US3642588A - Addition compositions for acid electroplating baths - Google Patents
Addition compositions for acid electroplating baths Download PDFInfo
- Publication number
- US3642588A US3642588A US2406A US3642588DA US3642588A US 3642588 A US3642588 A US 3642588A US 2406 A US2406 A US 2406A US 3642588D A US3642588D A US 3642588DA US 3642588 A US3642588 A US 3642588A
- Authority
- US
- United States
- Prior art keywords
- baths
- addition
- coatings
- bath
- employed
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000009713 electroplating Methods 0.000 title claims abstract description 10
- 239000002253 acid Substances 0.000 title abstract description 14
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001913 cellulose Substances 0.000 claims abstract description 17
- 229920002678 cellulose Polymers 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims abstract description 12
- -1 cyclic aldehyde Chemical class 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 230000026030 halogenation Effects 0.000 claims abstract description 5
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical class OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 150000008045 alkali metal halides Chemical class 0.000 claims description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 4
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 claims description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 4
- DAJDXKBYZZGECL-UHFFFAOYSA-N 1,3-oxathiolan-2-one Chemical compound O=C1OCCS1 DAJDXKBYZZGECL-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- KFGJUQRJVQDJHL-UHFFFAOYSA-N ethanethiol Chemical compound CCS.CCS KFGJUQRJVQDJHL-UHFFFAOYSA-N 0.000 claims description 3
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 claims 1
- 238000007792 addition Methods 0.000 abstract description 53
- 238000000576 coating method Methods 0.000 abstract description 22
- 238000007747 plating Methods 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 230000000149 penetrating effect Effects 0.000 abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 5
- 150000002576 ketones Chemical class 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 150000000475 acetylene derivatives Chemical class 0.000 abstract description 4
- 239000002671 adjuvant Substances 0.000 abstract description 4
- 239000010953 base metal Substances 0.000 abstract description 4
- 230000008094 contradictory effect Effects 0.000 abstract description 4
- 150000002730 mercury Chemical class 0.000 abstract description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 abstract description 4
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 abstract description 3
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical class C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 abstract description 3
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 abstract description 3
- HMKKIXGYKWDQSV-KAMYIIQDSA-N alpha-Amylcinnamaldehyde Chemical compound CCCCC\C(C=O)=C\C1=CC=CC=C1 HMKKIXGYKWDQSV-KAMYIIQDSA-N 0.000 abstract description 3
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229940117916 cinnamic aldehyde Drugs 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000717 retained effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- VREVKZLUMZQJRI-UHFFFAOYSA-N [SH2]=N Chemical class [SH2]=N VREVKZLUMZQJRI-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 abstract description 2
- 229960002327 chloral hydrate Drugs 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 235000005985 organic acids Nutrition 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 abstract description 2
- GINSRDSEEGBTJO-UHFFFAOYSA-N thietane 1-oxide Chemical compound O=S1CCC1 GINSRDSEEGBTJO-UHFFFAOYSA-N 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 150000003573 thiols Chemical class 0.000 abstract 1
- 239000011928 denatured alcohol Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000546 pharmaceutical excipient Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- JBNOVHJXQSHGRL-UHFFFAOYSA-N 7-amino-4-(trifluoromethyl)coumarin Chemical compound FC(F)(F)C1=CC(=O)OC2=CC(N)=CC=C21 JBNOVHJXQSHGRL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FBMGKRKUOZTARV-UHFFFAOYSA-N F.OB(O)O Chemical compound F.OB(O)O FBMGKRKUOZTARV-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 241000218998 Salicaceae Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000011 cadmium carbonate Inorganic materials 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 description 1
- XFHMDVKMKRZMIF-UHFFFAOYSA-L cadmium(2+);disulfamate Chemical compound [Cd+2].NS([O-])(=O)=O.NS([O-])(=O)=O XFHMDVKMKRZMIF-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical class C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 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
Definitions
- Cellulose is degraded in a strong acid (such as H2804 01' BC] in the presence of glycocoll and an alkali halide is added such as NaCl or NaF;
- a strong acid such as H2804 01' BC
- an alkali halide such as NaCl or NaF
- the present invention relates to the compositions used for making additions to baths in standard electroplating operations in order to obtain metallic coatings of better quality.
- the invention is primarily directed to a method of preparation of addition compositions.
- an ideal coating has good penetrating power (or in other words is capable of filling the porosities or cracks of the base metal), ensures uniform thickness, is nonporous (which entails a high surface density), has good adhesion, ductility and brightness.
