US3855010A - Composition and method for color passivation of zinc and cadmium - Google Patents
Composition and method for color passivation of zinc and cadmium Download PDFInfo
- Publication number
- US3855010A US3855010A US00319391A US31939172A US3855010A US 3855010 A US3855010 A US 3855010A US 00319391 A US00319391 A US 00319391A US 31939172 A US31939172 A US 31939172A US 3855010 A US3855010 A US 3855010A
- Authority
- US
- United States
- Prior art keywords
- zinc
- cadmium
- composition
- calculated
- compound
- 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 84
- 238000002161 passivation Methods 0.000 title claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 70
- 229910052725 zinc Inorganic materials 0.000 title claims description 70
- 239000011701 zinc Substances 0.000 title claims description 70
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 68
- 229910052793 cadmium Inorganic materials 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 21
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 47
- -1 NITRATE COMPOUND Chemical class 0.000 claims abstract description 39
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001413 amino acids Chemical class 0.000 claims abstract description 25
- 229910052796 boron Inorganic materials 0.000 claims abstract description 25
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 19
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 18
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 150000002823 nitrates Chemical class 0.000 claims abstract description 9
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052790 beryllium Inorganic materials 0.000 claims description 14
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 239000004615 ingredient Substances 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- FQLQNUZHYYPPBT-UHFFFAOYSA-N potassium;azane Chemical compound N.[K+] FQLQNUZHYYPPBT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052804 chromium Inorganic materials 0.000 abstract description 23
- 239000000243 solution Substances 0.000 description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 239000002253 acid Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 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
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229960002449 glycine Drugs 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 3
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 239000001120 potassium sulphate Substances 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- NFQAIWOMJQWGSS-UHFFFAOYSA-N 3-amino-3-methylbutanoic acid Chemical compound CC(C)(N)CC(O)=O NFQAIWOMJQWGSS-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- HEFYHDKCEOTPPW-UHFFFAOYSA-N 2-(octylamino)acetic acid Chemical compound CCCCCCCCNCC(O)=O HEFYHDKCEOTPPW-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 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
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PYUBPZNJWXUSID-UHFFFAOYSA-N pentadecapotassium;pentaborate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] PYUBPZNJWXUSID-UHFFFAOYSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/26—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
- C23C22/27—Acids
Definitions
- ABSTRACT A composition comprising a mixture of hexavalent chromium compounds such as chromic anhydride and soluble chromates, and soluble nitrates, soluble sulphates, soluble boron compounds, and an amino acid, said composition having the following content of the above components (in weight parts):
- hexavalent chromium compound (calculated as chromium) 1.7-70.0 nitrate compound (calculated as N00) 1.045.0 sulphate compound (calculated as SO 1. 25.0 boron compound (calculated as boron) 0.5l0.0 amino acid 0.5-6.0
- the present invention relates to improvements in compositions and methods for the chemical treatment of metal surfaces, and more particularly to a composition and a method for color passivation of zinc and cadmium.
- the invention is of particular advantage in providing a color passive film on zinc and cadmium in order to increase the corrosion resistance of articles made therefrom, or articles having a zinc or cadmium surface, such as zincor cadmium-based alloys, zinc castings, and, specifically, articles having a zincor cadmium-plated coating.
- Zinc and cadmium become corroded in a relatively short time under the effect of atmospheric moisture.
- they may be passivated in acid solutions of hexavalent chromium.
- Aqueous solutions are known in this art for passivating zinc and cadmium containing chromic anhydride, sulphate ions, boric and nitric acids (cf. US. Pat. No. 2,904,414), or hexavelent chromium, sulphate ions, nitrate ions and acetate or borate ions (cf. US. Pat. No. 3,121,032).
- the solution containing hexavalent chromium, sulphate ions, nitrate ions, and acetate or borate ions is conductive to the formation of colorless passive films on articles having a zinc or cadmium surface, but again their corrosion resistance fails to increase significantly.
- the above methods can be applied in order to obtain decorative films on articles having a Zinc or cadmium surface.
- a zinc or cadmium surface shows its first signs of corrosion even before a 20 to 30 hour period has expired.
- Another object of the invention is to provide a dry composition for adjusting the solution for color passivation of zinc and cadmium.
