EP3545118B1 - Composition et procédé de prétraitement sans chrome de surfaces d'aluminium - Google Patents
Composition et procédé de prétraitement sans chrome de surfaces d'aluminium Download PDFInfo
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- EP3545118B1 EP3545118B1 EP17792018.8A EP17792018A EP3545118B1 EP 3545118 B1 EP3545118 B1 EP 3545118B1 EP 17792018 A EP17792018 A EP 17792018A EP 3545118 B1 EP3545118 B1 EP 3545118B1
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- 239000000203 mixture Substances 0.000 title claims description 44
- 229910052782 aluminium Inorganic materials 0.000 title claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 14
- 239000004411 aluminium Substances 0.000 title 1
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 150000003609 titanium compounds Chemical class 0.000 claims description 16
- -1 phosphorus compound Chemical class 0.000 claims description 15
- 150000003755 zirconium compounds Chemical class 0.000 claims description 14
- 239000005078 molybdenum compound Substances 0.000 claims description 13
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical class [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
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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
- C23C22/05—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
- C23C22/36—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 containing also phosphates
- C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
Definitions
- the present invention relates to a chromium-free composition for the pretreatment of aluminum surfaces, a corresponding method and a correspondingly pretreated component or strip.
- composition according to claim 1 a concentrate according to claim 9, a method according to claim 10 and a component or band according to claim 14.
- aqueous is to be understood as meaning that more than 50% by weight of the solvent contained is water.
- Chromium-free composition means that only raw materials are used for their production that contain chromium as an impurity in the ppm range at most.
- an "aluminum surface” is to be understood as meaning a surface which consists at least partly of aluminum or an aluminum alloy.
- hexafluorozirconic acid is intended to encompass not only hexafluorozirconic acid itself but also its single and double deprotonated form. The same applies to "hexafluorotitanic acid”.
- phosphate is also intended to include pyrophosphate, polyphosphate, and in each case all mono- or multiply protonated forms.
- molybdate is also intended to include its singly or doubly protonated form.
- organic polymer is also intended to include organic copolymers and mixtures of organic polymers and / or copolymers.
- the present invention relates to an aqueous, chromium-free composition for the pretreatment of aluminum surfaces which contains at least one water-soluble phosphorus compound, at least one water-soluble zirconium compound, at least one water-soluble titanium compound and at least one water-soluble molybdenum compound, the phosphorus compound content in the range from 15 to 50 mg / l (calculated as phosphorus), the content of zirconium compound in the range from 400 to 600 mg / l (calculated as metal), the content of titanium compound in the range from 85 to 400 mg / l (calculated as metal) and the content of molybdenum compound in the Range from 40 to 150 mg / l (calculated as metal), and wherein the aqueous composition has a pH (at room temperature) in the range from 2.0 to 5.0.
- the content of phosphorus compound is preferably in the range from 25 to 40 mg / l (calculated as phosphorus), the content of zirconium compound in the range from 450 to 540 mg / l (calculated as metal), the content of titanium compound in the range from 200 to 400 mg / l (calculated as metal), and the content of molybdenum compound in the range from 60 to 130 mg / l (calculated as metal).
- the content of phosphorus compound is particularly preferably in the range from 30 to 38 mg / l (calculated as phosphorus), the content of zirconium compound in the range from 470 to 520 mg / l (calculated as metal), the content of titanium compound in the range from 350 to 380 mg / l (calculated as metal), and the content of molybdenum compound in the range from 80 to 125 mg / l (calculated as metal).
- the ratios of the individual contents of phosphorus compound, zirconium compound, titanium compound and molybdenum compound are preferably in the range from (0.04 to 0.40) to (1.4 to 5.8) to 1.0 to (0.10 to 1.4 ), particularly preferably in the range from (0.06 to 0.25) to (1.4 to 3.5) to 1.0 to (0.15 to 0.9) and very particularly preferably in the range from (0, 08 to 0.12) to (1.4 to 1.5) to 1.0 to (0.20 to 0.40) (normalized to the titanium compound content).
