EP3290543A1 - Method of treating metal surfaces with an aqueous composition and aqueous composition - Google Patents
Method of treating metal surfaces with an aqueous composition and aqueous composition Download PDFInfo
- Publication number
- EP3290543A1 EP3290543A1 EP17188548.6A EP17188548A EP3290543A1 EP 3290543 A1 EP3290543 A1 EP 3290543A1 EP 17188548 A EP17188548 A EP 17188548A EP 3290543 A1 EP3290543 A1 EP 3290543A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- iron
- aqueous composition
- composition
- range
- metal surface
- 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
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000007797 corrosion Effects 0.000 claims abstract description 42
- 238000005260 corrosion Methods 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 26
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 239000011651 chromium Substances 0.000 claims description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920003169 water-soluble polymer Polymers 0.000 claims description 6
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- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
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- 238000011282 treatment Methods 0.000 description 25
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- 239000000843 powder Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- -1 tetrafluoroborate Chemical compound 0.000 description 13
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
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- 239000003973 paint Substances 0.000 description 11
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- 239000000126 substance Substances 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 9
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 9
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 8
- 229920002125 SokalanĀ® Polymers 0.000 description 7
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 6
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
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- 239000004593 Epoxy Substances 0.000 description 4
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- 238000009736 wetting Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical compound O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
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- 238000004381 surface treatment Methods 0.000 description 3
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- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
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- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000009996 mechanical pre-treatment Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 238000005554 pickling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- HUKDRDNCGQSGGI-UPHRSURJSA-N (Z)-4-nitrooxy-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)O[N+]([O-])=O HUKDRDNCGQSGGI-UPHRSURJSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
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- 101100489922 Caenorhabditis elegans abf-2 gene Proteins 0.000 description 1
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- 239000001263 FEMA 3042 Substances 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UEUMIMKGIUYUGH-UHFFFAOYSA-H [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] UEUMIMKGIUYUGH-UHFFFAOYSA-H 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JUVGUSVNTPYZJL-UHFFFAOYSA-N chromium zirconium Chemical compound [Cr].[Zr] JUVGUSVNTPYZJL-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
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- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UXDZLUCNRYCZCG-UHFFFAOYSA-L zinc;phthalate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O UXDZLUCNRYCZCG-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C23C22/34—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 fluorides or complex fluorides
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- 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
- C23C22/83—Chemical after-treatment
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- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- the invention relates to a method of treating metal surfaces with an aqueous composition and to an aqueous composition for treatment of metal surfaces.
- phosphate coatings have been used to improve adhesion of coatings, such as paint, and corrosion resistance of steel. Some major disadvantages of phosphate coatings are necessity of several rinsing steps, sludge disposal and power consumption. Additionally these coatings are often sealed with a hexavalent chromium solution for optimum adhesion and corrosion. Therefore these phosphate coatings suffer from several environmental, health and safety drawbacks.
- WO 2006/088518 has disclosed a process for preparing zirconium-chromium conversion coatings on iron and iron alloys to improve the corrosion resistance and adhesive bonding strength.
- This known method comprises treating iron and iron alloys with an acidic aqueous solution having a pH ranging from about 2.5 to 5.5, preferably 3.7-4.0 for steel surfaces.
- the acidic aqueous solution comprises, per litre of solution, from about 0.01 to 22 grams of a trivalent chromium compound, about 0.01 to 12 grams of a hexafluorozirconate, about 0.0 to 12 grams of at least one fluorocompound selected from the group consisting of tetrafluoroborate, hexafluorosilicate and mixtures thereof, from about 0.0 to 10 grams of at least one divalent zinc compound, from 0.0 to about 10 grams of at least one water soluble thickener and from 0.0 to about 10 grams of at least one water soluble surfactant.
- Above known treatment contains at least zirconium and the preferred soluble trivalent chromium species is containing a sulphate anion.
- WO 2006/088519 A1 discloses a similar treatment, wherein the solution also comprises a stabilizing compound selected from polyhydroxy and carboxylic compounds.
- a stabilizing compound selected from polyhydroxy and carboxylic compounds.
- these preparations are used at low concentrations of the effective species to avoid over-etching and flash rust during drying.
- low concentrations result in less dense protective layers on the metal surface and therefore might affect the protective and/or bonding performance.
- a no-rinse process for treating metal surfaces is known, particularly for the subsequent application of organic coating compositions, in which the metal surface is wetted with an aqueous bath solution having a pH in the range of 2-3 and containing 0.5-10 g/L of chromium-(III) ions, 0.55-11 g/L of fluoride ions, 0.6-12.5 g/L of phosphate and 0.15-5.0 g/L of an organic film-forming agent which is soluble or homogeneously dispersible in water, like a water-soluble acrylic polymer.
- An object is to provide a method of protecting an organic coated surface of iron or iron alloy against corrosion and/or improving durable adhesion properties of such an organic coating or an adhesive using a metal surface treatment solution.
- Another object of the invention is the provision of an alternative metal treatment method and solution based on trivalent chromium for protection of an organic coated surface of iron or iron alloy against corrosion and/or for improvement of the adhesion properties of such an organic coating or an adhesive using a metal surface treatment solution.
- Yet another object is to provide a dry-in-place metal treatment method and solution requiring no rinse step after application.
- Yet another object is to provide a dry-in-place metal treatment solution for use at room temperature on iron and iron alloys without flash rusting.
- Still another object is to provide a metal treatment method and solution for application to an already phosphated surface of iron and iron alloy replacing a conventional chromate seal on such surface.
