CN113652720B - Cyanide-free copper plating bottoming method - Google Patents
Cyanide-free copper plating bottoming method Download PDFInfo
- Publication number
- CN113652720B CN113652720B CN202110801282.5A CN202110801282A CN113652720B CN 113652720 B CN113652720 B CN 113652720B CN 202110801282 A CN202110801282 A CN 202110801282A CN 113652720 B CN113652720 B CN 113652720B
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- China
- Prior art keywords
- cyanide
- free copper
- copper plating
- plating
- raw materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007747 plating Methods 0.000 title claims abstract description 151
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 146
- 239000010949 copper Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 116
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- -1 cycloalkyl sulfonate Chemical compound 0.000 claims abstract description 29
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229920000768 polyamine Polymers 0.000 claims abstract description 26
- 150000004291 polyenes Chemical class 0.000 claims abstract description 26
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 22
- 239000001989 lithium alloy Substances 0.000 claims abstract description 22
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 17
- 150000001879 copper Chemical class 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 14
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 51
- 229910052725 zinc Inorganic materials 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000007598 dipping method Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 229910002651 NO3 Inorganic materials 0.000 claims description 17
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 16
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 10
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 8
- 235000011180 diphosphates Nutrition 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 8
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 7
- 150000002823 nitrates Chemical class 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical class NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 5
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 150000004673 fluoride salts Chemical class 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- VYJWAACGBWHAEO-UHFFFAOYSA-L P(OC(CO)OP([O-])=O)([O-])=O.[Na+].[Na+] Chemical compound P(OC(CO)OP([O-])=O)([O-])=O.[Na+].[Na+] VYJWAACGBWHAEO-UHFFFAOYSA-L 0.000 claims 1
- IMPJIGYFRNDTFT-UHFFFAOYSA-N P1(=O)OC(CO)OP(O1)=O.[Na] Chemical compound P1(=O)OC(CO)OP(O1)=O.[Na] IMPJIGYFRNDTFT-UHFFFAOYSA-N 0.000 claims 1
- RQNVGUOKYSZUJN-UHFFFAOYSA-N [K].P1(=O)OC(CO)OP(O1)=O Chemical compound [K].P1(=O)OC(CO)OP(O1)=O RQNVGUOKYSZUJN-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 238000009776 industrial production Methods 0.000 abstract description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 2
- 150000002170 ethers Chemical class 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 40
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 20
- 238000009713 electroplating Methods 0.000 description 16
- 239000008139 complexing agent Substances 0.000 description 13
- 230000037452 priming Effects 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- 230000000536 complexating effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000002195 synergetic effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 229940048084 pyrophosphate Drugs 0.000 description 4
- UIFZRVHZTAYMBC-UHFFFAOYSA-N (1-hydroxy-1-phosphonoethyl)phosphonic acid;sodium Chemical compound [Na].OP(=O)(O)C(O)(C)P(O)(O)=O UIFZRVHZTAYMBC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000005536 corrosion prevention Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 238000009472 formulation Methods 0.000 description 2
- 150000002333 glycines Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- HCMGUYVGXYMWRB-UHFFFAOYSA-N 1-propoxyperoxypropane Chemical compound CCCOOOCCC HCMGUYVGXYMWRB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 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 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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Abstract
The invention discloses a cyanide-free copper plating bottoming method, which comprises the following steps: pretreating, presoaking, preplating cyanide-free copper and cyanide-free copper plating on the magnesium alloy; the preplating cyanide-free copper comprises the following preparation raw materials: copper salt I, organic phosphonate I, polyene polyamine compound I, carbonate I, thio-hybridized compound I and cycloalkyl sulfonate I; the cyanide-free copper plating solution comprises the following preparation raw materials: copper salts II, organic phosphonates II, polyene polyamines II, carbonates II, thio-hybridized compounds II, cycloalkyl sulfonates II and unsaturated hydrocarbyloxy ethers. The invention obtains a plating layer with even coverage and excellent binding force on the magnesium-lithium alloy material, meets the requirement of high binding force, has simple and stable process flow, and improves the yield of industrial production.
Description
Technical Field
The invention relates to the technical field of magnesium alloy material corrosion prevention, in particular to a cyanide-free copper plating bottoming method.
Background
The magnesium alloy is known as a green metal structural material in the 21 st century, has low density, high specific strength and specific rigidity, and excellent damping property, machinability and casting property, and is increasingly widely applied to various fields of automobile manufacturing, aerospace industry, electronic communication and the like.
The magnesium-lithium alloy is the lightest metal structural material in the magnesium alloy studied so far, has various advantages of the magnesium alloy, has the characteristics of outstanding shock absorption performance, high-energy particle penetration resistance, good mechanical processing and cold forming performance and the like, can meet the requirements of modern society on light materials, and has wider application prospects in the fields of aerospace, communication, weapon equipment manufacturing and '3C' products.
The standard electrode potential of magnesium is-2.38V, and the standard electrode potential of lithium is-3.05V, so that the magnesium-lithium alloy has higher activity than other magnesium alloys, and is extremely easy to corrode in air. In the related art, the research on the magnesium-lithium alloy is focused on the performance of the material, few reports are published on the corrosion prevention research of the surface of the material, and the application research on the surface metallization electroplating process is less. Compared with the common coating protection, the surface metallization has the advantages of high hardness, good wear resistance, excellent metal texture and high temperature resistance of the plating layer, and the special plating layer can achieve the effects of radiation resistance, electromagnetic shielding and the like, so that the metallization plating on the magnesium-lithium alloy is an indispensable surface treatment technology for industrial application.
