EP3137652A1 - Non chromate colored conversion coating for aluminum - Google Patents
Non chromate colored conversion coating for aluminumInfo
- Publication number
- EP3137652A1 EP3137652A1 EP15722112.8A EP15722112A EP3137652A1 EP 3137652 A1 EP3137652 A1 EP 3137652A1 EP 15722112 A EP15722112 A EP 15722112A EP 3137652 A1 EP3137652 A1 EP 3137652A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- component
- acidic aqueous
- aqueous composition
- ppm
- 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
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000007739 conversion coating Methods 0.000 title claims abstract description 17
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000011651 chromium Substances 0.000 claims abstract description 45
- 230000002378 acidificating effect Effects 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 62
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 5
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- -1 nitrate ions Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910011214 Ti—Mo Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012556 adjustment buffer Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940068911 chloride hexahydrate Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005211 surface analysis Methods 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- 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 present invention relates to a process for the formation of colored conversion coatings on aluminum substrates using an acidic aqueous composition.
- the invention further relates to an acidic aqueous composition that can be used in such a process and its use.
- the present invention provides such a coating process and is based on the inventors' finding that a colored conversion coating can be formed on aluminum substrates by bringing an aluminum substrate into contact with an acidic aqueous composition comprising chromium(lll), the elements Mo and/or W, a source of fluoride, and at least one oxidizing agent having a standard reduction potential in a range from +1 ,0 to +1 ,8 V (SHE).
- an acidic aqueous composition comprising chromium(lll), the elements Mo and/or W, a source of fluoride, and at least one oxidizing agent having a standard reduction potential in a range from +1 ,0 to +1 ,8 V (SHE).
- the advantages of the thus produced coatings are that they allow to judge homogeneity of the product by the human eye.
- the processes described herein provide for a corrosion resistant conversion with improved adhesion properties of organic layers which may be applied afterwards, for example in form of a paint, an adhesive layer or a protective layer, and the like.
- no expensive and time consuming disposal of hexavalent chromium substances is needed.
- the present invention is thus directed to a process for the formation of colored conversion coatings on aluminum substrates wherein an aluminum substrate is brought into contact with an acidic aqueous composition, comprising
- the present invention is directed to an acidic aqueous composition
- an acidic aqueous composition comprising a) 0.1 to 2 g/kg calculated with respect to the element Cr of at least one water-soluble compound as a source of chromium(lll),
- the molar ratio of total fluoride of the at least one water-soluble compound according to component c) to the element Cr of the at least one water-soluble compound according to component a) is at least 3 : 1.
- At least one refers to 1 and more, for instance 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more. If this terms refers to compounds of the herein described compositions, this term does not refer to the amount of molecules, but rather to the type of compound.
- at least one water-soluble compound as a source of chromium(lll) refers to one or more different types of water-soluble compounds as a source of chromium(lll), for example different salts. Used in combination with a given amount, the given amount is intended to cover the total amount of the respective type of constituent as described above.
- compositions are weight percentages relative to the total weight of the composition, unless explicitly otherwise indicated. Such amounts are intended to relate to the total amount of the type of component concerned in the composition, unless otherwise indicated.
- an amount given with respect to the "at least one water- soluble compound as a source of chromium(lll)” refers to the total amount of water-soluble compounds that can serve as a source of chromium(lll) in the composition.
- Water-soluble refers to a solubility of at least 1 g of the respective compound in 1 kg of deionised water ( ⁇ 1 ⁇ ) at 20°C.
- compositions used in the process of this invention are substantially free of hexavalent chromium.
- substantially free means that the hexavalent chromium content is below 5 mol%, preferably below 1 mol%, of the total chromium content.
- the acidic aqueous composition in a process according to the first aspect of this invention has a pH value between 0 and 7, preferably between 1 and 6, more preferably of 2,5 and 4, even more preferably of about 3.
- the pH value may be adjusted by an acid, for example, an aqueous acid and/or by a buffer system well known to the skilled person.
- the acids can be, without limited to, HCI, HNOs, H2SO4, and/or H3PO4, preferably H2SO4 or HNO3.
- HNO3 can be used as component d).