- the invention provides a method of treating a metal surface of iron or iron alloy for providing corrosion protection, adhesion of coating and/or adhesive, which method comprises the application of an aqueous composition onto the metal surface of iron or iron alloy, which composition consists of: trivalent chromium (Cr 3+ ): 1.16-7.0 g/l total fluoride (F - ): 1.3-7.7 g/l organic corrosion inhibitor: up to 2.0 g/l water soluble polymers: 0-4.0 g/l water soluble surfactant 0-1.0 g/l organo functional silane and/or oligomer 0-4.0 g/l pH adjusting agent 0-1.0 g/l fluoride adjusting agent 0-1.0 g/l wherein the molar ratio of Cr 3+ to : F - ranges from 0.25-0.4, and wherein the pH ranges from 2.0-4.4.
- the invention provides an aqueous composition as defined above for treating a metal surface of iron or iron alloy.
- the aqueous composition according to the invention is free of hexavalent chromium and contains as main constituents trivalent chromium ions and fluoride ions in a molar ratio of Cr 3+ to : F - ranging from 0.25-0.4.
- a solution having a relatively simple composition regarding its components without the need of specific more complex (fluorometalate) compounds as a source of fluoride ions offers good results regarding corrosion resistance and adhesion.
- the metal surface may have a conventional phosphate conversion coating applied to it, before it is exposed to the composition according to the invention.
- the composition can be easily applied, even in repair and maintenance conditions such as outdoor pipeline field applications, ship-building, road work, offshore, industrial equipment and other (non-mobile) steel structures.
- the composition can be applied directly to the metal surface, after conventional mechanical and/or chemical pre-treatment, such as grit blasting, sanding and scuffing and degreasing/pickling respectively. Rinsing after application of the composition is not necessary.
- the treatment solution can be dried in air under prevailing conditions and does not require any special measures or apparatuses. However the treated metal substrate should be dry before subsequent painting or adhesive bonding processes are carried out.
- forced drying methods can be used for example oven-drying, infra-red drying and forced-air drying.
- the thus treated surface of iron or iron alloy can be coated with an organic paint, optionally including the pre-application of a paint primer, and/or with an adhesive bonding system.
- the layer formed from the composition enhances the adhesion of the subsequently applied coating such as a paint layer system or adhesive bonding system.
- the enhanced adhesion offers good corrosion resistance when the thus coated metal surface is exposed to corrosive conditions.
- the layer formed may allow to reduce the layer thickness of a conventional paint primer or to waive the conventional primer at all .
- Trivalent chromium is present in amount of 1.16-7.0 g/l. A preferred range is 3.0-6.0 g/l. Total fluoride is in the range of 1.3-7.7 g/l.
- the molar ratio of Cr 3+ to : F - is 0.25-4.0, preferably 0.30-0.36, more preferably 0.32-0.34, such as 1:3. It has been found that the stoichiometric ratio of CrF 3 or slightly above offer good results regarding corrosion resistance and/or bonding characteristics.
- the trivalent chromium can be obtained by reducing chromic acid (H 2 CrO 4 ) with chemical agents that can be oxidized by chromic acid like methanol or hydrogen peroxide leaving no residual products in the starting solution after heating.
- Another attractive source is using CrF 3 .4H 2 O as a starting material. This compound is hardly soluble in water, but accompanied by acidic components like HF and acidic homopolymers and copolymers it is.
- HF is preferably used as it does not introduce extraneous anions.
- the pH ranges from 2.0-4.4, preferably 2.7-3.8, in particular 2.7-3.4.
- the composition may contain pH adjusting agents, such as alkali metal hydroxide like sodium hydroxide, potassium hydroxide, and ammonia, in an amount of 0-1.0 g/l. It is believed that alkali metal ions do not - or to a substantially lesser extent-contribute to the formation of the protective layer and thus its protection and/or bonding properties.
- the molar ratio of fluoride to trivalent chromium is preferably equal to or slightly above the stoichiometric ratio of CrF 3 .
- Adjustment may be carried out by incorporating of fluoride adjusting agents that offer an additional source of fluoride anions. If present, these fluoride adjusting agents are present in an amount up to 1.0 g/l.
- Preferred examples include fluoric acid, fluorides of alkali metals and ammonium, in particular sodium fluoride and ammonium bi fluoride.
- the composition according to the invention contains an organic corrosion inhibitor in amount up to 2.0 g/l, preferably 0.0001-2.0, more preferably 0.1-1.0 g/l.
- the organic corrosion inhibitor is a required component of the composition according to the invention.
- the organic corrosion inhibitor can act as a flash corrosion inhibitor, which inhibits so called "flash rusting" during drying of the applied treatment composition on iron and iron alloys surfaces.
- flash corrosion inhibitor is thought to contribute to the final corrosion resistance after application of a coating like paint.
- the organic corrosion inhibitor should be slightly soluble in water or miscible therewith.
- Examples include: N,N- dimethyl propylene urea, tolytriazole, zinc phthalate, imidazolinemaleate, caprylic acid, phtalic acid, phosphonic acid alkylesters, n-butyric acid, benzotriazole, tolytriazole, phthalate divalent salts, nitrobenzoate, 1-octanol, tannic acid, nitro maleate divalent salts, 2-mercaptobenzimidazole, propargyl alcohol, propargyl alcohol ethoxylates, iso nitro phtalate zinc salt, 2-butyn 1,4 diol, 2-butyn 1,4 diol alkoxylates, alkanolamine salt of a nitrogenous organic acids, quaternary amines and combinations thereof.
- Concentration and the nature of the organic corrosion inhibitor or a mixture of corrosion inhibitors should be chosen in a way that it will not block the trivalent chromium deposition on the metal during treatment..
- the composition may comprise additional components from a selected group of optional compounds.