In the related art, the electroplating process of the traditional magnesium alloy is directly applied to the electroplating process of the magnesium-lithium alloy, and is the most common corrosion prevention process, mainly a pre-plating process of cyanide copper plating after zinc immersion. As in ASTM B480-88 standard established by the american society for testing and materials, a method of plating a metal plating on a magnesium alloy surface, i.e., a cyanide pre-copper plating process, is suggested. There are also Dow processes, norskhydro processes, WCM processes, and the like. At present, although the cyanide copper preplating process of the magnesium-lithium alloy can meet the requirements of industrial application, the process uses highly toxic cyanide, has great harm to human health and pollutes the environment, does not accord with the development of environmental protection, and is inevitably eliminated.
In order to avoid the problems of health hazard to human body and environmental pollution caused by cyanide, the technology of bottoming such as chemical nickel, neutral electroplated nickel and cyanide-free copper plating is developed in the related technology.
The chemical nickel priming process has the advantages that: the process avoids cyanide, has strong covering and deep plating capability of the chemical nickel bottoming layer, and is suitable for workpieces with different shapes and complicated shapes. However, the pretreatment of the process is carried out by using an organic solvent and chromic anhydride, so that the harm to human bodies and environmental protection is great, the chemical nickel plating solution is a thermodynamically unstable system, the service life of the plating solution is short, the chemical nickel plating time is long, and the subsequent high-temperature baking heat treatment is often needed to improve the binding force, so that the process is complicated, the cost is high, and the development of industrial application is not favored.
The neutral nickel plating priming process has the advantages that chemical nickel treatment is not needed, neutral nickel is directly plated after zinc dipping, and the appearance of compactness and good binding force is obtained, so that the time consumption of the process is shortened, and the production cost is reduced. However, the process also uses chromic anhydride for pickling, so that the environmental pollution is large, the plating neutral nickel priming has a running difference, a low-current area cannot be covered with a plating layer, and the process is not suitable for workpieces with complex shapes, and limits the industrialized application development of the workpieces.
The cyanide-free copper plating bottoming process has the advantages of avoiding cyanide use, along with simple flow and good plating layer coverage capability in a low-electric area. But is unsafe and does not meet the environmental protection requirement; when the method is applied to a magnesium-lithium alloy material, a plurality of problems exist, on one hand, because the potential of a magnesium-lithium alloy electrode is lower, the substitution reaction is too fast during zinc dipping, the zinc layer is rough, and on the other hand, serious copper substitution reaction is generated during cyanide-free copper electroplating, a plating layer with good binding force cannot be obtained, and especially the binding force of a thermal shock test is unqualified, so that the method cannot meet the requirement of industrial application.
Therefore, there is a need to develop a method for cyanide-free copper plating priming, and the plating layer prepared by the method has good binding force.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a cyanide-free copper plating bottoming method, and the plating layer prepared by the method has good binding force.
The invention provides a cyanide-free copper plating bottoming method, which comprises the following steps:
pretreating, presoaking, preplating cyanide-free copper and cyanide-free copper plating on the magnesium alloy;
the preplating cyanide-free copper comprises the following preparation raw materials:
copper salt I, organic phosphonate I, polyene polyamine compound I, carbonate I, thio-hybridized compound I and cycloalkyl sulfonate I;
the cyanide-free copper plating solution comprises the following preparation raw materials:
copper salts II, organic phosphonates II, polyene polyamines II, carbonates II, thio-hybridized compounds II, cycloalkyl sulfonates II and unsaturated hydrocarbyloxy ethers.
The method for priming cyanide-free copper plating is composed of three working procedures of pre-dipping, pre-plating cyanide-free copper and cyanide-free copper plating, wherein the pre-dipping aims at neutralizing and adjusting the pH value of the surface of the zinc dipping layer, forming a complexing agent film-protecting layer and delaying the copper replacement speed of the zinc dipping layer in the pre-plating cyanide-free copper liquid medicine. Effectively solves the problem that the zinc layer rapidly generates displacement reaction in the preplating cyanide-free copper liquor to generate loose copper plating layer so as to influence the bonding force of the plating layer. Copper salt I in the preplating cyanide-free copper plating solution provides copper metal; the organic phosphonate I plays a main complexing role on copper metal, so that the plating layer is crystallized carefully, the copper substitution is inhibited, and the covering capacity of the plating layer is improved; the polyene polyamine compound I has auxiliary complexing effect on copper metal, and has synergistic effect with a main complexing agent, so that the copper complexing stability is improved, the copper substitution is further inhibited, and the corrosion of a magnesium alloy material is further inhibited; the carbonate I plays a role of conductive salt, increases the conductivity of the plating solution and has the pH buffering capacity; the thio-hybridized compound I is a steric inhibitor: the coverage performance of a low area of the plating layer is improved; cycloalkyl sulfonate I is a softener: reduces the internal stress of the copper coating and enhances the binding force between the copper coating and the substrate material.