- Still another object of the invention is to provide a solution for color passivation of zinc and cadmium which does not require frequent replacement, but which is makes -t possible to replenish or make adjustment during the course of passivating.
- Yet another object of the invention is to provide a method for obtaining color passive films on zinc and cadmium possessing high corrosion resistance.
- a novel composition which is, according to the invention, a mixture of hexavalent chromium compounds, such as chromic anhydride and/or soluble chromates, and soluble nitrate compounds, soluble sulphate compounds,
- hexavalent chromium compound (calculated as chromium) 1.7-70.0 nitrate compound (calculated as N0 1.0-45.0 sulphate compound (calculated as S0, 1.0-25.0 boron compound (calculated as boron) 0.5-10.0 amino acid 0.05-6.0
- Hexavalent chromium compounds constitute the basic passivating agent. Its content in a composition for color passivation of zinc and cadmium should be 1.7 to 70.0 weight parts.
- Sulphate compounds are the main activators of the passivating process. Their concentration in a passivating composition, when calculated as $0 should vary from 1.0 to 25.0 weight parts.
- Nitrate compounds act as the oxidizing and brightening agents. Their concentration in the passivating composition, when calculated as N0 should be maintained within 1.0 to 45.0 weight parts.
- Boron compounds impart the polishing and brightening properties to the composition. Their concentration in a composition, when calculated as boron, should be from 0.5 to 10.0 weight parts.
- Amino acids are the stabilizing and buffering agents ensuring an extremely long life for the passivating composition. Their content in a composition should be from 0.05 to 6.0 weight parts.
- apassivating composition contain (in weight parts):
- hexavalent chromium compound (calculated as chromium) l 1.0-21 0 nitrate compound (calculated as N0 2.4-6.0 sulphate compound (calculated as $0. 2.2-7.0 boron compound (calculated as boron) 1.1 .3 amino acid 0.05-0.1
- the hexavalent chromium be introduced into the composition as chromic anhydride compounds; chromates of ammonium, beryllium, potassium, cadmium, lithium, magnesium, sodium, zinc; bi chromates of ammonium, beryllium, potassium, cadmium, lithium, magnesium, sodium, zinc; mixtures of said chromates; mixtures of said bichromates; mixtures of said chromates and with bichromates; mixtures of chromic anhydride and chromates; mixtures of chromic anhydride and bichromates; and mixtures of chromic anydride, chromates and bichromates, all being taken separately or in combinations.
- the sulphate be introduced into the composition as sulphate compounds of ammonium, beryllium, potassium, cadmium, lithium, magnesium, sodium, zinc, bisulphate compounds of ammonium, potassium, lithium, and sodium, all being taken separately or in combinations.
- the boron should be preferably introduced into the composition as the following compounds: boric acid, magnesium orthoborate, and polyborates of ammonium, beryllium, potassium, lithium, magnesium, sodium, all being taken separately or in combinations.
- the invention can provide a composition having the following content of its ingredients in an aqueous solution thereof (in g/l):
- composition ingredients in an aqueous solution thereof be (in g/l):
- the content of the composition ingredients in the aqueous solution thereof be (in 8/ hexavalent chromium compound (calculated as chromium) 1 10-210 nitrate compound (calculated as h1g6) 2.4-6.0 sulphate compound (calculated as 2.2-7.0 boron compound (caclulated as boron) 1.1-4.3 amino acid 0.5-4.0
- the novel method for passivating zinc and cadmium by dipping them into an aqueous solution containing a hexavalent chromium compound comprises using a composition having the folowing ingredientcontents in an aqueous solution thereof (in g/l):
- the proposed composition for color passivating zinc and cadmium is a mixture of non-volatile solid substances which is easy to prepare, to transport, to store and to use. The latter requirement is attained by an easy preparation of the passivating solution, as well as in the facile adjustment and control thereof. If neces sary, the composition may be prepared on the spot by conventional mechanical blending starting ingredients.
- a bright color passive film is formed on the zinc or cadmium surface.
- This passive film has bright opalescent tints even if the zinc or cadmium surface was dull prior to treatment.
- the passive films obtained by the novel method are abrasion-resistant in the course of passivating, therefore use may be made of manually operated and automatic apparatus of both stationary and rotary type may be used.
- the passive films obtained by the method provided herein have a high corrosion resistance.