- optional compounds include water soluble homopolymers and copolymers that preferably are based on the following monomers: acrylic acid, methacrylic acid, vinylalcohol, vinylether, maleic acid, vinylphosphonic acid, vinylsulphonic acid, methyl vinylether and combinations thereof, up to 4.0 g/l, preferably 0.01-4.0 g/l, more preferably 0.1-1 g/l.
- Another optional compound is a water soluble surfactant, which may be present in an amount up to 1.0 g/l.
- a preferred concentration range is 0.001-0.5 g/l, while a more preferred concentration ranges from 0.01-0.1 g/l.
- Surfactant that can be used in the composition according to the invention include acid stable low foaming anionic and non-ionic surfactants like alkaryl sulfonates and poly ethylene glycol fatty amines. The surfactant provides uniform wetting of the substrate and efficient removal of oil and dirt. If the amount of surfactant is too high, it can cause excessive foaming in the process.
- an organo functional silane and/or a hydrolysed oligomer thereof is an organo functional silane and/or a hydrolysed oligomer thereof. If present, the concentration ranges up to 4.0 g/l.
- the reactive functional group is at least one selected from a mercapto group, an amino group, a vinyl group, an epoxy group and a methacryloxy group, advantageously in an amount of 1 to 40 mg/l based on Si.
- the method of treating a metal surface of iron or iron alloy for providing corrosion resistance and adhesion of a coating and or adhesive comprises a step of applying the aqueous composition according to the invention and outlined hereinabove to the metal surface.
- the metal surface to be treated with the composition according to the invention is pre-treated using known mechanical or chemical pre-treatment processes or acombination thereof for obtaining a better wettable surface, which typically requires the surface to be roughened and to be substantially free of rust, scale and oxides, fat, oil and the like.
- Mechanical pre-treatment processes comprise dry grit blasting, sanding, scuffing and abrading.
- Chemical pre-treatment include (acidic/alkaline/solvent) degreasing and pickling.
- a chemical pre-treatment is followed by a rinsing step using tap water or demineralised water. Combinations of mechanical pre-treatment and chemical pre-treatment in any order is also possible.
- the composition according to the invention can also replace degreasing using a solvent on oiled surfaces of iron or iron alloy, that are free of scale and oxides.
- a present composition containing a surfactant on such surfaces removal of oil, fat and dirt and building of the conversion layer occur simultaneously, rendering a preceding solvent degreasing step superfluous.
- a surfactant on such surfaces removal of oil, fat and dirt and building of the conversion layer occur simultaneously, rendering a preceding solvent degreasing step superfluous.
- the method according to the invention involves contacting an oiled, but scale and oxide free surface of iron or iron alloy with the present composition.
- composition according to the invention allows also to replace a conventional chromate seal on an already phosphated surface of iron and iron alloy.
- the way of applying the composition according to the invention to the metal surface is not limited. However, homogeneity and uniformity of the applied wet film on the substrate before drying will be advantageous. Suitable application methods include spraying, dipping, wiping, brushing, roll coating and the like. Excess of treatment fluid on parts with intricate geometries can be removed with compressed air before drying. After application it is not necessary to perform a rinsing step to remove unreactive and/or unreacted species from the formed layer. Instead thereof the metal surface to which the composition according to the invention is applied can be allowed to dry immediately, e.g. in air optionally at elevated temperature like an oven having conditioned air.
- the coating weight (after drying measured by XRF (X ray fluorescence) ranges from 20 to 200 mg chromium/m 2 . Higher coating weights will reduce adhesion properties of subsequently applied organic coating layers. At lower coating weights no beneficial effect in corrosion protection has been measured.
- XRF X ray fluorescence
- a subsequently applied paint system and/or adhesive bonding system can be applied using conventional methods and equipment, such as spraying, brushing and roll coating.
- the invention is illustrated by the following examples according to the invention and comparative examples.
- the trivalent chromium compound "Cr(III) Fluoride" as indicated in the below Tables was obtained by reducing a chromic acid solution in a stoichiometric ratio chromium to fluoride 1 to 3.
- the fluoride source was an aqueous solution of hydrogen fluoride.
- Methanol in water was used as a reducing agent. After 4 hours of reduction at 80 Ā°C no hexavalent chromium could be detected by using a s-diphenylcarbazide test method (detection limit for Cr(VI) is smaller than 0.03 ppm). Methanol and oxidation products of methanol like formalin and formic acid could not be detected by TOC (total organic carbon) measurements.
- Aqueous metal surface treatment liquids having a composition as indicated in Table 1 were prepared and applied to metal surfaces as indicated in Tables 2-4..
- Corrosion tests Accelerated corrosion testing according to ASTM B117 Neutral Salt Spray for iron, iron alloys and zinc coated steels .
- Tables 2 -4 summarize the test results. Table 1.
- Table 1. Examples composition Example Chromium compound (source) Concentration [Cr] g/L Fluoride source Molair ratio Cr :F Organic corrosion inhibitor (content mg/L) Surfactant Watersoluble polymer (content, mg/L) pH Ex1 dissolved CrF3*4aq 1,5 CrF3*4aq 1 :3 divalent, phthalate (200) PAA (200) 3.4 Ex2 dissolved CrF3*4aq 1,5 CrF3*4aq 1 :3 divalent, phthalate (200) Plurafac LF PAA (200) 3.4 Ex3 Cr(III), Fluoride 4 HF 1 :3 Dodicor (200) Plurafac LF PAA (200) 3.3 Ex4 Cr(III), Fluoride 4 HF 1 :3 Dodicor (200) 3.3 Ex5 Cr
- compositions according to the invention present better performance with respect to coating adhesion, wettability, flash rust inhibition and corrosion resistance than the comparative examples, that fail in one or more of these aspects or are worse.
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Abstract
Description
- The invention relates to a method of treating metal surfaces with an aqueous composition and to an aqueous composition for treatment of metal surfaces.