- Nickel plating bath which contains the basic composition (nickel sulphate or sulphamate solution) as well as an addition of propane-sulphone or of sulphonic organic acids linked with a polymethylene radical.
- This bath lacks penetrating power and produces a nonuniform deposit which exhibits porosity as a result of the codeposition of the addition agent and is brittle by reason of high internal stresses which tend to be relieved only at the cost of failure of the plating.
- the deposits have poor throwing power, result in only moderate penetration and cannot withstand high current densities in electrolytes which have low concentrations.
- the deposits are usually porous and nonductile, which makes it necessary in order to guard against corrosion to superpose two layers of nickel: the bottom layer is deposited with a different current density by employing a soluble anode in order to ensure a nonporous but mat surface.
- the surface layer is formed under conditions such as to ensure brightness but is nevertheless porous.
- acetylene derivatives have been employed as adjuvants with the addition of sulphonated derivatives (Kampschulte and Hanson van Wickle baths).
- the baths obtained have poor penetrating power and the deposits are highly porous.
- the baths contain compounds which have a multiple linkage with the carbon.
- the deposit does not offer any real guarantee against corrosion and has low ductility by reason of high internal stresses which probably arise partly from the presence of entrained organic substances in the deposit.
- the object of the invention is to provide a composition which is intended to be added to electroplating baths and meets practical requirements more effectively than addition compositions employed in the prior art, particularly insofar as the resultant baths permit the deposition of metallic coatings which are endowed at the same time with all the properties of freedom from porosity, good adhesion, ductility and brightness.
- the invention proposes in particular a method of preparation of an addition composition which is intended to be employed in acid baths for the electrodeposition of nickel, chromium, cadmium, zinc, gold, silver, platinum, copper, lead and tin or their alloys, wherein:
- Cellulose is degraded in a strong acid (such as H SO or HCl) in the presence of glycocoll and there is added an alkali metal halide such as NaCl or NaF;
- a strong acid such as H SO or HCl
- an alkali metal halide such as NaCl or NaF
- a ketone such as acetone
- a cyclic aldehyde such as furfural
- an alkali metal sulphide or a mercaptan is then added I in the presence of a mercury salt followed by halogenation and stabilization by addition of an oxidizing agent
- stage (b) is carried out and controlled in the following manner: the ketone fraction which is intended to be employed in this stage is mixed with aldehyde (furfural, for example) and with unsaturated alcohol (propargyl alcohol, for example) and possibly with a lower saturated alcohol such as denatured alcohol which is intended to perform the function of solvent having a low specific density soas to compensate for the specific density of furfural which is higher than that of water.
- aldehyde furfural, for example
- unsaturated alcohol propargyl alcohol, for example
- denatured alcohol which is intended to perform the function of solvent having a low specific density soas to compensate for the specific density of furfural which is higher than that of water.
- Controlled chlorination or fluorination of the mixture is carried out in an anhydrous medium after having added the mercaptan or the sulphide and a mercury salt to the mixture: the reaction starts up progressively and has the effect of stopping the evolution of gas which is resumed after a period of 5 to 10 minutes and indicates completion of the reaction.
- the color of the medium changes from pale yellow which is due to the sulphide to an amber shade which is probably due to the precipitation of a fraction of the sulphur, then to a greenish tinge if the reaction proceeds too far.
- Stage (a) begins with the degradation of the cellulose in strong acid in the presence of glycocoll which acts as a stabilizer. The alkali chloride or fluoride is then added.
- derivatives of acetone in particular in the form of sulphonated and chlorinated or fiuorinated derivatives, degraded cellulose in the form of hydrolyzed sugars and aldehydes,
- the addition composition can be considered to have three characteristic properties: it does not contain any compound having a multiple bond; if sodium hydroxide is added, for example, in order to bring the composition to a pH value which is higher than 7, the solution becomes turbid but again becomes clear if it is brought back to an acid pH value; the addition of hydrogen peroxide to a bath which contains the addition composition not only does not destroy this composition but also regenerates this latter to a partial extent. And by way of example, the addition of one-eighth to one-fourth of cc./l. of bath (hydrogen peroxide having a strength of l 10 volumes) makes it possible to extend the life of the bath as expressed in ampere-hours by approximately 1/5.
- propargyl alcohol 10 to 100 cm.
- denatured alcohol 10 to 200 cm.
- furfural 10 to 200 cm.