Copper salt II in the cyanide-free copper plating bath provides copper metal; the organic phosphonate II plays a main complexing role on copper metal, so that the crystallization of a plating layer is thinned, the replacement of copper is inhibited, and the plating solution is stabilized; the polyene polyamine compound II has auxiliary complexing effect on copper metal, has synergistic effect with a main complexing agent, improves copper complexing stability, further inhibits copper substitution, and inhibits corrosion of magnesium alloy materials; the carbonate II plays a role of conductive salt, increases the conductivity of the plating solution and has the pH buffering capacity; the thio-hybridized compound II is a dislocation agent: the coverage performance of a low area of the plating layer is improved; cycloalkyl sulfonate II is a softener: the internal stress of the copper coating is reduced, and the binding force between the copper coating and the substrate material is enhanced; unsaturated hydrocarbyloxy ether is a gloss agent: the crystallization is finer, and the brightness of the plating layer is increased.
According to some embodiments of the invention, the prepreg comprises the following preparation raw materials: organic phosphonate III and polyene polyamine compound III.
According to some embodiments of the invention, the prepreg comprises the following preparation raw materials: organic phosphonate III, polyene polyamine compound III and water.
According to some embodiments of the invention, the organophosphonate III comprises HEDP-Na 4 (sodium hydroxyethylidene) and HEDP-K 4 At least one of (sodium hydroxyethylidene) potassium.
The organic phosphonate III has a slightly soluble effect on the oxide film on the surface of the zinc layer, so that the zinc layer is activated.
The polyene polyamine compound III is adsorbed on the surface of the metal zinc layer to form a complexing agent film layer, so that the zinc layer is prevented from being oxidized in the air, copper substitution is inhibited, and the binding force of a plating layer is improved.
According to some embodiments of the invention, the prepreg comprises the following weight fraction preparation raw materials: 1-5% of organic phosphonate III, 5-12% of polyene polyamine compound III and the balance of water.
According to some embodiments of the invention, the prepreg comprises the following weight fraction preparation raw materials: 2-3% of organic phosphonate III, 8-10% of polyene polyamine compound III and the balance of water.
According to some embodiments of the invention, the polyene polyamine compound iii comprises diethylenetriamine.
According to some embodiments of the invention, the preplating cyanide-free copper, the plating solution consists of the following preparation raw materials in parts by weight:
copper salt I, organic phosphonate I, polyene polyamine compound I, carbonate I, thio-hybridized compound I, cycloalkyl sulfonate I and water.
According to some embodiments of the invention, the preplating cyanide-free copper, the plating solution consists of the following preparation raw materials in parts by weight:
copper salt I3-6%;
15% -25% of organic phosphonate I;
5 to 12 percent of polyene polyamine compound I;
5% -12% of carbonate I;
0.01 to 0.03 percent of thio-hybridized compound I;
0.1 to 0.4 percent of cycloalkyl sulfonate I;
and the balance being water.
According to some embodiments of the invention, the preplating cyanide-free copper, the plating solution consists of the following preparation raw materials in parts by weight:
4% -5% of copper salt I;
18-20% of organic phosphonate I;
8% -10% of polyene polyamine compound I;
8% -10% of carbonate I;
0.02% -0.025% of thio-hybridized compound I;
0.25 to 0.3 percent of cycloalkyl sulfonate I;
and the balance being water.
According to some embodiments of the invention, the cyanide-free copper plating solution consists of the following preparation raw materials in parts by weight:
copper salt II, organic phosphonate II, polyene polyamine compound II, carbonate II, thio-hybridized compound II, cycloalkyl sulfonate II, unsaturated hydrocarbyloxy ether and water.
According to some embodiments of the invention, the cyanide-free copper plating solution consists of the following preparation raw materials in parts by weight:
6% -10% of copper salt II;
18% -28% of organic phosphonate II;
4% -8% of polyene polyamine compound II;
5-12% of carbonate II;
0.02% -0.05% of a thio-hybridized compound II;
0.2 to 0.5 percent of cycloalkyl sulfonate II;
0.01 to 0.03 percent of unsaturated alkoxy ether;
and the balance being water.
According to some embodiments of the invention, the cyanide-free copper plating solution consists of the following preparation raw materials in parts by weight:
copper salt II 7% -8%;
20% -24% of organic phosphonate II;
5 to 6 percent of polyene polyamine compound II;
8% -10% of carbonate II;
0.03 to 0.04 percent of sulfur-based hybrid compound II;
0.3 to 0.4 percent of cycloalkyl sulfonate II;
0.02 to 0.025 percent of unsaturated alkoxy ether;
and the balance being water.
According to some embodiments of the invention, the copper salt i and the copper salt ii are each independently selected from at least one of copper chloride, copper sulfate and copper nitrate.
According to some embodiments of the invention, the organophosphonate I and organophosphonate II are each independently selected from HEDP-Na 4 (sodium hydroxyethylidene) and HEDP-K 4 At least one of (sodium hydroxyethylidene) potassium.
According to some embodiments of the invention, the polyene polyamine compound i comprises diethylenetriamine.
According to some embodiments of the invention, the polyene polyamine compound ii comprises diethylenetriamine.
According to some embodiments of the invention, the carbonate i comprises at least one of sodium carbonate and potassium carbonate.
According to some embodiments of the invention, the carbonate ii comprises at least one of sodium carbonate and potassium carbonate.
According to some embodiments of the invention, the thio-hybridized compound I comprises 2-mercaptobenzothiazole.
According to some embodiments of the invention, the thio-hybridized compound II comprises 2-mercaptobenzothiazole.
