EP0716163A1 - Lösung und Verfahren zum Chromatieren zur Endbehandlung von Zink, Zinklegierungen oder Cadmium - Google Patents
Lösung und Verfahren zum Chromatieren zur Endbehandlung von Zink, Zinklegierungen oder Cadmium Download PDFInfo
- Publication number
- EP0716163A1 EP0716163A1 EP95402602A EP95402602A EP0716163A1 EP 0716163 A1 EP0716163 A1 EP 0716163A1 EP 95402602 A EP95402602 A EP 95402602A EP 95402602 A EP95402602 A EP 95402602A EP 0716163 A1 EP0716163 A1 EP 0716163A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- bath
- zinc
- finishing
- acid
- 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.)
- Granted
Links
- 238000004532 chromating Methods 0.000 title claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 8
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 239000011701 zinc Substances 0.000 title claims description 7
- 229910052793 cadmium Inorganic materials 0.000 title claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- -1 sulphate ions Chemical class 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000019253 formic acid Nutrition 0.000 claims abstract description 3
- 230000007797 corrosion Effects 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008119 colloidal silica Substances 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910001430 chromium ion Inorganic materials 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract 3
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 1
- 230000035939 shock Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 239000007921 spray Substances 0.000 description 5
- 235000016804 zinc Nutrition 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 1
- JHDXAQHGAJXNBY-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JHDXAQHGAJXNBY-UHFFFAOYSA-M 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-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
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003378 silver Chemical class 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
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 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
- C23C22/30—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 trivalent chromium
-
- 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
-
- 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
- C23C22/82—After-treatment
- C23C22/84—Dyeing
Definitions
- the present invention relates to the finishing of surfaces of zinc, of zinc alloy, or of cadmium in order to give them a high resistance to corrosion.
- Corrosion resistance is assessed in the laboratory by an accelerated salt spray test, carried out according to AFNOR NFX41002 / ASTM B117-73 / DIN40046-11.
- the automotive industry requires that parts that have undergone thermal shock show no zinc salt point (or white rust) after 200 hours of exposure to salt spray and no red rust point after 400 hours, even 600 hours. In addition, also after thermal shock, said parts must also successfully undergo natural corrosion tests.
- the parts intended for the automobile industry must satisfy aesthetic requirements of color: yellow, green, and more particularly black.
- This black color which must be deep, shiny and uniform, is particularly difficult to obtain when at the same time a high resistance to corrosion after thermal shock of one hour at 120 ° C. is required.
- a chromating bath comprising an acrylic polymer and a phosphate makes it possible, according to patent EP 264 472, to obtain a beautiful black coloration resistant to corrosion in salt spray after thermal shock.
- the implementation of such a bath is more delicate than that of a conventional chromating bath.
- the film obtained turns out to be unstable (formation of yellow chromium salts) and the use of a polymer leads to the appearance of "drops" on the parts treated with the fastener and difficulties in cleaning the 'apparatus (assemblies and wringer baskets) used for treatment.
- the present invention therefore relates to a process for finishing surfaces of zinc, zinc alloy, or cadmium, characterized in that the parts to be treated are first brought into contact with an acid chromate bath based on of chromium, cobalt and silver salts, then with an aqueous finishing bath comprising a colloidal silica, a corrosion inhibitor, a complexing agent, a surfactant and a black dye.
- the chromating bath according to the invention is an aqueous solution having a pH of between 1 and 2 and containing per liter:
- sodium bichromate, cobalt sulphate and silver nitrate are preferably used, but it would not depart from the scope of the present invention to use other water-soluble salts of hexavalent chromium, cobalt or silver.
- the weak organic acid the role of which is to reduce hexavalent chromium and to regulate the attack of zinc
- acetic acid, formic acid or oxalic acid are preferably used.
- the pH of the chromating bath advantageously adjusted by means of sulfuric acid, is preferably between 1.2 and 1.8.
- the finishing bath must be able to operate at a pH of between 1 and 5, preferably between 2.5 and 4, and have excellent chemical stability without any gelling of the colloidal silica during storage or working.
- the colloidal silica is present at a concentration such that there is from 20 to 40 g / l expressed as Si0 2 .