- sodium sulphide 2 to 10 g.
- glycocoll 2 to 100 g.
- mercury bromide traces hydrogen peroxide: 1 cm. at 1 l volumes.
- the proportion of addition composition which can be adopted varies between 0.10 cm. and 1 cm. per liter in nickel plating acid baths containing sulphate, sulphamate, chloride or fluoborate, the optimum proportion being evidently dependent on the concentration of the composition.
- An increase in the proportion results in a progressive increase in the ratio of metal deposited to hydrogen released but correlatively entails the need to adopt high current densities above a certain value. Since all the products employed in the composition are relatively stable, it is possible to operate at a temperature which attains 70 C.
- Current densities can be as follows in the case of a composition which is prepared from the following compounds (in respect of a quantity of 20 liters):
- electrodeposition is carried out only at low current densities.
- the pH value can be selected from a wide range which depends in any case on the type of coating which it is desired to obtain.
- a low value of the order of pH2 may be preferable in order to obtain a metal having a high value of hardness.
- the plating bath which contains the addition composition can be employed either in a tank which has no partition or in a tank which is provided with a porous barrier between the anode and the cathode.
- Changeover to a low pH value can be carried out by addition of a mineral acid such as HCl or H 50
- a mineral acid such as HCl or H 50
- the deposits obtained are nonporous and crackfree.
- the coatings are both bright and penetrating (or in other words fill the porosities or fissures of the base metal) as well as being ductile and adherent if the base metal has been subjected to a correct surface preparation.
- Denatured ethyl alcohol 50 cm Acetone 20 cmf Propargyl alcohol 50 emf Furfural 50 cm.
- Mercaptans dimethylsulphoxide 5 g. Cellulose 10 g. Glycoeoll 5 g. Excipient brought to 1 liter The pH of this bath can be adjusted by addition of boric acid.
- composition as thus constituted can in particular be added to the following baths in a proportion which is com- After neutralization, the last-mentioned bath is reacidified by hydrofluoric acid and the operating conditions are:
- EXAMPLE 3 Plating baths for electrodeposition of a lead-tin alloy.
- the addition composition is prepared from the following constituents, again by means of the same method.
- EXAMPLE 4 Plating baths for electrodeposition of lead.
- Example 3 can be 200 to 250 g./l. to 30 gJl. 5 to g./l. 0.5 g to 5 all l to 2.5 a./dm. to C. 120 m 300 g./l. 150 m 500 g./l. 80 to 220 g./l.
- EXAMPLE 5 Plating baths for deposition of zinc.
- Zinc fluoborate Ammonium fluoborate Ammonium chloride Current density Temperature Addition of Zinc sulphate Boric acid Ammonium sulphate Addition Current density Temperature Zinc Fluoborate Ammonium fluoborate Ammonium chloride Addition Current density Temperature Zinc fluosilicate Aluminum sulphate Ammonium chloride Temperature Current density Addition Dibasic potassium phosphate Potassium pyrophosphate Zinc sulphate (thioacetic acid 150 to 350 g./l. 301540 g./l. 20 to so g./l.
- EXAMPLE 6 Gold plating baths
- the addition composition can be prepared from the following constituents:
- composition can be added to of composition are also given:
- EXAMPLE 7 Cadmiumplating baths The addition composition is prepared from the following constituents:
- compositions for addition to quality protective layer on a base one of the two basic baths given below, in which the operating condition and proportion their alloys to obtain plated coatings of better quality the steps of a. degrading cellulose in a strong acid selected from H SO and HCl in the presence of glycocoll and adding an alkali metal halide;
- a ketone in an anhydrous medium having an alkaline pH value with a cyclic aldehyde and with at least one third compound selected from the group consisting of the unsaturated alcohols, amyl aldehyde, cinnamic aldehyde and amylcinnamic aldehyde; then adding an alkali sulphide or a mercaptan in the presence ofa mercury salt; then halogenating and stabilizing the mixture by addition of an oxidizing agent;
- alkali metal halide is selected from the group consisting of N aCl and NaF.
- step (b) is carried out until an amber shade appears in the mixture.