According to some embodiments of the invention, the cycloalkyl sulfonate i comprises sodium benzene sulfinate.
According to some embodiments of the invention, the cycloalkyl sulfonate ii comprises sodium benzene sulfinate.
According to some embodiments of the invention, the unsaturated hydrocarbyloxy ether comprises a propargyl alcohol propoxy ether.
According to some embodiments of the invention, the pretreatment comprises the steps of: and (3) acid etching, activating and zinc leaching the magnesium alloy.
The acid etching, activation and zinc leaching used in the pretreatment are all aimed at the characteristics of the magnesium-lithium alloy material, the surface of the magnesium-lithium alloy is effectively cleaned and activated by adjusting the formula components and the operation conditions of each procedure, a fine zinc layer with excellent binding force is obtained in the zinc leaching, and the uniform coverage with a subsequent priming copper layer is ensured, so that a plating layer with excellent binding force can be obtained.
According to some embodiments of the invention, the acid etching solution comprises the following preparation raw materials: inorganic acids, organic phosphonic compounds and nitrates I.
According to some embodiments of the invention, the inorganic acid comprises at least one of phosphoric acid and nitric acid.
The inorganic acid dissolves metal oxides and impurities, and promotes the activation of the metal surface.
According to some embodiments of the invention, the organic phosphonic acid compound comprises hydroxyethylidene diphosphate (HEDP).
The organic phosphonic acid compound promotes the activation of the metal surface, plays a role in complexing the metal, and improves the solution stability.
According to some embodiments of the invention, the nitrate i comprises at least one of sodium nitrate and potassium nitrate.
Nitrate i promotes oxidation and dissolution of surface impurities.
According to some embodiments of the invention, the acid etching solution consists of the following preparation raw materials: inorganic acid, organic phosphonic acid compound, nitrate I and water.
According to some embodiments of the invention, the acid etching solution consists of the following preparation raw materials in parts by weight: inorganic acid 0.5-2.5%, organic phosphonic acid compound 0.8-3%, nitrate I0.05-0.5% and water for the rest.
According to some embodiments of the invention, the acid etching solution consists of the following preparation raw materials in parts by weight: 1 to 2 percent of inorganic acid, 1.2 to 2.5 percent of organic phosphonic acid compound, 0.1 to 0.3 percent of nitrate I and the balance of water.
According to some embodiments of the invention, the activating solution consists of the following preparation raw materials in weight fraction: persulfates, nitrates II, inorganic bases and organic phosphonates IV.
According to some embodiments of the invention, the activation solution consists of the following preparation raw materials: persulfate, nitrate II, inorganic base, organic phosphonate IV and water.
According to some embodiments of the invention, the persulfate salt comprises at least one of sodium persulfate and potassium persulfate.
Potassium persulfate as the main activator: mainly plays roles of dissolving and alloying surface metal oxide and cleaning the surface.
The inorganic base forms hydroxide with magnesium, which inhibits the corrosion of magnesium.
According to some embodiments of the invention, the nitrate ii comprises at least one of sodium nitrate and potassium nitrate.
Nitrate II acts as an auxiliary activator: the method has synergistic effect with persulfate, so that oxide of metal impurities on the surface is removed thoroughly, and the surface is activated to be off-white.
According to some embodiments of the invention, the organophosphonate IV comprises HEDP-Na 4 (sodium hydroxyethylidene) and HEDP-K 4 At least one of (sodium hydroxyethylidene) potassium.
The organic phosphonate IV and gluconate have complexation effect on metal, and the solution stability is improved.
According to some embodiments of the invention, the inorganic base comprises at least one of sodium hydroxide and potassium hydroxide.
According to some embodiments of the invention, the activating solution consists of the following preparation raw materials in weight fraction: 2-6% of persulfate, 1-5% of nitrate II, 10-20% of inorganic alkali, 1-5% of organic phosphonate IV and the balance of water.
According to some embodiments of the invention, the activating solution consists of the following preparation raw materials in weight fraction:
3 to 5 percent of persulfate, 2 to 3 percent of nitrate II, 12 to 16 percent of inorganic alkali, 2 to 3 percent of organic phosphonate IV and the balance of water.
According to some embodiments of the invention, the zincating solution comprises the following preparation raw materials: zinc-containing compounds, acetates, pyrophosphates, fluoro salts, aminoacetates and nitrates III.
According to some embodiments of the invention, the zincating solution consists of zinc-containing compounds, acetates, pyrophosphates, fluorides, aminoacetates and nitrates III and water from the following preparation raw materials.
According to some embodiments of the invention, the zinc-containing compound comprises at least one of zinc sulfate, zinc chloride, and zinc nitrate.
The zinc-containing compound provides elemental zinc.
According to some embodiments of the invention, the acetate comprises at least one of sodium acetate and potassium acetate.
Acetate is a pH buffer and plays a role in stabilizing the pH of the zinc leaching solution.
According to some embodiments of the invention, the pyrophosphate comprises at least one of sodium pyrophosphate and potassium pyrophosphate.
The pyrophosphate is used as a main complexing agent, and plays roles in dissolving metal oxide, promoting the replacement reaction of zinc, complexing metal and improving the stability of zinc leaching solution.
According to some embodiments of the invention, the fluoride comprises at least one of ammonium bifluoride, sodium bifluoride, potassium bifluoride, sodium fluoride, potassium fluoride and ammonium fluoride.
