexing agent is chitosan.
Example 3
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is sodium persulfate; the complexing agent is chitosan.
Example 4
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is chitosan.
Example 5
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of glycine, 0.2 wt% of 5,5 diethyl hydantoin and the balance of deionized water, and adjusting the pH value to 11 by using 2mol/L of sodium hydroxide;
the electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is sulfhydryl chitosan.
The preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 30-50 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, carrying out suction filtration, washing for 3 times by using the absolute ethyl alcohol, carrying out vacuum drying at 50 ℃ for 10h, and carrying out cold storage at 4 ℃ to obtain the sulfhydryl chitosan; the sulfhydryl compound is N-acetyl-L-cysteine.
Example 6
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is sulfhydryl chitosan.
The preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 30-50 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, carrying out suction filtration, washing for 3 times by using the absolute ethyl alcohol, carrying out vacuum drying at 50 ℃ for 10h, and carrying out cold storage at 4 ℃ to obtain the sulfhydryl chitosan;
the mercapto compound is mercapto polyethyleneimine;
the preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 1.5 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 2 parts by weight of methyl thioglycolate, mixing, stirring at 60 ℃ and 400rpm for 8 hours to obtain a mixed solution A, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution A, adding 3 parts by weight of deionized water for dissolution, adding 5 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine.
Example 7
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin;
the complexing agent is sulfhydryl chitosan; the preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 40 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, performing suction filtration, washing for 3 times by using the absolute ethyl alcohol, performing vacuum drying at 50 ℃ for 10h, and performing cold storage at 4 ℃ to obtain sulfhydryl chitosan;
the mercapto compound is a mixture of mercapto polyethyleneimine and N-acetyl-L-cysteine according to a mass ratio of 1: 2;
the preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 1.5 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 2 parts by weight of methyl thioglycolate, mixing, stirring at 60 ℃ and 400rpm for 8 hours to obtain a mixed solution A, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution A, adding 3 parts by weight of deionized water for dissolution, adding 5 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine.
Example 8
The preparation method of the wear-resistant ABS plastic comprises the following steps:
s1, preprocessing: firstly, cleaning ABS plastic for 10min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 8.5 at 60 deg.C for 10 min; cleaning with acetic acid water solution with pH of 6.5 for 3min, and cleaning with deionized water at 50 deg.C for 5min to obtain pretreated ABS plastic;
s2, coarsening: soaking the pretreated ABS plastic in swelling solution at 50 ℃ for 15min, then placing the soaked ABS plastic in microetching solution at 65 ℃ for 25min under the ultrasonic power of 200W and the ultrasonic frequency of 40kHz to obtain the microetching ABS plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl groupTrimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the micro-etched ABS plastic into a neutralization solution, and stirring for 15min at 70 ℃ and 500rpm, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized ABS plastic into a sensitizing solution, and soaking for 40min at 50 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized ABS plastic in an activating solution, and activating at room temperature and 500rpm for 10min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated ABS plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 30 ℃, and the current density is 2.0A/dm2Electroplating time is 50 min;
s7, finished product: drying the electroplated ABS plastic at 70 ℃ for 3h, and cooling to room temperature to obtain the wear-resistant ABS plastic.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is chitosan. The method of test example 2 is adopted to test the wear resistance of the wear-resistant ABS plastic of example 8, and the specific steps are as follows: the plastic surface was rubbed using a 7-IBB RCA abrader manufactured by nomen instruments, usa under 175 grams of force, and when the plastic matrix material was exposed, the number of revolutions of the rubber wheel was recorded, tested in parallel for 5 times, and averaged. Example 8 abrasion resistant ABS plastic has abrasion resistance 3510 cycles.