- the passive film formed on a zinc or cadmium surface is tested for corrosion resistance by the so-called salt fog method whereby the film is subjected to a continuous action of a fog produced by spraying in a testing cabinet with a 5% aqueous neutral solution of sodium chloride at a temperature of 35 2*: 1C.
- the corrosion resistance of a film is determined by the time interval between the onset of the test and the moment of the ap- Example 1.
- chromic anhydride (calculated as chromium) potassium chromate (calculated as chromium) cadmium nitrate (calculated as N0 potassium sulphate (calculated as 50 sodium tetraborate (calculated as boron) 0: -amino glutaric acid Example 2.
- a-aminoisoca roic acid 30. a-amino B-p enyl-propionic acid.
- a passivating solution is prepared by dissolving the dry passivating composition in water.
- the solution is, if necessary, adjusted with an acid such I as sulphuric acid, or a hydroxide such as sodium hydroxide, to maintain the solution pH within a range of from 1.1 to 2.8.
- the preferable pH of the passivating solution within this range depends on the time of the treatment of a zinc or cadmium surface by the solution. In case the passivation takes little time (3 to 8 seconds), the optimum pH would be 1.1 to 1.7, and if passivating treatment lasts longer (20 to 16 seconds), the optimum pH would be from 1.7 to 2.5.
- the optimum pH of the solution would be from 1.6 to 2.3.
- the time for treatment of a zinc or cadmium surface with a passivating solution may vary from 3 to sec, but usually it lies within 10 to 35 seconds.
- articles having a zinc or cadmium surface are dipped into a passivating solution for a definite period of time depending on the properties of the solution, then removed therefrom, rinsed in running cold water, then in heated water, and, finally, dried.
- the zinc or cadmium surface is coated with a color opalescent passive film of high corrosion resistance.
- the solution contain less amino acid.
- the concentration of the solution ingredients is constantly diminishing due to a reaction between the workpiece surface and the solution, and a dilution of the solution.
- An outstanding feature of the present invention is the possibility of replenishing and adjusting the passivating solution, in the course of passivating the treatment, by adding the above dry passivating compositions and an acid in the amounts is dictated by the assays, e.g. hexavalent chromium and pH.
- Example 1 208.74 g of the dry composition of Example 1 were dissolved in 3 of water. After adding 1.0 ml/l of H 80, (d 1.83) to a pH of 1.86, a passivating solution was obtained containing (in g/l):
- Said solution was further used for passivating zinc articles. ln the'course of passivating, the solution was replenished with sulphuric acid and the dry passivating composition of Example 1 in amounts as based on the assays for pH and hexavalent chromium. Throughout the passivating process, the solution was adjusted by adding an amount of dry composition sufficient for the volume of the solution to become five-fold of that of which it originally was. After passivating zinc plated surfaces of 0.1, 1.0, 10.0 and 30.0 square meters the, samples were taken for corrosion tests in a salt-fog cabinet. The first signs of corrosion appeared, in the first three cases, after 120 hours and, in the fourth case, after hours of testing.
- the passivation of the cadmium-plated workpieces continued in said apparatus.
- the solution was replenished with sulphuric acid and the dry passivating composition of Example 2 in amounts as based on the assay for pH and hexavalent v chromium.
- the solution was adjusted by adding an amount of dry composition sufficient to attain a twenty-fold increase of the initial solution volume.
- passivating 0.4, 4.0, 40 and square meters of the cadmiumplated surface the samples were taken for corrosion tests in a salt-fog cabinet. The first signs of corrosion appeared, in the first three cases, after 148 hours and, in the fourth case, after 120 hours of testing.
- a passivating solution was prepared by dissolving in water the respective amounts of potassium chromate,
- beryllium nitrate zinc sulphate, boric acid, and a-amino-B(phenyl)-propionic acid.
- a passivating solution was prepared by dissolving in water the respective amounts of ammonium bichromate, potassium nitrate, potassium sulphate, lithium tetraborate, and a-amino-isocaproic acid.
- a passivating solution was prepared by dissolving in water the composition of Example 6.
- a passivating solution was prepared by dissolving in water the respective amounts of sodium chromate, sodium nitrate, sodium sulphate, potassium tetraborate, and ,B-aminopropionic acid.