- the aqueous composition preferably contains free fluoride, the content of free fluoride being in the range from 40 to 100 mg / l, preferably in the range from 60 to 80 mg / l, and the total content of fluoride in the range from 1 to 2 g / l , preferably in the range from 1.4 to 1.8 g / l.
- the content of free fluoride is determined potentiometrically by means of a fluoride-sensitive electrode at room temperature, the total fluoride content by distillation according to Seel and potentiometrically.
- the at least one zirconium compound here preferably comprises hexafluorozirconic acid and the at least one titanium compound comprises hexafluorotitanic acid.
- the at least one zirconium compound is particularly preferably hexafluorozirconic acid and the at least one titanium compound is hexafluorotitanic acid.
- the at least one phosphorus compound is preferably phosphate.
- the at least one molybdenum compound is preferably molybdate.
- the at least one phosphorus compound is particularly preferably phosphate and the at least one molybdenum compound is molybdate.
- the at least one zirconium compound is hexafluorozirconic acid
- the at least one titanium compound is hexafluorotitanic acid
- the at least one phosphorus compound is phosphate
- the at least one molybdenum compound is molybdate.
- the aqueous composition preferably has a pH (at room temperature) in the range from 3.0 to 4.0. Furthermore, the aqueous composition preferably has Free acid points in the range from 3.9 to 4.5 and total acid points no greater than 25.
- the aqueous composition has a pH (at room temperature) in the range from 3.0 to 4.0, free acid points in the range from 3.9 to 4.5 and total acid points of not more than 25 .
- aqueous composition 25 ml of the aqueous composition are diluted with 100 ml of distilled water in a suitable vessel and mixed with approx. 5 ml of a 25% potassium fluoride solution and 5 drops of a phenolphthalein solution. With 0.1 M sodium hydroxide solution the color changes to red, i.e. titrated to pH 8.6. The volume in ml of the sodium hydroxide solution consumed in the titration gives the free acid points.
- aqueous composition 25 ml of the aqueous composition are diluted in a suitable vessel with 100 ml of distilled water and 5 drops of a phenolphthalein solution are added.
- a phenolphthalein solution With 0.1 M sodium hydroxide solution the color changes to red, i.e. titrated to pH 8.6.
- the volume in ml of the sodium hydroxide solution used in the titration gives the total acid points.
- the aqueous composition preferably contains a total of no more than 1 mg / l, particularly preferably no more than 0.5 mg / l and very particularly preferably no more than 0.1 mg / l of organic polymer.
- organic polymers in particular of polyacrylic acid, can in fact have a detrimental effect on the paint adhesion achieved.
- the aqueous composition preferably contains no more than 300 mg / l, particularly preferably no more than 100 mg / l, of aluminum.
- Aluminum is not added during the production of the aqueous composition, but it enters the latter via the chemical reaction between the aluminum surface to be treated and the treatment solution.
- the aqueous composition preferably contains not more than 20 mg / l, particularly preferably not more than 10 mg / l, of the elements As, Ba, Cd, Co, Cu, Mn, Ni, Pb, Sb, Sn, Sr, V and Ce .
- the present invention also relates to a concentrate from which the aqueous composition according to the invention can be obtained by diluting with water and optionally adjusting the pH value with a suitable acid or base.
- the present invention also relates to a method for the chromium-free pretreatment of aluminum surfaces, in which an optionally cleaned and rinsed surface, which consists at least partially of aluminum or an aluminum alloy, with the The aqueous composition according to the invention is brought into contact and then optionally rinsed and / or dried.
- Said surface is in particular the surface of a component or of a strip.
- the surface preferably consists predominantly, particularly preferably exclusively or almost exclusively, of aluminum or at least one aluminum alloy.