- Mechanical and chemical treatment of metal surfaces for enhancing corrosion resistance and/or improving bonding to a subsequently applied coating such as an adhesive layer, paint layer, lacquer layer or other finishing layer is well known in the art. E.g. mechanical treatment for example grid blasting has been used to remove scale and/or oxides from the metal surface and to improve adhesion, when chemical treatment steps were not practical to apply. Only waterborne cleaning of metal parts made of especially iron and iron alloys without any suitable chemical treatment will result in flash rusting (also known as "rapid corrosion"), if the parts are not painted within a few hours. Degreasing of oiled surfaces using a suitable solvent like thinner or heptane does not give rise to flash rusting. However, solvent degreasing offers considerable health and safety risks for personnel and the environment. Chemical treatment of metal surfaces of zinc (alloy) coated steel, mild steel, or aluminium and their alloys with aqueous chromate (chromium VI) solutions results in a so called "chromate conversion layer", which offers corrosion resistance and improved adhesion, and avoids the occurrence of flash rusting before painting.
- It is also recognized that these chromate based aqueous solutions suffer from the toxicity of the Cr6+ component thereof. Cr6+ is classified as carcinogenic and will be banned from most industrial applications with high exposure risks for the co-workers. Disposal of the toxic treatment composition is also a problem, although to a lesser extent if it is converted into the comparatively innocuous trivalent chromium. However, such a conversion brings about additional costs and expenses.
- Also phosphate coatings have been used to improve adhesion of coatings, such as paint, and corrosion resistance of steel. Some major disadvantages of phosphate coatings are necessity of several rinsing steps, sludge disposal and power consumption. Additionally these coatings are often sealed with a hexavalent chromium solution for optimum adhesion and corrosion. Therefore these phosphate coatings suffer from several environmental, health and safety drawbacks.
- Today the use of chromate-free (paint) primers has become more common. It has appeared that mechanical and chemical pre-treatments of metals become more important to guaranty corrosion protection performance of metal paint systems.
- Ongoing legislation is also developed and comes gradually into force in order to reduce and ultimately abandon hexavalent chromium based metal treatment compositions.
- Therefore, in the art there is a need for treatments that are substantially free of hexavalent chromium compounds, that offer corrosion resistance and bonding performance to the metal surfaces treated similar to those obtained by treating these metal surfaces with conventional solutions comprising hexavalent chromium.
- Various proposals to satisfy this need have been disclosed in the patent literature. E.g.
WO 2006/088518 has disclosed a process for preparing zirconium-chromium conversion coatings on iron and iron alloys to improve the corrosion resistance and adhesive bonding strength. This known method comprises treating iron and iron alloys with an acidic aqueous solution having a pH ranging from about 2.5 to 5.5, preferably 3.7-4.0 for steel surfaces. The acidic aqueous solution comprises, per litre of solution, from about 0.01 to 22 grams of a trivalent chromium compound, about 0.01 to 12 grams of a hexafluorozirconate, about 0.0 to 12 grams of at least one fluorocompound selected from the group consisting of tetrafluoroborate, hexafluorosilicate and mixtures thereof, from about 0.0 to 10 grams of at least one divalent zinc compound, from 0.0 to about 10 grams of at least one water soluble thickener and from 0.0 to about 10 grams of at least one water soluble surfactant. Above known treatment contains at least zirconium and the preferred soluble trivalent chromium species is containing a sulphate anion. These extraneous cations and anions will affect the formation to insoluble species negatively. Therefore the remaining unreacted solution should be rinsed from the substrate with tap or demineralised water resulting in an additional waste stream that requires disposal or other processing. -
WO 2006/088519 A1 discloses a similar treatment, wherein the solution also comprises a stabilizing compound selected from polyhydroxy and carboxylic compounds. In practice, these preparations are used at low concentrations of the effective species to avoid over-etching and flash rust during drying. However, low concentrations result in less dense protective layers on the metal surface and therefore might affect the protective and/or bonding performance. - From EP 111897 A1 a no-rinse process for treating metal surfaces is known, particularly for the subsequent application of organic coating compositions, in which the metal surface is wetted with an aqueous bath solution having a pH in the range of 2-3 and containing 0.5-10 g/L of chromium-(III) ions, 0.55-11 g/L of fluoride ions, 0.6-12.5 g/L of phosphate and 0.15-5.0 g/L of an organic film-forming agent which is soluble or homogeneously dispersible in water, like a water-soluble acrylic polymer.
- An object is to provide a method of protecting an organic coated surface of iron or iron alloy against corrosion and/or improving durable adhesion properties of such an organic coating or an adhesive using a metal surface treatment solution.
- Another object of the invention is the provision of an alternative metal treatment method and solution based on trivalent chromium for protection of an organic coated surface of iron or iron alloy against corrosion and/or for improvement of the adhesion properties of such an organic coating or an adhesive using a metal surface treatment solution..
- Yet another object is to provide a dry-in-place metal treatment method and solution requiring no rinse step after application.
- Yet another object is to provide a dry-in-place metal treatment solution for use at room temperature on iron and iron alloys without flash rusting.
- Still another object is to provide a metal treatment method and solution for application to an already phosphated surface of iron and iron alloy replacing a conventional chromate seal on such surface.
- Accordingly, in a first aspect the invention provides a method of treating a metal surface of iron or iron alloy for providing corrosion protection, adhesion of coating and/or adhesive, which method comprises the application of an aqueous composition onto the metal surface of iron or iron alloy,
which composition consists of:trivalent chromium (Cr3+): 1.16-7.0 g/l total fluoride (F-): 1.3-7.7 g/l organic corrosion inhibitor: up to 2.0 g/l water soluble polymers: 0-4.0 g/l water soluble surfactant 0-1.0 g/l organo functional silane and/or oligomer 0-4.0 g/l pH adjusting agent 0-1.0 g/l fluoride adjusting agent 0-1.0 g/l - In a second aspect the invention provides an aqueous composition as defined above for treating a metal surface of iron or iron alloy.