The fluoride inhibits excessive corrosion of magnesium and refines the zinc layer.
According to some embodiments of the invention, the glycine salt comprises at least one of sodium glycine and potassium glycine.
The glycine salt has a refining effect on zinc layer crystallization, and the thickness of zinc layer is controlled.
According to some embodiments of the invention, the nitrate iii comprises at least one of sodium nitrate and potassium nitrate.
The nitrate III dissolves surface impurities and oxides, and cooperates with a main complexing agent to promote the activation of the metal surface.
According to some embodiments of the invention, the zincating solution consists of the following preparation raw materials in parts by weight:
3 to 5 percent of zinc-containing compound, 1.5 to 3 percent of acetate, 4 to 7 percent of pyrophosphate, 0.1 to 1 percent of fluoride salt, 0.2 to 2 percent of aminoacetate, 0.2 to 2 percent of nitrate III and the balance of water.
According to some embodiments of the invention, the zincating solution consists of the following preparation raw materials in parts by weight:
4 to 4.5 percent of zinc-containing compound, 2 to 2.5 percent of acetate, 5 to 6 percent of pyrophosphate, 0.3 to 0.8 percent of fluoride salt, 0.5 to 1 percent of aminoacetate, 0.5 to 1 percent of nitrate III and the balance of water.
The prepreg according to some embodiments of the invention comprises the following process conditions:
the temperature is 15-30 ℃; the pH value is 8.5-10.0; the time is 10 s-30 s.
According to some embodiments of the invention, the preplating cyanide-free copper comprises the following process conditions:
the temperature is 15-30 ℃; the pH value is 8.5-10.0; the current was 1.5A/dm 2 ～3A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time is 5 min-10 min.
The cyanide-free copper preplating process has the advantages that the operation temperature is reduced to 15-30 ℃, the ratio of the complexing agent to metal is improved, the copper replacement speed is obviously reduced, the binding force of a plating layer is greatly improved, the deep plating capacity of the plating layer is improved, and the plating layer with good coverage is obtained.
According to some embodiments of the invention, the cyanide-free copper plating comprises the following process conditions:
the temperature is 45-60 ℃; the pH value is 8.5-10.0; the current was 1.5A/dm 2 ～2.5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time is 10 min-20 min.
The cyanide-free copper plating process utilizes high current efficiency and excellent coverage performance, rapidly increases the thickness of copper layers, effectively protects the material from being corroded by acidic liquid medicine in the subsequent electroplating process, and ensures the binding force of a plating layer. The electroplating priming process can also obtain a plating layer with uniform coverage and excellent binding force on the magnesium alloy workpiece in a wider operation range, meets the binding force requirements of thermal shock tests with various plating layers and high thickness, has simple process flow and short priming plating time, and improves the efficiency of industrial production and the yield of products.
According to some embodiments of the invention, the cyanide-free copper plating comprises the following process conditions:
the temperature is 45-60 ℃; the pH value is 8.5-10.0; the current was 1.5A/dm 2 ～2.5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time is 10 min-20 min.
According to some embodiments of the invention, the magnesium alloy is a magnesium lithium alloy.
The invention has at least the following beneficial effects:
the invention adopts a bottoming method of cyanide-free copper plating consisting of three working procedures of pre-dip, pre-plating cyanide-free copper and cyanide-free copper plating, wherein the pre-dip mainly neutralizes and adjusts the pH value of the surface of the zinc dipping layer, and forms a complexing agent protecting film layer, and the protecting film layer prevents the zinc dipping layer from directly contacting copper metal in the pre-plating cyanide-free copper liquid medicine, thereby reducing the copper replacement reaction speed; the method has the advantages that the operation temperature is reduced during preplating cyanide-free copper, meanwhile, two complexing agents are combined according to a certain proportion and are mutually synergistic, copper replacement reaction is further restrained, the aim that a zinc-immersed layer does not replace copper in the preplating cyanide-free copper liquid medicine for 20 seconds is achieved, and therefore the surface of the zinc layer has enough time to be plated with copper through electrolysis, and a copper plating layer with good, uniform and fine coverage is obtained; the cyanide-free copper plating solution utilizes high current efficiency and excellent coverage performance, and rapidly increases the thickness of a copper layer, so that the material is effectively protected from being corroded by acidic liquid medicine in the subsequent electroplating process, and the stability of the binding force of a plating layer is ensured.
Drawings
Fig. 1 is a view of a magnesium-lithium alloy material selected for use in an embodiment of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The magnesium-lithium alloy test materials selected in the embodiment of the invention are as follows:
the LZ-91 magnesium lithium alloy 320mm multiplied by 240mm of a certain brand 13 inch notebook shell is made of a punched plate material, the thickness of the punched plate material is 0.4 mm-0.6 mm, and the appearance is shown in figure 1.
| Element(s) | Mg | Li | Zn | Si | Mn | Other impurities |
| Content (%) | Allowance of | 8.0～10.0 | 0.5～1.0 | <0.2 | <0.2 | <0.3 |
The electroplating process flow in the embodiment of the invention is as follows:
deoiling, acid etching, activating, zinc dipping, presoaking, preplating cyanide-free copper, cyanide-free copper plating, acid copper, semi-gloss nickel and full-gloss nickel.
Wherein, the acid etching and activation are required to be repeatedly processed for 1 to 2 times, so that the surface impurities are processed thoroughly and cleanly, and the binding force of the subsequent plating layer can be obviously improved.