- a buffer system may be formed, for example, with a conjugated base of H3PO4 and/or ammonia.
- the pH in the context of this invention relates to the negative logarithm to base 10 of the activity of hydronium ions at a temperature of 25 °C.
- the aluminum substrate is brought into contact with an acidic aqueous composition with the contacting being achieved by any suitable method known in the art. Those can, for example, include spray-coating, dip-coating, spin- coating, printing and the like.
- the contacting step can be conducted manually or automatically.
- the aluminum substrate can be brought once or several times into contact with the acidic aqueous composition according to the present invention, for example, 1 , 2, 3, 4, 5, 6, 7, 8, 9, and more times.
- the aluminum substrate is brought into contact with the acidic aqueous composition in an immersion or spraying process, preferably in a spraying process.
- the contact time is at least 10 seconds, but preferably not more than 600 seconds, more preferably not more than 200 seconds.
- the temperature of the acidic aqueous composition in a process of this invention is at least 15 °C, but preferably not higher than 80 °C, more preferably not more than 70 °C.
- the acidic aqueous composition according to the first aspect of this invention comprises the components described above being characterized herein further.
- the at least one water-soluble compound as a source of chromium(lll) may be any compound that is soluble in water according to the above definition.
- the preferred source for Cr(lll) are salts of Cr(lll), including, but not limited to, chromium(lll)trifluoride (CrF3), chromium(lll)nitrate, chromium(lll)acetate, chromium(lll)gluconate and/or chromium(lll)sulfate, preferably the source is chromium(lll)trifluoride.
- CrF3 chromium(lll)trifluoride
- CrF3 chromium(lll)nitrate
- chromium(lll)acetate chromium(lll)gluconate and/or chromium(lll)sulfate
- the source is chromium(lll)trifluoride.
- other suitable salts may also be used, all of which are
- component a) of the acidic aqueous composition amounts to at least 10 ppm, preferably 100 ppm, more preferably more than 500 ppm, but preferably not more than 2 g/kg, more preferably not more than 1 ,5g/kg calculated with respect to the element Cr and relative to the aqueous acidic composition.
- ppm in the context of this invention relates to "parts per million of weight", so that 1 ppm equals to 0,0001 wt.-%.
- the at least one water-soluble compound of the element Mo and/or W according to component b) of the acidic aqueous composition may be any compound that is soluble in water according to the above definition.
- suitable compounds include, for example and without limitation, molybdates, phosphomolybdic acid, molybdenum chloride, tungstates, such as sodium tungstate, and the like.
- the water-soluble compound of the element Mo is a molybdate. Molybdates can be discrete or polymeric and have any suitable counterion.
- component b) of the acidic aqueous composition amounts to at least 10 ppm, preferably to at least 20 ppm, but preferably to not more than 200 ppm, more preferably to not more than 100 ppm calculated with respect to the elements Mo and/or W and relative to the aqueous acidic composition.
- the water-soluble compound as a source of fluoride according to component c) of the acidic aqueous composition may be selected from hydrofluoric acid, simple fluorides, such as sodium fluoride or chromium(lll)fluoride, and also complex fluoro acids, such as fluorotitanic acid or fluorozirconic acid as well as their water-soluble salts.
- the at least one oxidizing agent which is different from the components a) to c), has a standard reduction potential in a range from +1 ,0 to +1 ,8 V (SHE).
- This standard reduction potential refers to the commonly known standard hydrogen electrode (SHE), which is a redox electrode and the hydrogen's standard electrode potential is declared to be zero at all temperature to form a basis for comparison with all other electrode reactions.
- An "oxidizing agent" according to compound d) of this invention preferably does not encompass dissolved oxygen or water-soluble compounds of metal elements. Accordingly, "different from the components a) to c)" means that none of the compounds a) to c) can simultaneously be considered the oxidizing agent in the sense of the present invention, but that both have to be different species.
- the oxidizing agent is not a compound that falls within the definition of components a) to c), i.e. is no source for chromium(lll), molybdenum, tungsten, or fluoride.
- the at least one oxidizing agent different from the components a) to c) may be, for example, HNO3 or H2O2.