Example 9
The preparation method of the wear-resistant ABS plastic comprises the following steps:
s1, preprocessing: firstly, cleaning ABS plastic for 10min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 8.5 at 60 deg.C for 10 min; cleaning with acetic acid water solution with pH of 6.5 for 3min, and cleaning with deionized water at 50 deg.C for 5min to obtain pretreated ABS plastic;
s2, coarsening: soaking the pretreated ABS plastic in swelling solution at 50 ℃ for 15min, then placing the soaked ABS plastic in microetching solution at 65 ℃ for 25min under the ultrasonic power of 200W and the ultrasonic frequency of 40kHz to obtain the microetching ABS plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the micro-etched ABS plastic into a neutralization solution, and stirring for 15min at 70 ℃ and 500rpm, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized ABS plastic into a sensitizing solution, and soaking for 40min at 50 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized ABS plastic in an activating solution, and activating at room temperature and 500rpm for 10min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated ABS plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 30 ℃, and the current density is 2A/dm2Electroplating time is 50 min;
s7, finished product: drying the electroplated ABS plastic at 70 ℃ for 3h, and cooling to room temperature to obtain the wear-resistant ABS plastic.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin;
the complexing agent is sulfhydryl chitosan; the preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 40 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, performing suction filtration, washing for 3 times by using the absolute ethyl alcohol, performing vacuum drying at 50 ℃ for 10h, and performing cold storage at 4 ℃ to obtain sulfhydryl chitosan;
the mercapto compound is a mixture of mercapto polyethyleneimine and N-acetyl-L-cysteine according to a mass ratio of 1: 2;
the preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 1.5 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 2 parts by weight of methyl thioglycolate, mixing, stirring at 60 ℃ and 400rpm for 8 hours to obtain a mixed solution A, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution A, adding 3 parts by weight of deionized water for dissolution, adding 5 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine. The wear resistance test of the wear-resistant ABS plastic of example 9 by the method of test example 2 comprises the following steps: the plastic surface was rubbed using a 7-IBB RCA abrader manufactured by nomen instruments, usa under 175 grams of force, and when the plastic matrix material was exposed, the number of revolutions of the rubber wheel was recorded, tested in parallel for 5 times, and averaged. Example 9 the abrasion resistant ABS plastic had 4652 cycles of abrasion resistance.
Test example 1
Coating bonding strength: taking the sectional area (S) as 1cm2Copper cylinder (D) and plastic sheets prepared in examples 1 to 7And (3) bonding the surface metal coating by using an adhesive, performing pressure curing at room temperature for 24h, removing the adhesive around the copper column by using a knife, and cutting the coating around the copper column (to a plastic substrate) to obtain a sample. The sample is arranged on a tensile machine, a pull-off experiment is carried out by using a force vertical to the surface of a plated part until a metal plating layer is separated from a plastic substrate, a tensile value (N) is recorded, and the peel strength Fr can be obtained by calculating according to the following formula:
FH＝N/S；
Fr＝FH·σ3/4/5.5；
wherein, FHThe pull-off strength (N/cm) of the plastic coating2) Fr is the peel strength (N/cm) of the plastic plating layer, and σ is the thickness (cm) of the metal layer to be peeled;
bonding strength of a hot stamping circulating plating layer at-55 ℃ to +125 ℃: the plastic surface metal-plated parts described in examples 1 to 7 were sequentially subjected to standing at-55 deg.C for 60 minutes, at 25 deg.C for 60 minutes, at 125 deg.C for 60 minutes, and at 25 deg.C for 60 minutes, to complete 1 cycle of warm punching at-55 deg.C to +125 deg.C. After 5-55 to +125 ℃ warm punching cycles are carried out on the plastic surface metal coating piece, whether bubbles, peeling, layering or other visible deformation and damage appear on the metal coating layer of the plastic surface metal coating piece is observed, and if no visible deformation and damage appear, a coating bonding strength test is carried out on the plastic piece subjected to the 5-55 to 125 ℃ warm punching cycles.
TABLE 1 test results of coating bonding strength of plastic surface metal-coated parts
The above results show that the swelling treatment and then the microetching treatment are carried out in the roughening process, which can effectively improve the bonding strength between the plastic and the metal coating, and the specific comparison example 1-2 shows that the swelling treatment and then the microetching treatment are carried out in the roughening process, which has better effect because the swelling agent can penetrate through the surface of the polymer to form a porous channel which can penetrate into the polymer, increase the contact surface area between the plastic and the microetching agent, and form a microscopic rugged appearance on the surface of the substrate through the redox effect in the microetching process, so that the appearance not only can increase the contact area between the surface of the substrate and the coating, but also can enable the coating to deposit on the surface of the substrate to generate an anchor effect, and simultaneously, when the plastic surface is formed, hydrophilic polar groups such as-COOH, -CHO, -OH and the like can be formed on the surface of the substrate, the adhesive force between the plastic surface and the chemical plating layer is improved; compared with the examples 4-5, the mercapto chitosan is added into the electroplating solution as a complexing agent, so that the bonding performance of the plating layer can be improved, and the adhesion and the complexing performance are further enhanced after the mercapto is grafted on the chitosan molecules, so that the mercapto chitosan can be effectively adsorbed on the surface of an electrode and easily oxidized to form a disulfide bond, thereby forming a network structure and having a remarkable adsorption effect;
compared with examples 5-7, the compound of sulfhydrylation polyethyleneimine and N-acetyl-L-cysteine is added in example 7 to modify chitosan, and the complexation strength of sulfhydryl in the N-acetyl-L-cysteine and chitosan is very high, and the adsorbability is very strong; the complexing strength of the sulfhydrylation polyethyleneimine and the chitosan is not as strong as that of sulfhydrylation and the chitosan in the N-acetyl-L-cysteine, but the sulfhydrylation polyethyleneimine can play a role of a surfactant and effectively stabilize the stability of the electroplating solution, so that the sulfhydrylation polyethyleneimine can be uniformly adsorbed on an electrode in the electroplating process, and the sulfhydrylation polyethyleneimine and the electrode are synergistic, so that the binding force between metal and plastic is enhanced, and the service life is prolonged.