The steps are carried out for 2 times (except the steps from pre-soaking to cyanide-free copper plating, and the three steps do not need to be washed with water).
And (3) neutralizing and activating the acid copper, the semi-gloss nickel and the full-gloss nickel by using sulfuric acid with the mass fraction of 8-10%.
The roles, formulations and operating conditions of each process in the embodiments of the present invention are shown in table 1.
TABLE 1 effects, formulations and operating conditions of the various processes in embodiments of the invention
The additives (RP-980 MU, RP-980A, RP-980B, RN-3110MU, RN-3110A, RN-664, RN-781, RN-672PT, RN-664, RN-781, RN-672PT and RN-664) in the copper acid, semi-gloss nickel and all gloss nickel processes are all commercial products of Ruiyan corporation.
The density of the acid etching liquid used in the acid etching in the embodiment of the invention is 1.05 g/mL-1.06 g/mL.
The density of the activation liquid used in the activation in the embodiment of the present invention is 1.14g/mL to 1.16g/mL.
The density of the zinc leaching solution used in the zinc leaching in the embodiment of the invention is 1.10 g/mL-1.12 g/mL.
The density of the prepreg used in the prepreg according to the embodiment of the present invention is 1.08g/mL to 1.10g/mL.
The density of the plating solution used in preplating cyanide-free copper in the embodiment of the invention is 1.15 g/mL-1.20 g/mL.
The density of the plating solution used in the cyanide-free copper plating in the embodiment of the invention is 1.15 g/mL-1.20 g/mL.
The process conditions in the electroplating process of examples 1-3 of the present invention are shown in Table 2.
TABLE 2 Process conditions during electroplating according to examples 1 to 3 of the invention
Note that: example 2 intermediate value calculation example: the concentration (g/L) of sodium hydroxide in the oil removal process is as follows: (20+50)/2=35).
Comparative example 1
The comparative example is a copper plating process.
The pretreatment step and the subsequent plating process conditions of this comparative example were the same as in example 2, except that the prepreg process was not used in this comparative example.
Comparative example 2
The comparative example is a copper plating process.
The pretreatment step and the subsequent plating process conditions of this comparative example were the same as in example 2, except that this comparative example did not have a preplating cyanide-free copper process.
Comparative example 3
The comparative example is a copper plating process.
The pretreatment step and the subsequent plating process conditions of this comparative example were the same as in example 2, except that this comparative example did not have a cyanide-free copper plating process and the plating time of the pre-plating cyanide-free copper plating process was 15 minutes.
Comparative example 4
The comparative example is a copper plating process.
The process flow of this comparative example is:
deoiling, acid etching, activating, zinc dipping, cyanide copper plating, cyanide-free copper plating, acid copper, semi-gloss nickel and full-gloss nickel; degreasing, pickling, activating and zincating are the same as in example 2, and the step of cyanide copper plating adopts the DOW (Dow) process, and the cyanide copper plating formula and the operation conditions are as follows:
about 40g/L of cuprous cyanide, about 68g/L of potassium cyanide, about 30g/L of potassium fluoride, pH about 10, temperature about 60 ℃, cathodic current density: 2A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The electroplating time was 8min.
The process conditions for the subsequent plating are the same as in example 2.
The plating adhesion force detection methods prepared in examples 1 to 3 and comparative examples 1 to 4 of the present invention:
the test is carried out by adopting the file test method, the bending test method and the thermal shock test method in GB/T5270-2005, and the total thickness of the electroplated layer is 20 mu m to 40 mu m.
File test method: and (3) filing the edge of the workpiece along the direction from the base metal to the electroplating coating layer at an included angle of 45 degrees with the plating surface until the base metal can be seen, and observing whether the coating layer and the base can be peeled off.
Evaluation mode: "good" indicates no peeling and good bonding force; "Deltay" indicates that the chips are peeled off and the bonding force is general; "×" indicates that the sheet-like peeling and the bonding force was poor.
Bending test method: the workpiece is bent by hand to one side for 90 degrees and then bent to the other side for 90 degrees until the workpiece is bent and broken, and whether the coating layer at the fracture can be peeled off or not is observed.
Evaluation mode: "good" indicates no peeling and good bonding force; "Deltay" indicates that the chips are peeled off and the bonding force is general; "×" indicates that the sheet-like peeling and the bonding force was poor.
Thermal shock test method: baking the electroplated workpiece at 200 ℃ for 60min, taking out, immediately putting into water at normal temperature for quenching, and repeatedly testing for 3 times. The plating layer was observed for bubbling or flaking.
Evaluation mode: "goodbinding force, no bubbling; "Deltay" represents a local bubble, and the binding force is general; "×" indicates severe foaming and poor bonding force.
The results of the performance test of the plating layers prepared in examples 1 to 3 and comparative examples 1 to 4 of the present invention are shown in Table 3.
Table 3 the plating performance test results obtained in examples 1 to 3 of the present invention and comparative examples 1 to 4.
As can be seen from table 3, in the binding force results of the plating layers and the magnesium-lithium alloy substrates prepared in examples 1 to 3 and comparative examples 1 to 4 according to the present invention, the plating binding force performance of the process according to the present invention is optimal for the magnesium-lithium alloy materials, and the combination of the pre-dip+pre-plating cyanide-free copper and cyanide-free copper plating according to comparative examples 1 to 3 according to the present invention has a synergistic effect; compared with comparative example 4, the binding force performance of the plating layer reaches the cyanide copper plating process, can completely meet the requirement of industrial application, and meets the requirement of environmental protection.