- a passivating solution was prepared by dissolving in water the respective amounts of potassium bichromate, beryllium sulphate, zinc nitrate, potassium pentaborate, and a-amino-succinic acid.
- a passivating solution was prepared by dissolving in water the respective amounts of chromic anhydride,
- a passivating solution was prepared by dissolving in water the respective amounts of chromic anhydride, potassium chromate, zinc nitrate, lithium sulphate, zinc borate, and a-aminoisovaleric acid.
- a passivating solution was prepared by dissolving in water the respective amounts of chromic anhydride, lithium sulphate, potassium nitrate, sodium tetraborate, and a-aminopropionic acid.
- a passivating solution was prepared by dissolving in water the respective amounts of chromic anhydride, sodium chromate, beryllium nitrate, potassium sulphate, lithium tetraborate, and N N-diethyl-aminoacetic acid.
- Steel workpieces were passivated in Examples 10, ll 15, 18 and 20 having a bright zinc coating obtained in a cyanide bath, in Example 16, steel workpieces with a matte zinc coating obtained in a cyanide bath were passivated, and in Examples 9, l3 and 19, steel workpieces with a bright cadmium coating obtained in a cyanide bath, in Example 21, steel workpieces with a matte cadmium coating obtained in a cyanide bath, in Example l2, workpieces made of a zinc alloy, in Example 14, workpieces made of a zinc casting, and in Example 17, a steel workpiece coated with zinc by a hot process were also passivated.
- the treated workpieces were coated with a color opalescent film.
- the brightest films were obtained in Examples 9, l0, l3, l8 and 20.
- a composition for the color passivation of zinc and cadmium consisting essentially of a mixture of hexava-- lent chromium compounds selected from the group consisting of chromic anhydride and soluble chromates, and soluble nitrate compounds, soluble sulphate compounds, soluble boron compounds, and an amino acid of the general formula:
- R R R R l-l alkyl (C -C phenyl, substituted alkyls and phenyls, containing substituents OH, R, -COR, COOH, COOR, CONH 'CN,, -NH NHR, -RNR, (R alkyl, and aryl), n l 5, said composition having the following content of the above components (in weight parts):
- hexavalent chromium compound (calculated as chromium 1.7-70.0 nitrate compound (calculated as N0 1.0-4S.0 sulphate compound (calculated as S0 l.0-25.0 boron compound (calculated as boron) 0.5-l0.0 amino acid 0.05-6.0.
- hexa alent chromium compound 1 (calculated as chromium) 11.0-21.0 nitrate compound (calculated as NO;,) 2.4-6.0 sulphate compound (calculated as S0,, 7) 2.2-7.0 boron compound (calculated as boron) 1.1-4.3 amino acid ODS-0.1.
- hexavalent chromium compound (calculated as chromium) 11.0-21.0 nitrate compound (calculated as N0 2.4-6.0 sulphate compound (calculated as SO 2.2-7.0 boron compound (calculated as boron) 1.1-4.3 amino acid 0.5-4.0.
- hexavalent chromium compound (calculated as chromium 1.7-70.0 "see sweep-l su e com un cu a e as bor'on compo iid (calculated as boron) 0.5-l0.0 amino acid 005-61) and the solution pH 1.1-2.8.