- step (a) is carried out using about g. of glycocoll and 100 g. of NaCl per 20 g. of cellulose and step (b) is carried out starting with 600 cm. of acetone, 1,200 cm. of propargyl alcohol, 1,000 cm. of furfural, 200 g. of Na S, and 20 cm. of hydrogen peroxide.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR6900327A FR2029120A5 (enrdf_load_stackoverflow) | 1969-01-10 | 1969-01-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3642588A true US3642588A (en) | 1972-02-15 |
Family
ID=9027742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2406A Expired - Lifetime US3642588A (en) | 1969-01-10 | 1970-01-12 | Addition compositions for acid electroplating baths |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3642588A (enrdf_load_stackoverflow) |
| DE (1) | DE2000821A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2029120A5 (enrdf_load_stackoverflow) |
| GB (1) | GB1281981A (enrdf_load_stackoverflow) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4078979A (en) * | 1976-02-09 | 1978-03-14 | The International Nickel Company, Inc. | Nickel electrowinning process |
| US20050230264A1 (en) * | 2004-04-02 | 2005-10-20 | Richard Lacey | Electroplating solution and method for electroplating |
| EP1897975A1 (en) * | 2006-09-07 | 2008-03-12 | Enthone, Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| EP1897973A1 (en) * | 2006-09-07 | 2008-03-12 | Enthone, Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| US20100012500A1 (en) * | 2006-09-07 | 2010-01-21 | Enthone Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| US10509705B2 (en) * | 2011-11-04 | 2019-12-17 | Veritas Technologies Llc | Application protection through a combined functionality failure manager |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA762380B (en) * | 1975-05-16 | 1977-04-27 | M & T Chemicals Inc | Bright nickel-iron plating |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1464149A (en) * | 1921-11-08 | 1923-08-07 | Classen Alexander | Process for the production of glossy-metal coatings on metals |
| US2149344A (en) * | 1935-03-22 | 1939-03-07 | Du Pont | Apparatus and process for the study of plating solutions |
| US2312097A (en) * | 1939-07-20 | 1943-02-23 | Du Pont | Electroplating |
| US2526999A (en) * | 1947-06-07 | 1950-10-24 | Hanson Van Winkle Munning Co | Cadmium plating bath |
| US2848393A (en) * | 1955-11-08 | 1958-08-19 | Hanson Van Winkle Munning Co | Bright cadmium plating |
| US2912370A (en) * | 1957-10-07 | 1959-11-10 | Allied Res Products Inc | Addition agent for cadmium plating solution |
-
1969
- 1969-01-10 FR FR6900327A patent/FR2029120A5/fr not_active Expired
-
1970
- 1970-01-09 DE DE19702000821 patent/DE2000821A1/de active Pending
- 1970-01-12 GB GB0366/70A patent/GB1281981A/en not_active Expired
- 1970-01-12 US US2406A patent/US3642588A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1464149A (en) * | 1921-11-08 | 1923-08-07 | Classen Alexander | Process for the production of glossy-metal coatings on metals |
| US2149344A (en) * | 1935-03-22 | 1939-03-07 | Du Pont | Apparatus and process for the study of plating solutions |
| US2312097A (en) * | 1939-07-20 | 1943-02-23 | Du Pont | Electroplating |
| US2526999A (en) * | 1947-06-07 | 1950-10-24 | Hanson Van Winkle Munning Co | Cadmium plating bath |
| US2848393A (en) * | 1955-11-08 | 1958-08-19 | Hanson Van Winkle Munning Co | Bright cadmium plating |
| US2912370A (en) * | 1957-10-07 | 1959-11-10 | Allied Res Products Inc | Addition agent for cadmium plating solution |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4078979A (en) * | 1976-02-09 | 1978-03-14 | The International Nickel Company, Inc. | Nickel electrowinning process |
| US20050230264A1 (en) * | 2004-04-02 | 2005-10-20 | Richard Lacey | Electroplating solution and method for electroplating |
| US7235165B2 (en) | 2004-04-02 | 2007-06-26 | Richard Lacey | Electroplating solution and method for electroplating |
| EP1897975A1 (en) * | 2006-09-07 | 2008-03-12 | Enthone, Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| EP1897973A1 (en) * | 2006-09-07 | 2008-03-12 | Enthone, Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| US20100012500A1 (en) * | 2006-09-07 | 2010-01-21 | Enthone Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| US8366901B2 (en) | 2006-09-07 | 2013-02-05 | Enthone Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| US10509705B2 (en) * | 2011-11-04 | 2019-12-17 | Veritas Technologies Llc | Application protection through a combined functionality failure manager |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1281981A (en) | 1972-07-19 |
| DE2000821A1 (de) | 1970-07-16 |
| FR2029120A5 (enrdf_load_stackoverflow) | 1970-10-16 |
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