- the weak complexing agent, used in a concentration of 0.1 to 2 g / l, can be for example gluconic acid, oxalic acid, citric acid, maleic acid, phthalic acid, or a salt potassium, sodium or ammonium of such an acid.
- Corrosion inhibitor is used at a concentration of 0.01 to 1 g / l and can be, for example, hydrazine hydrate or a benzoate such as sodium benzoate.
- the surfactant used at a concentration of 0.01 to 2 g / l can be of nonionic or anionic nature.
- a black water-soluble dye preferably a dye of the azo metalliferous complex type, can be added to the finishing bath, at a concentration of 1 to 8 g / l.
- particles of PTFE of about 0.1 to 0.2 microns can be added to the finishing bath.
- This product must be compatible with the pH of the medium of use; for a 60% aqueous dispersion of PTFE, the concentration can range from 1 to 10 ml / l. This also makes it possible, during the barrel treatment of the fasteners, to obtain an adequate coefficient of friction.
- an acrylic polymer can be incorporated into the finishing bath, for example an aqueous emulsion with density 1.055 g / ml at a concentration of 10 to 100 ml / l; it is also possible to use a polyethylene glycol.
- the parts are brought into contact with the chromating bath, then with the finishing bath, by spraying, but preferably by immersion.
- this operation can be carried out using a fastener (dead bath) or a barrel (in bulk), with or without taking up the basket in the case of barrel treatment.
- the treatment can be carried out at a temperature ranging from 15 to 40 ° C, but it is preferably carried out at a temperature between 20 and 30 ° C.
- the duration of contacting of the parts with each of the baths can vary within wide limits. It is generally between 10 seconds and 10 minutes, but is preferably one to two minutes.
- the chromating is advantageously carried out with stirring, the latter being preferably obtained by means of an air ramp.
- the parts are not dried, but only rinsed with water before bringing them into contact with the finishing bath, this treatment preferably being carried out without stirring.
- the parts are dried for 5 to 15 minutes at a temperature ranging from 60 to 100 ° C. Their corrosion resistance is only tested after storage for at least 48 hours so that the film formed is stabilized.
- an aqueous chromating bath was prepared with 30 g / l of sodium dichromate dihydrate, 5 g / l of anhydrous sodium sulfate, 8 g / l of sulfuric acid, 0.6 g / l of cobalt sulfate heptahydrate, 0.37 g / l of silver nitrate and 85 ml / l of acetic acid.
Landscapes
- 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 And Plating Baths Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9414701A FR2727983B1 (fr) | 1994-12-07 | 1994-12-07 | Bain de chromatation et procede pour la finition de surfaces de zinc, d'alliage de zinc, ou de cadmium |
| FR9414701 | 1994-12-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0716163A1 true EP0716163A1 (de) | 1996-06-12 |
| EP0716163B1 EP0716163B1 (de) | 1999-01-20 |
Family
ID=9469556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95402602A Expired - Lifetime EP0716163B1 (de) | 1994-12-07 | 1995-11-20 | Lösung und Verfahren zum Chromatieren zur Endbehandlung von Zink, Zinklegierungen oder Cadmium |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5876517A (de) |
| EP (1) | EP0716163B1 (de) |
| JP (1) | JPH08218182A (de) |
| KR (1) | KR100322935B1 (de) |
| CA (1) | CA2164555C (de) |
| DE (1) | DE69507441T2 (de) |
| ES (1) | ES2128679T3 (de) |