- Below the invention is explained first of all in terms of composition and components thereof. The aqueous composition according to the invention is free of hexavalent chromium and contains as main constituents trivalent chromium ions and fluoride ions in a molar ratio of Cr3+to :F- ranging from 0.25-0.4. Surprisingly it has been found that a solution having a relatively simple composition regarding its components without the need of specific more complex (fluorometalate) compounds as a source of fluoride ions offers good results regarding corrosion resistance and adhesion. These fluorometalate compounds as used in the prior art will introduce extraneous polyvalent metal ions and these are believed not to play a significant role regarding corrosion resistance and adhesion and could complicate the preparation of the composition regarding desired ratios of components. Contrary thereto the composition according to the invention can be easily prepared. Inorganic anions other than fluorides like phosphates are advantageously absent in the composition according to the invention. These other inorganic anions increase the solubility of the resulting conversion layer and affect its performance. Also stability and maintenance of the treatment bath might become more complicated. Metal surfaces that can be suitably treated with the composition according to the invention include iron and iron alloys such as cold rolled steel, mild steel and carbon steels. The metal surface may have a conventional phosphate conversion coating applied to it, before it is exposed to the composition according to the invention. The composition can be easily applied, even in repair and maintenance conditions such as outdoor pipeline field applications, ship-building, road work, offshore, industrial equipment and other (non-mobile) steel structures. Typically the composition can be applied directly to the metal surface, after conventional mechanical and/or chemical pre-treatment, such as grit blasting, sanding and scuffing and degreasing/pickling respectively. Rinsing after application of the composition is not necessary. The treatment solution can be dried in air under prevailing conditions and does not require any special measures or apparatuses. However the treated metal substrate should be dry before subsequent painting or adhesive bonding processes are carried out. In order to reduce process time forced drying methods can be used for example oven-drying, infra-red drying and forced-air drying. After the composition has been applied and sufficiently dried, the thus treated surface of iron or iron alloy can be coated with an organic paint, optionally including the pre-application of a paint primer, and/or with an adhesive bonding system.
- The layer formed from the composition enhances the adhesion of the subsequently applied coating such as a paint layer system or adhesive bonding system. The enhanced adhesion offers good corrosion resistance when the thus coated metal surface is exposed to corrosive conditions. Furthermore, it has appeared that the layer formed may allow to reduce the layer thickness of a conventional paint primer or to waive the conventional primer at all .. Trivalent chromium is present in amount of 1.16-7.0 g/l. A preferred range is 3.0-6.0 g/l. Total fluoride is in the range of 1.3-7.7 g/l. The molar ratio of Cr3+ to :F- is 0.25-4.0, preferably 0.30-0.36, more preferably 0.32-0.34, such as 1:3. It has been found that the stoichiometric ratio of CrF3 or slightly above offer good results regarding corrosion resistance and/or bonding characteristics.
- The trivalent chromium can be obtained by reducing chromic acid (H2CrO4) with chemical agents that can be oxidized by chromic acid like methanol or hydrogen peroxide leaving no residual products in the starting solution after heating. Another attractive source is using CrF3.4H2O as a starting material. This compound is hardly soluble in water, but accompanied by acidic components like HF and acidic homopolymers and copolymers it is. HF is preferably used as it does not introduce extraneous anions.
- The pH ranges from 2.0-4.4, preferably 2.7-3.8, in particular 2.7-3.4. In order to set the acidity at the required level the composition may contain pH adjusting agents, such as alkali metal hydroxide like sodium hydroxide, potassium hydroxide, and ammonia, in an amount of 0-1.0 g/l. It is believed that alkali metal ions do not - or to a substantially lesser extent-contribute to the formation of the protective layer and thus its protection and/or bonding properties.
- As said, the molar ratio of fluoride to trivalent chromium is preferably equal to or slightly above the stoichiometric ratio of CrF3. Adjustment may be carried out by incorporating of fluoride adjusting agents that offer an additional source of fluoride anions. If present, these fluoride adjusting agents are present in an amount up to 1.0 g/l. Preferred examples include fluoric acid, fluorides of alkali metals and ammonium, in particular sodium fluoride and ammonium bi fluoride.
- The composition according to the invention contains an organic corrosion inhibitor in amount up to 2.0 g/l, preferably 0.0001-2.0, more preferably 0.1-1.0 g/l. Thus the organic corrosion inhibitor is a required component of the composition according to the invention. The organic corrosion inhibitor can act as a flash corrosion inhibitor, which inhibits so called "flash rusting" during drying of the applied treatment composition on iron and iron alloys surfaces. In addition the organic corrosion inhibitor is thought to contribute to the final corrosion resistance after application of a coating like paint. The organic corrosion inhibitor should be slightly soluble in water or miscible therewith. Examples include: N,N- dimethyl propylene urea, tolytriazole, zinc phthalate, imidazolinemaleate, caprylic acid, phtalic acid, phosphonic acid alkylesters, n-butyric acid, benzotriazole, tolytriazole, phthalate divalent salts, nitrobenzoate, 1-octanol, tannic acid, nitro maleate divalent salts, 2-mercaptobenzimidazole, propargyl alcohol, propargyl alcohol ethoxylates, iso nitro phtalate zinc salt, 2-butyn 1,4 diol, 2-butyn 1,4 diol alkoxylates, alkanolamine salt of a nitrogenous organic acids, quaternary amines and combinations thereof.