The invention is a cyanide-free copper plating bottoming process specially researched and developed aiming at the characteristics of magnesium-lithium alloy materials, the process comprises four procedures of pretreatment oil removal, acid etching, activation and zinc dipping, then a bottoming method of cyanide-free copper plating consisting of three procedures of pre-dipping, pre-plating cyanide-free copper and cyanide-free copper plating is adopted, and then subsequent plating such as copper electroplating, semi-gloss nickel, full-gloss nickel, trivalent chromium and the like can be directly carried out.
The acid etching, activation and zinc leaching used in the pretreatment are all specific to the characteristics of the magnesium-lithium alloy material, the surface of the magnesium-lithium alloy is effectively cleaned and activated by adjusting the formula components and the operation conditions of each procedure, a fine zinc layer with excellent binding force is obtained in zinc leaching, and the uniform coverage with a subsequent priming copper layer is ensured, so that a plating layer with excellent binding force can be obtained.
The method comprises three working procedures of pre-dipping, pre-plating cyanide-free copper and cyanide-free copper plating, namely, a bottoming method of cyanide-free copper plating is adopted, wherein the pre-dipping mainly comprises the steps of neutralizing and adjusting the pH value of the surface of a zinc dipping layer, and forming a complexing agent film protecting layer, and the film protecting layer prevents the zinc dipping layer from directly contacting copper metal in the pre-plating cyanide-free copper liquid medicine, so that the copper replacement reaction speed is reduced; the method has the advantages that the operation temperature is reduced to 20-30 ℃ during preplating cyanide-free copper, meanwhile, two complexing agents are preferably combined according to a certain proportion and are mutually synergistic, so that the copper replacement reaction is further inhibited, the aim that a zinc dipping layer does not replace copper in 20 seconds in preplating cyanide-free copper liquid medicine is fulfilled, the surface of the zinc layer is ensured to have enough time to be plated with copper through electrolysis, and a copper plating layer with good, uniform and fine coverage is obtained, and is the key for improving the bonding force of the plating layer; the cyanide-free copper plating solution utilizes high current efficiency and excellent coverage performance to rapidly increase the thickness of copper layers so as to effectively protect the materials from being corroded by acidic liquid medicine during subsequent electroplating and ensure the stability of the binding force of the plating layer.
The electroplating priming process provided by the invention has the advantages that under a wider operation range, a plating layer which is uniformly covered and has excellent binding force is obtained on a magnesium-lithium alloy workpiece, the binding force requirement of thermal shock tests with high thickness of various plating layers is met, the process flow is simple, the priming plating time is short, and the efficiency of industrial production and the yield of products are improved.
The invention replaces cyanide-containing plating solution in the related technology, meets the environmental protection trend requirement, has wide process operation condition range, and meets the industrial production requirement; and the plating performance and the plating process stability are superior to those of the priming process flow in the related technology.
In summary, the invention adopts the bottoming method of cyanide-free copper plating consisting of three procedures of pre-dipping, pre-plating cyanide-free copper and cyanide-free copper plating, wherein the pre-dipping mainly is to neutralize and adjust the pH value of the surface of the zinc dipping layer, and form a complexing agent film protecting layer, and the film protecting layer prevents the zinc dipping layer from directly contacting copper metal in the pre-plating cyanide-free copper liquid medicine, thereby reducing the copper replacement reaction speed; the method has the advantages that the operation temperature is reduced during preplating cyanide-free copper, meanwhile, two complexing agents are combined according to a certain proportion and are mutually synergistic, copper replacement reaction is further restrained, the aim that a zinc-immersed layer does not replace copper in the preplating cyanide-free copper liquid medicine for 20 seconds is achieved, and therefore the surface of the zinc layer has enough time to be plated with copper through electrolysis, and a copper plating layer with good, uniform and fine coverage is obtained; the cyanide-free copper plating solution utilizes high current efficiency and excellent coverage performance, and rapidly increases the thickness of a copper layer, so that the material is effectively protected from being corroded by acidic liquid medicine in the subsequent electroplating process, and the stability of the binding force of a plating layer is ensured; the method meets the requirement of high binding force, has simple and stable process flow, and improves the yield and popularization possibility of industrial production.