Test example 2
And (3) testing the wear resistance: the plastic surface metal coatings of examples 1-7 were rubbed using a 7-IBB RCA abrader from Noman instruments and Equipment, USA, under 175 grams of force, and when the electroplated product was exposed to the plastic substrate, the number of rubber wheel revolutions was recorded and was found to be acceptable, and the test was performed 5 times in parallel, and the average was taken.
TABLE 2 abrasion resistance test results
Compared with the embodiment 1-2, before electroplating, swelling treatment is firstly carried out and then micro-etching is carried out in the roughening process, so that the thickness of the plating layer can be effectively improved, the swelling agent can penetrate through the surface of the polymer to form a porous channel capable of penetrating into the polymer, the contact surface area between the plastic and the micro-etching agent is increased, the roughness of the surface of the plastic is increased, and meanwhile, when the roughening is formed on the surface of the plastic, hydrophilic polar groups such as-COOH, -CHO, -OH and the like are formed on the surface of the substrate, so that the binding force between the surface of the plastic and the chemical plating layer is improved, the thickness of the plating layer is increased, and the wear resistance is further improved; comparing examples 2-4, in example 4, glycine is added as an accelerator and 5, 5-diethylhydantoin is added as a stabilizer, so that the thickness of the plating layer can be increased within the same time, the accelerator is added, the polarization phenomenon can be reduced to the maximum extent, the generation of overvoltage is reduced, the mass transfer of copper ions is promoted, the uniformity and the thickness of the plating layer are improved, and the wear resistance is improved; in comparative examples 4 to 7, the concentration of free copper ions present in the plating solution after the complexing agent is added is reduced, and the rapid action of the plating layer can be effectively controlled, while the addition of the stabilizing agent reduces the surface tension of the plating solution, inhibits the precipitation of copper on the inactive surface, improves the utilization rate of the substance and the efficiency of the plating layer, and further improves the wear resistance.
Test example 3
Salt spray test: the plastic surface metal coatings of examples 1-7 were placed in a salt spray box, the plastic surface metal coatings were sprayed with 5 wt% sodium chloride brine at 35 ℃, the surface of the coatings was observed, the time taken for the appearance of white spots or rust on the surface of the plated products was recorded, and the test was conducted 5 times in parallel, and the average value was taken, if the time was more than 48 hours, the pass was determined.
TABLE 3 salt spray test results
From the above results, it can be seen that the addition of the accelerator and the stabilizer to the electroplating solution can improve the salt spray resistance of the metal coating on the plastic surface to some extent, and the possible reason is that the electroplating solution is more stable in the presence of the accelerator and the stabilizer, so that the coating can be uniformly electroplated on the plastic shell, and the salt spray resistance can be further improved; the addition of the complexing agent can obviously improve the salt spray resistance of the metal coating on the surface of the plastic, and the reason is that the copper ion binding property of the mercapto chitosan complex is stronger, a part of mercapto chitosan is adsorbed on an electroplated layer, and the mercapto chitosan has the sodium chloride corrosion resistance, so that the salt spray resistance of the metal coating on the surface of the whole plastic is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for preparing an electroplating solution, comprising the steps of: mixing 1-3 wt% of copper sulfate, 1.5-5 wt% of sodium hypophosphite, 1-3 wt% of complexing agent, 0.1-1 wt% of accelerator, 0.1-1 wt% of stabilizer and the balance of water, and adjusting the pH value to 10-13 by using 1-4mol/L of sodium hydroxide to obtain the copper-nickel-zinc-copper alloy.
2. The method for preparing an electroplating bath according to claim 1, wherein the accelerator is any one of guanidine, glycine, benzotriazole, mercaptopyridine, and mercaptopyrimidine; the stabilizer is any one of 5, 5-diethyl hydantoin, thiourea derivatives, persulfate or thiosulfate.