- the amount of component d) of the acidic aqueous composition is in the range of 0.01 to 1.0 g/kg, more preferably of 0.05 to 0.5 g/kg calculated on a H2O2 equivalent basis.
- component d) is selected from water-soluble peroxides and/or oxyacids of the elements nitrogen, sulfur or chlorine as well as their water-soluble salts, preferably from hydrogen peroxide.
- the amount of free fluoride within the acidic aqueous composition is in the range of 10 to 200 ppm and relative to the aqueous acidic composition.
- the free fluoride content in the acidic aqueous composition in a process of this invention can be determined directly in an acidic aqueous composition of this invention by making use of a calibrated fluoride-sensitive electrode at a temperature of 25 °C.
- the acidic aqueous composition comprises in total less than 50 ppm, more preferably less than 10 ppm of water- soluble compounds of the elements Zr and/or Ti relative to the total composition. These compounds tend to interfere with the formation of a colored conversion coating based on chromium(lll) so that their presence is less preferred.
- the metal surfaces can be rinsed with water, for example with deionized water.
- the metal surfaces are optionally dried after rinsing with water. If the coating with organic polymers is carried out, for example, by immersing the metal surfaces in a water-based paint dispersion, there is no need for drying after rinsing. However, if the coating based on organic polymers is an adhesive or powder coating, for example, the metal surfaces are preferably dried before this step.
- the aluminum substrate may be provided in any shape, for example, as aluminum stripes, aluminum plates, or aluminum parts.
- the aluminum parts treated in accordance with the invention may be joined to other metal parts through the adhesive layer.
- the aluminum substrate in a process of this invention may be provided in any shape, for example, as aluminum stripes, aluminum plates, or aluminum parts.
- the aluminum substrate that is brought into contact with the acidic aqueous composition according to the first aspect of this invention can be used without any pre-treatment or can be pre-treated, for example, with an alkaline cleaning solution or acidic descaling solution suitable for the inventive process. All of the pre-treatment methods and agents are well known to the skilled person.
- the pre-treating can be conducted manually or automatically.
- the aluminum substrate can be briefly pickled in cold concentrated nitric acid or the surfaces may be alternatively rubbed down with a squeegee.
- the substrate can be simply rinsed with water, for example with deionized water, and may additionally be descaled with an acidic solution.
- the solutions used for any pre-treatment may have a temperature suitable for the pre-treatment, preferably in a range from 10 to 70 °C, from 20 to 55 °C, or about 25 °C, depending on the solution and the desired effect of the solution.
- the aluminum substrates can be pre-treated for 0.5 to 20 minutes, preferably for 1 to 10 minutes, more preferably for about 3 minutes.
- an acidic aqueous composition that comprises
- the molar ratio of compounds according to component a) with respect to the element Cr to compounds according to component b) with respect to the elements Mo and/or W preferably ranges from 15 : 1 to 25 : 1 , and
- the molar ratio of total fluoride of the at least one water-soluble compound according to component c) to the element Cr of the at least one water-soluble compound according to component a) is at least 3 : 1. It is not necessary that the components a) to c) originate from different compounds. In that respect the water-soluble compound chromium(lll)fluoride is both a component a) as well as a component c). On the other hand, a compound according to component d) by definition of this invention cannot be at the same time a compound of one of the components a) to c) and is thus different from these components.
- the molar ratio of total fluoride of the at least one water-soluble compounds according to component c) to the element Cr of the at least one water-soluble compounds according to component a) of the composition is not more than 10 : 1.
- the total fluoride content in acidic aqueous compositions according to the second aspect of this invention can be determined as described in DIN 38 405-D-4-1 in a buffered sample volume (TISAB: "Total Ionic Strength Adjustment Buffer") taken from the acidic aqueous composition by making use of a calibrated fluoride-sensitive electrode at 25 °C sample volume temperature.
- aluminum panels (AA6060) have been treated in order to yield colored coatings.
- the coatings have been tested with respect to adhesion properties towards a polyester-based organic resin.
- the pH value was 3.0 ⁇ 0.1.
- Example E3 Conversion Coating Composition of Example E1 comprising 25 ppm Molybdenum from ammonium heptamolybdate as the source compound.