- hexavalent chromium compound (calculated as chromium? 11.0-21.0 nitrate compound Scalcu ated as N06) 2.4-6.0 sulphate compoun (calculated as S 2.2-7.0 boron compound (calculated as boron) 1.1-4.3 ammo aci 0.05-0.1
- hexavalent chromium compound (calculated as chromium) l 1.0-2l.0 nitrate compound (calculated as N0 2.4-6.0 sulphate compound (calculated as S0 2.2-7.0 boron compound (calculated as boron) 1.1-4.0 amino acid 0.5-4.0
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU7201762901A SU384443A1 (ru) | 1972-04-05 | 1972-04-05 | Состав дл приготовлени раствора, пассивирующего поверхность цинка и кадми |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3855010A true US3855010A (en) | 1974-12-17 |
Family
ID=20507624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00319391A Expired - Lifetime US3855010A (en) | 1972-04-05 | 1972-12-29 | Composition and method for color passivation of zinc and cadmium |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3855010A (it) |
| CA (1) | CA994219A (it) |
| CS (1) | CS169955B1 (it) |
| DD (1) | DD102165A1 (it) |
| DE (1) | DE2301096C3 (it) |
| FR (1) | FR2179112B1 (it) |
| GB (1) | GB1400681A (it) |
| HU (1) | HU166110B (it) |
| IT (1) | IT974434B (it) |
| PL (1) | PL91823B1 (it) |
| SU (1) | SU384443A1 (it) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4591416A (en) * | 1983-01-04 | 1986-05-27 | Ebara-Udylite Co., Ltd. | Chromate composition and process for treating zinc-nickel alloys |
| US5735972A (en) * | 1996-05-23 | 1998-04-07 | Dipsol Chemicals Co., Ltd. | Black chromate-treatment solution for Zn-Ni alloy plated film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2483510A (en) * | 1945-04-14 | 1949-10-04 | United Chromium Inc | Composition for dip coating solution and dip process for coloring zinc |
| US2904414A (en) * | 1954-08-04 | 1959-09-15 | Allied Res Products Inc | Formulation for producing a protective bright chemically polished surface on zinc and cadmium |
| US3121032A (en) * | 1960-09-27 | 1964-02-11 | M & T Chemicals Inc | Process for applying a protective transparent coating to zinc and cadmium and composition therefor |
| US3307980A (en) * | 1962-08-15 | 1967-03-07 | Hooker Chemical Corp | Treatment of metal surfaces |
| US3519501A (en) * | 1968-04-16 | 1970-07-07 | Diamond Shamrock Corp | Chromic acid-organic coating compositions |
-
1972
- 1972-04-05 SU SU7201762901A patent/SU384443A1/ru active
- 1972-12-29 US US00319391A patent/US3855010A/en not_active Expired - Lifetime
- 1972-12-29 IT IT55176/72A patent/IT974434B/it active
-
1973
- 1973-01-10 DE DE2301096A patent/DE2301096C3/de not_active Expired
- 1973-01-16 GB GB222173A patent/GB1400681A/en not_active Expired
- 1973-01-19 CA CA161,600A patent/CA994219A/en not_active Expired
- 1973-02-07 DD DD168737A patent/DD102165A1/xx unknown
- 1973-04-03 PL PL1973161690A patent/PL91823B1/pl unknown
- 1973-04-04 FR FR7312139A patent/FR2179112B1/fr not_active Expired
- 1973-04-04 CS CS2413A patent/CS169955B1/cs unknown
- 1973-04-05 HU HUII140A patent/HU166110B/hu unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2483510A (en) * | 1945-04-14 | 1949-10-04 | United Chromium Inc | Composition for dip coating solution and dip process for coloring zinc |
| US2904414A (en) * | 1954-08-04 | 1959-09-15 | Allied Res Products Inc | Formulation for producing a protective bright chemically polished surface on zinc and cadmium |
| US3121032A (en) * | 1960-09-27 | 1964-02-11 | M & T Chemicals Inc | Process for applying a protective transparent coating to zinc and cadmium and composition therefor |
| US3307980A (en) * | 1962-08-15 | 1967-03-07 | Hooker Chemical Corp | Treatment of metal surfaces |
| US3519501A (en) * | 1968-04-16 | 1970-07-07 | Diamond Shamrock Corp | Chromic acid-organic coating compositions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4591416A (en) * | 1983-01-04 | 1986-05-27 | Ebara-Udylite Co., Ltd. | Chromate composition and process for treating zinc-nickel alloys |
| US5735972A (en) * | 1996-05-23 | 1998-04-07 | Dipsol Chemicals Co., Ltd. | Black chromate-treatment solution for Zn-Ni alloy plated film |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2179112A1 (it) | 1973-11-16 |
| DE2301096A1 (de) | 1973-10-18 |
| CA994219A (en) | 1976-08-03 |
| PL91823B1 (it) | 1977-03-31 |
| SU384443A1 (ru) | 1977-12-05 |
| DE2301096B2 (de) | 1978-04-13 |
| HU166110B (it) | 1975-01-28 |
| DD102165A1 (it) | 1973-12-12 |
| FR2179112B1 (it) | 1976-06-11 |
| DE2301096C3 (de) | 1978-12-14 |
| CS169955B1 (it) | 1976-08-27 |
| IT974434B (it) | 1974-06-20 |
| GB1400681A (en) | 1975-07-23 |
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