3. The method for preparing an electroplating solution according to claim 1, wherein the complexing agent is chitosan or mercaptochitosan; the preparation method of the mercapto chitosan comprises the following steps:
mixing 0.5-3 parts by weight of chitosan, 0.5-1.5 parts by weight of N-hydroxysuccinimide and 50-100 parts by weight of water, stirring at the room temperature of 500rpm for 1-5min under 300-2 mol/LNaOH, adding 1-6 parts by weight of sulfhydryl compound, adjusting the pH value of the reaction solution to 4-6, reacting at the stirring temperature of 800rpm under 500-50 ℃ for 1-3h, adding 50-80 parts by weight of absolute ethyl alcohol, standing for 1-3h, performing suction filtration, washing for 2-5 times with absolute ethyl alcohol, performing vacuum drying at the temperature of 40-70 ℃ for 6-12h, and performing refrigeration storage at the temperature of 0-8 ℃ to obtain the sulfhydryl chitosan.
4. The method for preparing an electroplating bath according to claim 3, wherein the mercapto compound is a mercapto polyethyleneimine and/or N-acetyl-L-cysteine; the preparation method of the sulfhydrylation polyethyleneimine comprises the following steps:
dissolving 0.5-2 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 1-4 parts by weight of methyl thioglycolate for mixing, stirring at 50-70 ℃ and 300-500rpm for 6-10h to obtain a mixed solution A, carrying out reduced pressure concentration at the vacuum degree of 0.06-0.09MPa and the temperature of 40-60 ℃ until 1/5-1/3 of the mixed solution A, adding 2-10 parts by weight of deionized water for dissolving, adding 2-8 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at the vacuum degree of 0.05-0.1MPa and the temperature of 40-60 ℃ until 1/5-1/3 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine.
5. An electroplating bath prepared by the method of any one of claims 1 to 4.
6. Use of the electroplating solution according to claim 5 for electroplating plastic surfaces.
7. Use of the electroplating solution according to claim 6, wherein the method for electroplating a plastic surface comprises the following steps:
s1, preprocessing: firstly, cleaning the surface of the plastic for 5-10min at room temperature by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1 (1-2); cleaning with 40-60 deg.C sodium carbonate water solution with pH of 7-8.5 for 3-10min, ultrasonic cleaning with acetic acid with pH of 5-6.5 at room temperature for 1-3min, and cleaning with 30-50 deg.C water for 2-5min to obtain pretreated plastic;
s2, coarsening: soaking the pretreated plastic in swelling solution at 30-50 deg.C for 5-15min, and then in microetching solution at 50-65 deg.C, and treating at ultrasonic frequency of 20-40kHz and ultrasonic power of 120-;
s3, neutralization: immersing the microetching plastic into a neutralization solution, stirring for 5-15min at 50-70 ℃ and 200-500rpm, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, 15-50 wt% of sulfuric acid and 1-5 wt% of oxalic acid are taken out and washed for 2-5min by deionized water;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 20-40min at 30-50 ℃, wherein the sensitizing solution is prepared by mixing 0.01-0.1 wt% of palladium chloride, 1-5 wt% of stannous chloride, 30-40 wt% of hydrochloric acid with the concentration of 20-40ml/L, 10-25 wt% of potassium chloride and the balance of deionized water;
s5, activation: placing the sensitized plastic in an activating solution, and activating at the room temperature and at the speed of 300-500rpm for 3-10min, wherein the activating solution is formed by mixing 1-5 wt% of silver nitrate, 0.5-2 wt% of ammonia water, 2-10 wt% of glyoxal, 0.5-3 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 20-30 ℃, and the current density is 0.5-2.0A/dm2Electroplating for 20-50 min;
s7, finished product: drying the electroplated plastic at 50-70 deg.C for 1-3h, and cooling to room temperature to obtain the plastic surface metal coating.
8. The use of the electroplating bath according to claim 7, wherein the swelling solution is formed by mixing 10-25 wt% of 5-carboxybenzotriazole, 20-40 wt% of N-methylpyrrolidone, 10-20 wt% of potassium hydroxide, 5-15 wt% of N, N-dimethylformamide, and the balance being deionized water; the micro-etching solution is 20-30 wt% of phosphoric acid, 50-65 wt% of sulfuric acid and 3-8 wt% of MnO20.01-0.05 wt% of hexadecaneTrimethyl ammonium bromide, 0.1-1 wt% of sodium tripolyphosphate and the balance of deionized water.
9. The method for electroplating a surface of a plastic according to claim 7, wherein the plastic is any one of polycarbonate plastic, ABS plastic and polyimide plastic.
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| CN113817203A (en) * | 2021-09-22 | 2021-12-21 | 华南理工大学 | Method for preparing Cu-CNTs super-hydrophobic coating on plastic surface |
| CN117758104A (en) * | 2023-12-28 | 2024-03-26 | 余姚市爱迪升电镀科技有限公司 | Copper-molybdenum alloy wire for electronic device, manganese plating process and manganese plating solution thereof |
| CN118292061A (en) * | 2024-04-08 | 2024-07-05 | 重庆大学 | Copper electroplating solution for chip packaging and preparation method thereof |
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