| FR (1) | FR2727983B1 (de) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999014398A1 (de) * | 1997-09-12 | 1999-03-25 | Henkel Kommanditgesellschaft Auf Aktien | CHROMATIERUNG ODER NACHPASSIVIERUNG MIT STABILISIERTEN Cr(III)/Cr(VI)-HALTIGEN LÖSUNGEN |
| US6866896B2 (en) | 2002-02-05 | 2005-03-15 | Elisha Holding Llc | Method for treating metallic surfaces and products formed thereby |
| US6994779B2 (en) | 1997-01-31 | 2006-02-07 | Elisha Holding Llc | Energy enhanced process for treating a conductive surface and products formed thereby |
| CN105088325A (zh) * | 2015-07-20 | 2015-11-25 | 中国船舶重工集团公司第十二研究所 | 一种磁控溅射类石墨碳膜的退镀方法 |
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| US6849063B1 (en) | 1994-03-11 | 2005-02-01 | Wit Ip Corporation | Thermal treatment apparatus |
| GB9425030D0 (en) | 1994-12-09 | 1995-02-08 | Alpha Metals Ltd | Silver plating |
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| US6544397B2 (en) | 1996-03-22 | 2003-04-08 | Ronald Redline | Method for enhancing the solderability of a surface |
| US6905587B2 (en) | 1996-03-22 | 2005-06-14 | Ronald Redline | Method for enhancing the solderability of a surface |
| US7314671B1 (en) | 1996-04-19 | 2008-01-01 | Surtec International Gmbh | Chromium(VI)-free conversion layer and method for producing it |
| DE19615664A1 (de) | 1996-04-19 | 1997-10-23 | Surtec Produkte Und Systeme Fu | Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung |
| US6592738B2 (en) | 1997-01-31 | 2003-07-15 | Elisha Holding Llc | Electrolytic process for treating a conductive surface and products formed thereby |
| US6322687B1 (en) | 1997-01-31 | 2001-11-27 | Elisha Technologies Co Llc | Electrolytic process for forming a mineral |
| US6893430B2 (en) | 1998-02-04 | 2005-05-17 | Wit Ip Corporation | Urethral catheter and guide |
| USRE45842E1 (en) | 1999-02-17 | 2016-01-12 | Ronald Redline | Method for enhancing the solderability of a surface |
| US20040188262A1 (en) * | 2002-02-05 | 2004-09-30 | Heimann Robert L. | Method for treating metallic surfaces and products formed thereby |
| US7144637B2 (en) | 2004-07-12 | 2006-12-05 | Thomae Kurt J | Multilayer, corrosion-resistant finish and method |
| US20070119715A1 (en) * | 2005-11-25 | 2007-05-31 | Sacks Abraham J | Corrosion Resistant Wire Products and Method of Making Same |
| DE102006025847A1 (de) * | 2006-06-02 | 2007-12-06 | Merck Patent Gmbh | Verwendung von Phosphinsäure in der Galvanotechnik |
| JP2007333186A (ja) * | 2006-06-19 | 2007-12-27 | Japan Power Fastening Co Ltd | ねじ式ファスナー及びその製造方法 |
| US20100221574A1 (en) * | 2009-02-27 | 2010-09-02 | Rochester Thomas H | Zinc alloy mechanically deposited coatings and methods of making the same |
| US10717922B2 (en) * | 2009-05-13 | 2020-07-21 | Abdullah Al-Dhafeeri | Composition and method for stimulation of oil production in sandstone formations |
| US20110070429A1 (en) * | 2009-09-18 | 2011-03-24 | Thomas H. Rochester | Corrosion-resistant coating for active metals |
| US20120203210A1 (en) * | 2011-02-07 | 2012-08-09 | Schanz Richard W | Urinary catheter and method |
| KR102285559B1 (ko) | 2014-08-29 | 2021-08-04 | 신헌철 | 농작물 재배용 점적 조절장치 |
| KR101902044B1 (ko) | 2014-09-02 | 2018-09-27 | 홍학표 | 관수 시설용 점적 버튼 |
| CN112176376B (zh) * | 2020-10-09 | 2022-03-11 | 伸荣(上海)水处理环保工程有限公司 | 一种金属表面的处理工艺 |
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| FR947164A (fr) * | 1945-04-14 | 1949-06-24 | United Chromium | Compositions et procédé de trempage pour la coloration des métaux |
| FR2522023A1 (fr) | 1982-02-19 | 1983-08-26 | Waldberg | Bains et procedes utilisables pour realiser le chromatage de surfaces de zinc et de cadmium |