- Example E3 Conversion Coating Composition of Example E1 comprising 25 ppm Molybdenum from ammonium heptamolybdate as the source compound.
- Example E1 Conversion Coating Composition of Example E1 comprising 25 ppm Molybdenum from ammonium heptamolybdate as the source compound.
- Example E1 Conversion Coating Composition of Example E1 comprising 100 ppm Molybdenum from ammonium heptamolybdate as the source compound.
- All treated parts have been painted with a polyester powder coating (Corro-Coat PE-F series 2403, Jotun A S, Norway) and cured for 20 min at 180-190°C.
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)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB1407690.5A GB201407690D0 (en) | 2014-05-01 | 2014-05-01 | Non chromate coloured conversion coating for aluminum |
PCT/EP2015/059322 WO2015165956A1 (en) | 2014-05-01 | 2015-04-29 | Non chromate colored conversion coating for aluminum |
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EP3137652A1 true EP3137652A1 (en) | 2017-03-08 |
EP3137652B1 EP3137652B1 (en) | 2018-10-10 |
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EP15722112.8A Active EP3137652B1 (en) | 2014-05-01 | 2015-04-29 | Non chromate colored conversion coating for aluminum |
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EP (1) | EP3137652B1 (en) |
CN (1) | CN106232872B (en) |
ES (1) | ES2703560T3 (en) |
GB (1) | GB201407690D0 (en) |
TW (1) | TW201602410A (en) |
WO (1) | WO2015165956A1 (en) |
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FR3073529B1 (en) * | 2017-11-14 | 2021-07-02 | Mecaprotec Ind | PROCESS FOR SURFACE TREATMENT OF A PART COATED WITH A CADMIUM COATING AND COMPOSITION FOR THE IMPLEMENTATION OF SUCH A PROCESS |
CN110983411A (en) * | 2020-01-07 | 2020-04-10 | 昆明理工大学 | Preparation method of natural color conversion film on surface of aluminum alloy |
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CA1228000A (en) * | 1981-04-16 | 1987-10-13 | David E. Crotty | Chromium appearance passivate solution and process |
RO113063B1 (en) * | 1997-03-24 | 1998-03-30 | Inst Cercetare Si Proiectare T | Low-pollution solution for colourless-bluish passivation of electrochemical zinc and zinc alloy deposits |
US7402214B2 (en) * | 2002-04-29 | 2008-07-22 | Ppg Industries Ohio, Inc. | Conversion coatings including alkaline earth metal fluoride complexes |
JP4628726B2 (en) * | 2004-03-02 | 2011-02-09 | 日本表面化学株式会社 | Aluminum member, method for producing the same, and chemical for production |
US20070243397A1 (en) * | 2006-04-17 | 2007-10-18 | Ludwig Robert J | Chromium(VI)-free, aqueous acidic chromium(III) conversion solutions |
CN1858303B (en) * | 2006-06-09 | 2010-07-21 | 广东多正化工科技有限公司 | Normal temperature passivated zinc coating trivalent chromium color passivating agent |
CN101338421A (en) * | 2007-07-03 | 2009-01-07 | 天津市瀚隆镀锌有限公司 | Preparation of colorful passivation treatment agent after steel galvanization |
KR101664637B1 (en) * | 2012-02-23 | 2016-10-10 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Replenishing compositions and methods of replenishing pretreatment compositions |
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2014
- 2014-05-01 GB GBGB1407690.5A patent/GB201407690D0/en not_active Ceased
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2015
- 2015-04-29 WO PCT/EP2015/059322 patent/WO2015165956A1/en active Application Filing
- 2015-04-29 EP EP15722112.8A patent/EP3137652B1/en active Active
- 2015-04-29 ES ES15722112T patent/ES2703560T3/en active Active
- 2015-04-29 CN CN201580021874.8A patent/CN106232872B/en active Active
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ES2703560T3 (en) | 2019-03-11 |
TW201602410A (en) | 2016-01-16 |
CN106232872B (en) | 2019-04-23 |
EP3137652B1 (en) | 2018-10-10 |
WO2015165956A1 (en) | 2015-11-05 |
CN106232872A (en) | 2016-12-14 |
GB201407690D0 (en) | 2014-06-18 |
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