- Concentration and the nature of the organic corrosion inhibitor or a mixture of corrosion inhibitors should be chosen in a way that it will not block the trivalent chromium deposition on the metal during treatment..
- In addition to the above components the composition may comprise additional components from a selected group of optional compounds. These optional compounds include water soluble homopolymers and copolymers that preferably are based on the following monomers: acrylic acid, methacrylic acid, vinylalcohol, vinylether, maleic acid, vinylphosphonic acid, vinylsulphonic acid, methyl vinylether and combinations thereof, up to 4.0 g/l, preferably 0.01-4.0 g/l, more preferably 0.1-1 g/l. These polymers improve wetting behaviour of the treatment composition, as well as adhesion of subsequently applied organic coatings. Too high concentrations will reduce wet adhesion of an organic coating. Another optional compound is a water soluble surfactant, which may be present in an amount up to 1.0 g/l. A preferred concentration range is 0.001-0.5 g/l, while a more preferred concentration ranges from 0.01-0.1 g/l. Surfactant that can be used in the composition according to the invention include acid stable low foaming anionic and non-ionic surfactants like alkaryl sulfonates and poly ethylene glycol fatty amines. The surfactant provides uniform wetting of the substrate and efficient removal of oil and dirt. If the amount of surfactant is too high, it can cause excessive foaming in the process.
- Yet another component that may be present, is an organo functional silane and/or a hydrolysed oligomer thereof. If present, the concentration ranges up to 4.0 g/l. The reactive functional group is at least one selected from a mercapto group, an amino group, a vinyl group, an epoxy group and a methacryloxy group, advantageously in an amount of 1 to 40 mg/l based on Si.
- The method of treating a metal surface of iron or iron alloy for providing corrosion resistance and adhesion of a coating and or adhesive, comprises a step of applying the aqueous composition according to the invention and outlined hereinabove to the metal surface. Typically the metal surface to be treated with the composition according to the invention is pre-treated using known mechanical or chemical pre-treatment processes or acombination thereof for obtaining a better wettable surface, which typically requires the surface to be roughened and to be substantially free of rust, scale and oxides, fat, oil and the like. Mechanical pre-treatment processes comprise dry grit blasting, sanding, scuffing and abrading. Chemical pre-treatment include (acidic/alkaline/solvent) degreasing and pickling. Typically a chemical pre-treatment is followed by a rinsing step using tap water or demineralised water. Combinations of mechanical pre-treatment and chemical pre-treatment in any order is also possible.
- It has surprisingly been found that the composition according to the invention can also replace degreasing using a solvent on oiled surfaces of iron or iron alloy, that are free of scale and oxides. Upon application of the composition according to the invention, in particular a present composition containing a surfactant, on such surfaces removal of oil, fat and dirt and building of the conversion layer occur simultaneously, rendering a preceding solvent degreasing step superfluous. Thus in an embodiment of the method according to the invention involves contacting an oiled, but scale and oxide free surface of iron or iron alloy with the present composition.
- The composition according to the invention allows also to replace a conventional chromate seal on an already phosphated surface of iron and iron alloy.
- The way of applying the composition according to the invention to the metal surface is not limited. However, homogeneity and uniformity of the applied wet film on the substrate before drying will be advantageous. Suitable application methods include spraying, dipping, wiping, brushing, roll coating and the like. Excess of treatment fluid on parts with intricate geometries can be removed with compressed air before drying. After application it is not necessary to perform a rinsing step to remove unreactive and/or unreacted species from the formed layer. Instead thereof the metal surface to which the composition according to the invention is applied can be allowed to dry immediately, e.g. in air optionally at elevated temperature like an oven having conditioned air.
- Advantageously the coating weight (after drying measured by XRF (X ray fluorescence)) ranges from 20 to 200 mg chromium/m2. Higher coating weights will reduce adhesion properties of subsequently applied organic coating layers. At lower coating weights no beneficial effect in corrosion protection has been measured.
- A subsequently applied paint system and/or adhesive bonding system can be applied using conventional methods and equipment, such as spraying, brushing and roll coating.
- The various features of the treatment composition as discussed above are equally applicable to the method according to the invention.
- The invention is illustrated by the following examples according to the invention and comparative examples.
- The trivalent chromium compound "Cr(III) Fluoride" as indicated in the below Tables was obtained by reducing a chromic acid solution in a stoichiometric ratio chromium to fluoride 1 to 3.The fluoride source was an aqueous solution of hydrogen fluoride. Methanol in water was used as a reducing agent. After 4 hours of reduction at 80 Ā°C no hexavalent chromium could be detected by using a s-diphenylcarbazide test method (detection limit for Cr(VI) is smaller than 0.03 ppm). Methanol and oxidation products of methanol like formalin and formic acid could not be detected by TOC (total organic carbon) measurements.
- Aqueous metal surface treatment liquids having a composition as indicated in Table 1 were prepared and applied to metal surfaces as indicated in Tables 2-4..
- The thus pre-treated, treated and organic coated surfaces were subjected to adhesion tests and corrosion tests according to quality regulations prescribed GSB and Qualitysteelcoat: Adhesion Cross cut adhesion pull-off EN ISO 16276-2; ASTM D3359
- Adhesion Reversed impact ASTM D2794 or EN ISO 6272-1 and
- Corrosion tests: Accelerated corrosion testing according to ASTM B117 Neutral Salt Spray for iron, iron alloys and zinc coated steels . Tables 2 -4 summarize the test results.