While the embodiments of the present invention have been described in detail with reference to the specification and drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (12)
1. A cyanide-free copper plating bottoming method is characterized in that: the method comprises the following steps:
pretreating, presoaking, preplating cyanide-free copper and cyanide-free copper plating on the magnesium alloy;
the presoaking liquid comprises the following preparation raw materials in parts by weight: 1% -5% of organic phosphonate III, 5% -12% of polyene polyamine compound III and the balance of water;
the organic phosphonate III is at least one selected from sodium hydroxyethylidene bisphosphonate and potassium hydroxyethylidene bisphosphonate;
the polyene polyamine compound III is selected from diethylenetriamine;
the preplating cyanide-free copper comprises the following preparation raw materials in parts by weight:
copper salt I3% -6%; 15% -25% of organic phosphonate I; 5% -12% of polyene polyamine compound I; 5% -12% of carbonate I; 0.01% -0.03% of a thio-hybridized compound I; 0.1% -0.4% of cycloalkyl sulfonate I; and the balance being water;
the cyanide-free copper plating solution consists of the following preparation raw materials in parts by weight:
6% -10% of copper salt II; 18% -28% of organic phosphonate II; 4% -8% of polyene polyamine compound II; 5% -12% of carbonate II; 0.02% -0.05% of a thio-hybridized compound II; 0.2% -0.5% of cycloalkyl sulfonate II; 0.01% -0.03% of unsaturated alkoxy ether; and the balance being water;
the organic phosphonate I and the organic phosphonate II are respectively and independently selected from at least one of sodium hydroxyethylidene diphosphonate and potassium hydroxyethylidene diphosphonate;
the polyene polyamine compound I is selected from diethylenetriamine;
the polyene polyamine compound II is selected from diethylenetriamine;
the thio-hybridized compound I is selected from 2-mercaptobenzothiazole;
the thio-hybridized compound II is selected from 2-mercaptobenzothiazole;
the cycloalkyl sulfonate I is selected from sodium benzene sulfinate;
the cycloalkyl sulfonate II is selected from sodium benzene sulfinate;
the unsaturated hydrocarbyloxy ether is selected from the group consisting of propargyl alcohol propoxyl ethers;
the temperature of the preplating cyanide-free copper is 15-30 ℃.
2. The method for cyanide-free copper plating bottoming according to claim 1, characterized in that: the pretreatment comprises the following steps: and (3) acid etching, activating and zinc leaching the magnesium alloy.
3. The method for cyanide-free copper plating bottoming according to claim 2, characterized in that: the acid etching solution comprises the following preparation raw materials: inorganic acids, organic phosphonic compounds and nitrates I.
4. The method for cyanide-free copper plating bottoming according to claim 2, characterized in that: the acid etching liquid consists of the following preparation raw materials in parts by weight: inorganic acid 0.5-2.5%, organic phosphonic acid compound 0.8-3%, nitrate I0.05-0.5% and water in balance.
5. The method for cyanide-free copper plating bottoming according to claim 2, characterized in that: the activation liquid comprises the following preparation raw materials: persulfates, nitrates II, inorganic bases and organic phosphonates IV.
6. The method for cyanide-free copper plating bottoming according to claim 2, characterized in that: the activating liquid comprises the following raw materials in parts by weight: 2% -6% of persulfate, 1% -5% of nitrate II, 10% -20% of inorganic base, 1% -5% of organic phosphonate IV and the balance of water.
7. The method for cyanide-free copper plating bottoming according to claim 2, characterized in that: the zinc dipping liquid comprises the following preparation raw materials: zinc-containing compounds, acetates, pyrophosphates, fluoro salts, aminoacetates and nitrates III.
8. The method for cyanide-free copper plating bottoming according to claim 2, characterized in that: the zinc dipping liquid comprises the following raw materials in parts by weight: 3% -5% of zinc-containing compound, 1.5% -3% of acetate, 4% -7% of pyrophosphate, 0.1% -1% of fluoride salt, 0.2% -2% of aminoacetate, 0.2% -2% of nitrate III and the balance of water.
9. The method for cyanide-free copper plating bottoming according to claim 1, characterized in that:
the presoaking comprises the following process conditions:
the temperature is 15-30 ℃; the pH is 8.5-10.0; the time is 10 s-30 s.
10. The method for cyanide-free copper plating bottoming according to claim 1, characterized in that: the preplating cyanide-free copper comprises the following process conditions:
the pH is 8.5-10.0; the current was 1.5A/dm 2 ~3A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time is 5 min-10 min.
11. The method for cyanide-free copper plating bottoming according to claim 1, characterized in that: the cyanide-free copper plating comprises the following process conditions:
the temperature is 45-60 ℃; the pH is 8.5-10.0; the current was 1.5A/dm 2 ~2.5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time is 10 min-20 min.
12. The method for cyanide-free copper plating bottoming according to claim 1, characterized in that: the magnesium alloy is magnesium-lithium alloy.
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| DE3347593A1 (en) * | 1983-01-03 | 1984-07-05 | Omi International Corp., Warren, Mich. | AQUEOUS ALKALINE CYANIDE-FREE COPPER ELECTROLYTE AND METHOD FOR GALVANICALLY DEPOSITING A GRAIN-REFINED DUCTILE AND ADHESIVE COPPER LAYER ON A CONDUCTIVE SUBSTRATE |
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| CN101063217B (en) * | 2007-04-28 | 2011-01-05 | 广州市三孚化工有限公司 | Non-cyanogen high-density copper plating solution and aluminium alloy wheel hub electroplating technique using same |
| CN101245479A (en) * | 2008-03-17 | 2008-08-20 | 哈尔滨工业大学 | Cyanideless electro-coppering method for magnesium alloy casting parts |
| CN103806033A (en) * | 2012-11-12 | 2014-05-21 | 无锡三洲冷轧硅钢有限公司 | Method of electroplating metal layer on surface of zinc pressure casting |
| CN105543917A (en) * | 2016-01-05 | 2016-05-04 | 张颖 | Double-bottoming electroplating method for nickel-plating magnesium alloy hub |
| CN107904586A (en) * | 2017-11-24 | 2018-04-13 | 重庆赛格尔汽车配件有限公司 | A kind of copper pipe surface anticorrosive treatment process |
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