| RO94238A2 (ro) * | 1986-09-17 | 1988-03-30 | Institutul De Cercetare Stiintifica Si Inginerie Tehnologica Pentru Industria Constructiilor De Masini,Ro | Procedeu pentru pasivarea neagra a depunerilor de zinc sau cadmiu |
| EP0264472A1 (de) | 1986-10-21 | 1988-04-27 | Procoat, S.A. | Wässrige Zusammensetzung zum Passivieren von Zink- und Kadmiumoberflächen |
| EP0274543A1 (de) * | 1986-07-14 | 1988-07-20 | Nihon Parkerizing Co., Ltd. | Zusammensetzung zur behandlung einer metallfläche und behandlungsverfahren |
| JPS6456877A (en) * | 1987-08-28 | 1989-03-03 | Kobe Steel Ltd | Production of chromated galvanized steel sheet |
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- 1994-12-07 FR FR9414701A patent/FR2727983B1/fr not_active Expired - Fee Related
-
1995
- 1995-11-20 ES ES95402602T patent/ES2128679T3/es not_active Expired - Lifetime
- 1995-11-20 DE DE69507441T patent/DE69507441T2/de not_active Expired - Lifetime
- 1995-11-20 EP EP95402602A patent/EP0716163B1/de not_active Expired - Lifetime
- 1995-11-29 JP JP7310842A patent/JPH08218182A/ja active Pending
- 1995-12-06 KR KR1019950047170A patent/KR100322935B1/ko not_active Expired - Fee Related
- 1995-12-06 CA CA002164555A patent/CA2164555C/fr not_active Expired - Fee Related
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1997
- 1997-10-28 US US08/959,713 patent/US5876517A/en not_active Expired - Lifetime
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| FR947164A (fr) * | 1945-04-14 | 1949-06-24 | United Chromium | Compositions et procédé de trempage pour la coloration des métaux |
| FR2522023A1 (fr) | 1982-02-19 | 1983-08-26 | Waldberg | Bains et procedes utilisables pour realiser le chromatage de surfaces de zinc et de cadmium |
| EP0087288A1 (de) * | 1982-02-19 | 1983-08-31 | M & T Chemicals, Inc. | Lösung und Verfahren zum Schwarzchromatisieren von Zink- und Cadmiumoberflächen |
| EP0274543A1 (de) * | 1986-07-14 | 1988-07-20 | Nihon Parkerizing Co., Ltd. | Zusammensetzung zur behandlung einer metallfläche und behandlungsverfahren |
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| EP0264472A1 (de) | 1986-10-21 | 1988-04-27 | Procoat, S.A. | Wässrige Zusammensetzung zum Passivieren von Zink- und Kadmiumoberflächen |
| JPS6456877A (en) * | 1987-08-28 | 1989-03-03 | Kobe Steel Ltd | Production of chromated galvanized steel sheet |
| GB2216905A (en) * | 1988-03-30 | 1989-10-18 | Nihon Parkerizing | Method for forming a black coating on surfaces |
| JPH0297682A (ja) * | 1988-10-05 | 1990-04-10 | Nippon Hyomen Kagaku Kk | 亜鉛・ニッケル合金メッキに黒色クロメート皮膜を化成せしめる処理液 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6994779B2 (en) | 1997-01-31 | 2006-02-07 | Elisha Holding Llc | Energy enhanced process for treating a conductive surface and products formed thereby |
| WO1999014398A1 (de) * | 1997-09-12 | 1999-03-25 | Henkel Kommanditgesellschaft Auf Aktien | CHROMATIERUNG ODER NACHPASSIVIERUNG MIT STABILISIERTEN Cr(III)/Cr(VI)-HALTIGEN LÖSUNGEN |
| US6866896B2 (en) | 2002-02-05 | 2005-03-15 | Elisha Holding Llc | Method for treating metallic surfaces and products formed thereby |
| CN105088325A (zh) * | 2015-07-20 | 2015-11-25 | 中国船舶重工集团公司第十二研究所 | 一种磁控溅射类石墨碳膜的退镀方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2727983B1 (fr) | 1997-01-24 |
| JPH08218182A (ja) | 1996-08-27 |
| KR960023236A (ko) | 1996-07-18 |
| DE69507441D1 (de) | 1999-03-04 |
| FR2727983A1 (fr) | 1996-06-14 |
| ES2128679T3 (es) | 1999-05-16 |
| EP0716163B1 (de) | 1999-01-20 |
| DE69507441T2 (de) | 1999-07-15 |
| US5876517A (en) | 1999-03-02 |
| CA2164555A1 (fr) | 1996-06-08 |
| CA2164555C (fr) | 2001-09-11 |
| KR100322935B1 (ko) | 2002-06-27 |
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