Table 1. Examples composition Example Chromium compound (source) Concentration [Cr] g/L Fluoride source Molair ratio Cr :F Organic corrosion inhibitor (content mg/L) Surfactant Watersoluble polymer (content, mg/L) pH Ex1 dissolved CrF3*4aq 1,5 CrF3*4aq 1 :3 divalent, phthalate (200) PAA (200) 3.4 Ex2 dissolved CrF3*4aq 1,5 CrF3*4aq 1 :3 divalent, phthalate (200) Plurafac LF PAA (200) 3.4 Ex3 Cr(III), Fluoride 4 HF 1 :3 Dodicor (200) Plurafac LF PAA (200) 3.3 Ex4 Cr(III), Fluoride 4 HF 1 :3 Dodicor (200) 3.3 Ex5 Cr(III), Fluoride 4 HF 1 :3 divalent, phthalate (200) 3.0 Ex6 Cr(III), Fluoride 4 HF 1: 3 propargyl alcohol (20) 2.9 Comp 1 dissolved CrF3*4aq 1,5 CrF3*4aq 1 :3 PAA (200) 3.0 Comp 2 Cr(III), Fluoride 0,28 HF 1 : 3 3.1 Comp 3 Cr(III), Fluoride 4 HF + ABF 2 :7 3.4 Comp 4 Cr(III), Fluoride 4 HF 1 :3 Plurafac LF PAA(100), PVA (50) 3.0 Comp 5 DiChromiumTriSulphate 4 H2ZrF6 1 :6 caprylic acid (50) 3.0 Comp 6 Comp 7 Cr(III), Fluoride 4 HF 1 :3 PAA (100), PVA (50) 2.9 Comp 8 HF Hydrogen Fluoride
ABF Ammonium bi Fluoride
CrF3.4H2O Chromium Trifluoride
H2ZrF6 HexafluoroZirconium Acid
Dodicor (Clariant) commercial blend of corrosion inhibitors: benzyl quaternary amine imidazoline salt and propynol
Plurafac LF (BASF) commercial branched and linear ethoxylated fatty alcohol
PAA Poly acrylic acid (Mw = 100000 g/mol)
PVA Poly vinyl alcohol (Mw = 60000 g/mol)Tabel 2. Examples method and results Examples Metal substrate Pretreatment Application room temperature Discoloration / flash rust during unforced drying Coating wt (mg Cr/m2) Type of organic coating Adhesion test #cut impact < 2mm Corrosion after x hours Ex5 CRS alk cleaned immersion 3 min no flash rust 80 coil coat pass 500 Comp 1 CRS alk cleaned immersion 3 min slightly yellow stains 50 coil coat pass n/a Comp 2 CRS alk cleaned immersion 3 min yellow/ orange stains 40 coil coat failed n/a Comp 3 CRS alk cleaned immersion 3 min slightly yellow stains 120 coil coat pass 240 Comp 4 CRS alk cleaned immersion 3 min slightly yellow stains 60 coil coat pass 240 Comp 5 CRS alk cleaned immersion 3 min no flash rust 40 coil coat failed <168 Ex6 C-steel grid blasted spray 2 min no flash rust 90 epoxy powder pass 1000 Comp 6 C-steel grid blasted no flash rust epoxy powder pass <500 Comp 7 C-steel grid blasted spray 2 min slightly yellow stains 75 powder pass 500 Comp 8 C-steel grid blasted no flash rust powder pass <240 CRS Oiled cold rolled steel
C steel Low carbon steel DC-1
alkaline cleaned alkaline cleaning (pH =10) during 3 minutes at 52 Ā°C
grid blasted mechanical roughening and removal of rust and oxides
coil coat liquid polyester coating (7 micrometres)cured at 240Ā° C in 40 - 60 seconds
epoxy powder epoxy primer powder coating (300 micrometres) cured at room temperature in 2 weeks
powder powder coating (80 micrometres) cured at 175oC in 15 minutes
corrosion test SST is neutral salt spray test according to ASTM B117Table 3: Test results Carbon steels with mill scale or rusted/oxidized surfaces Example Inv Com p Comp Inv Comp Inv Comp Inv Comp Inv Comp Mechanical removal of rust and mill scale Dry abrasive grit blast cleaniing x x x x x x x x Scuffing disc/followed by grit blasting x x Chemical Treatment Commercial alkaline cleaned surface x x x Commercial iron phosphated surface x x x Ex1 spray application (2 min) x x x Ex2 wipe application x x Commercial Zr treated spray application x Organic Coating Type wet wet powder powder powder wet wet wet wet powder powder Coating thickness (Āµm) 95 95 60 60 60 1500 1500 1500 1500 90 90 Adhesion test Adhesion cross-cut 1 mm + tape Corrosion NEN en ISO 92227 Neutral Salt Spray Test (ASTM B117) Creepage from the scribe (ISO 4628-8) After 500 hrs exposure (mm) 4 0 >50 1.5 3.4 2.3 3.7 After 1000 hrs exposure (mm) 3 >20 2 14 Table 4. Test results Slightly oiled mild steel substrate without oxide/mill scale Without solvent degreasing x x x x Solvent degreasing by wiping x x x Wipe/brush application of treatment compostion Comp 7 x Comp 4 x x Ex5 x Ex3 x Properties after treatment Wetting pretreatment n/a n/a poor good good poor good Flash rust during drying no no yes yes yes no no Wetting of powder paint (100 Āµm) very poor poor good good good good good - From the above examples and test results it appears that the compositions according to the invention present better performance with respect to coating adhesion, wettability, flash rust inhibition and corrosion resistance than the comparative examples, that fail in one or more of these aspects or are worse.
Claims (15)
- A method of treating a metal surface of iron or iron alloy for providing corrosion protection, adhesion of coating and/or adhesive, which method comprises the application of an aqueous composition onto the metal surface of iron or iron alloy,
which composition consists of:trivalent chromium (Cr3+): 1.16-7.0 g/l total fluoride (F-): 1.3-7.7 g/l organic corrosion inhibitor: up to 2.0 g/l water soluble polymers: 0-4.0 g/l water soluble surfactant 0-1.0 g/l organo functional silane and/or oligomer 0-4.0 g/l pH adjusting agent 0-1.0 g/l fluoride adjusting agent 0-1.0 g/l - The method according to claim 1, wherein the concentration trivalent chromium (Cr3+) in the aqueous composition is in the range of 3.0-6.0 g/L.
- The method according to claim 1 or 2, wherein the mol ratio Cr3+: F- in the aqueous composition is in the range of 0.30-0.36, preferably 0.32-0.34 and more preferably 1:3.
- The method according to any one of the preceding claims, wherein the composition comprises dissociated CrF3.4H2O.
- The method according to any one of the preceding claims, wherein the concentration organic corrosion inhibitor in the aqueous composition is in the range of 0.0001-2.0, preferably 0.1-1.0 g/L.
- The method according to any one of the preceding claims, wherein the concentration of the water soluble polymers in the aqueous composition ranges from 0.01-4.0, preferably 0.1-1.0 g/L.
- The method according to any one of the preceding claims, wherein the concentration of the water soluble surfactant in the aqueous composition is in the range of 0.001-0.5, preferably 0.01-0.1 g/L.
- The method according to any one of the preceding claims, wherein the pH ranges from 2.7-3.8, preferably from 2.7 to 3.4.
- The method according to any one of the preceding claims, wherein the coating weight, measured by XRF after drying, is in the range of 20-200 mg chromium/m2.
- The method according to any one of the preceding claims, wherein the metal surface is selected from a solvent degreased metal surface of iron or iron alloy, a metal surface of iron or iron alloy from which scale and oxides have been removed mechanically, a metal surface of iron or iron alloy that has already been provided with a phosphate conversion coating, and an oiled metal surface of iron and iron alloy that is free from scale and oxides.
- An aqueous composition for treating a metal surface of iron or iron alloy, in particular for use in the method according to any one of the preceding claims, which composition consists of:
trivalent chromium (Cr3+): 1.16-7.0 g/l total fluoride (F-): 1.3-7.7 g/l organic corrosion inhibitor: up to 2.0 g/l water soluble polymers: 0-4.0 g/l water soluble surfactant 0-1.0 g/l organo functional silane and/or oligomer 0-4.0 g/l pH adjusting agent 0-1.0 g/l fluoride adjusting agent 0-1.0 g/l - The composition according to claim 11, wherein the concentration trivalent chromium (Cr3+) is in the range of 3.0-6.0 g/L
- The composition according to claim 11 or 12, wherein the mol ratio Cr3+: F- is in the range of 0.30-0.36, preferably 0.32-0.34 and more preferably 1:3.
- The composition according to any one of the preceding claims 11-13, wherein the concentration organic corrosion inhibitor is in the range of 0.0001-2.0, preferably 0.1-1.0 g/L.
- The composition according to any one of the preceding claims 11-14, wherein the concentration of the water soluble polymers in the aqueous composition ranges from 0.01 - 4.0, preferably 0.1-1.0 g/L; and/or the concentration of the water soluble surfactant in the aqueous composition is in the range of 0.001-0.5, preferably 0.01-0.1 g/L; and/or the pH is in the range of 2.7-3.8, preferably 2.7-3.4.
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NL2017398A NL2017398B1 (en) | 2016-08-31 | 2016-08-31 | Method of treating metal surfaces with an aqueous composition and aqueous composition |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0111897A1 (en) * | 1982-12-23 | 1984-06-27 | Gerhard Collardin GmbH | Process for the treatment of metal surfaces, especially aluminium, aluminium alloy and steel ones, and aqueous bath solutions suitable therefor |
EP0337411A2 (en) * | 1988-04-12 | 1989-10-18 | SurTec GmbH | Process for preparing an acidic passivating bath for zinc, zinc alloys an cadmium surfaces, containing chromium III and fluoride |
US20050103229A1 (en) * | 2002-01-11 | 2005-05-19 | Kazuya Tanaka | Aqueous agent for treating substrate, method for treating substrated and treated substrate |
US20110100513A1 (en) * | 2009-11-04 | 2011-05-05 | Bulk Chemicals, Inc. | Trivalent chromium passivation and pretreatment composition and method for zinc-containing metals |
-
2016
- 2016-08-31 NL NL2017398A patent/NL2017398B1/en not_active IP Right Cessation
-
2017
- 2017-08-30 EP EP17188548.6A patent/EP3290543B1/en active Active
- 2017-08-30 PL PL17188548T patent/PL3290543T3/en unknown
- 2017-08-30 ES ES17188548T patent/ES2865428T3/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0111897A1 (en) * | 1982-12-23 | 1984-06-27 | Gerhard Collardin GmbH | Process for the treatment of metal surfaces, especially aluminium, aluminium alloy and steel ones, and aqueous bath solutions suitable therefor |
EP0337411A2 (en) * | 1988-04-12 | 1989-10-18 | SurTec GmbH | Process for preparing an acidic passivating bath for zinc, zinc alloys an cadmium surfaces, containing chromium III and fluoride |
US20050103229A1 (en) * | 2002-01-11 | 2005-05-19 | Kazuya Tanaka | Aqueous agent for treating substrate, method for treating substrated and treated substrate |
US20110100513A1 (en) * | 2009-11-04 | 2011-05-05 | Bulk Chemicals, Inc. | Trivalent chromium passivation and pretreatment composition and method for zinc-containing metals |
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EP3290543B1 (en) | 2021-01-27 |
NL2017398B1 (en) | 2018-03-08 |
ES2865428T3 (en) | 2021-10-15 |
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