- Suitable aluminum alloys are in particular aluminum-magnesium alloys such as those of the 5000 series and aluminum-magnesium-silicon alloys such as those of the 2000 series.
- the surface can be brought into contact with the composition according to the invention by immersion application or by spray application.
- the surface is preferably brought into contact with the composition according to the invention for 4 to 10 seconds at 45 to 60 ° C., particularly preferably for 5 to 7 seconds at 50 to 55 ° C.
- the surface is preferably brought into contact with the aqueous treatment solution in such a way that a phosphor layer (calculated as P 2 O 5 ) in the range from 8 to 17 mg / m 2 , preferably in the range from 10 to 15 mg / m 2 , a zirconium layer in Range from 1 to 6 mg / m 2 , preferably in the range from 1 to 2 mg / m 2 , a titanium layer in the range from 7 to 19 mg / m 2 , preferably in the range from 11 to 16 mg / m 2 , and a molybdenum layer in the range from 6 to 18 mg / m 2 , preferably in the range from 9 to 14 mg / m 2 , results on the surface.
- a phosphor layer (calculated as P 2 O 5 ) in the range from 8 to 17 mg / m 2 , preferably in the range from 10 to 15 mg / m 2
- a zirconium layer in Range from 1 to
- the surface is the surface of a tape, the surface being immersed in the aqueous composition for 5 to 10 seconds at 50 to 55 ° C.
- the surface is first cleaned with alkaline or alkaline and acidic, then thoroughly, preferably in several stages, rinsed with water and immersed in the aqueous composition.
- the present invention also relates to a component or strip with a surface which at least partially consists of aluminum or an aluminum alloy, the component or strip being obtainable using the method according to the invention and optionally being painted.
- the surface of the component or strip preferably has a phosphor layer (calculated as P 2 O 5 ) in the range from 8 to 17 mg / m 2 , preferably in the range from 10 to 15 mg / m 2 , and a zirconium layer in the range from 1 to 6 mg / m 2 , preferably in the range from 1 to 2 mg / m 2 , a titanium layer in the range from 7 to 19 mg / m 2 , preferably in the range from 11 to 16 mg / m 2 , and a molybdenum layer in the range from 6 to 18 mg / m 2 , preferably in the range from 9 to 14 mg / m 2 .
- a phosphor layer (calculated as P 2 O 5 ) in the range from 8 to 17 mg / m 2 , preferably in the range from 10 to 15 mg / m 2
- a zirconium layer in the range from 1 to 6 mg / m 2 , preferably in the range
- the present invention can improve paint adhesion.
- compositions B1 to B6 according to the invention shown in Table 1 and the compositions VB1 to VB4 not according to the invention were produced as follows.
- the amounts of phosphorus (as P 2 O 5 ), zirconium, titanium and molybdenum were each determined by means of X-ray fluorescence analysis (XRF) (see Tab. 2 ).
- the metal sheets were then coated with a polyamino resin combination using a 30 ⁇ m doctor blade.
- the lacquer was then baked in the oven for 45 seconds at 250 ° C. (max. Temperature of the metal sheets: 224 ° C.) so that a lacquer layer thickness of 7 ⁇ m was obtained.
- compositions B1 to B6 according to the invention both in the T-bend test and in the cross-cut test.
- B1 and B2 deliver the best results.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Claims (15)
- Composition aqueuse, sans chrome pour le prétraitement de surfaces d'aluminium, caractérisée en ce qu'elle contient au moins un composé de phosphore hydrosoluble, au moins un composé de zirconium hydrosoluble, au moins un composé de titane hydrosoluble et au moins un composé de molybdène hydrosoluble, la teneur en composé de phosphore se situant dans la plage de 15 à 50 mg/l calculée en tant que phosphore, la teneur en composé de zirconium se situant dans la plage de 400 à 600 mg/l calculée en tant que métal, la teneur en composé de titane se situant dans la plage de 85 à 400 mg/l calculée en tant que métal et la teneur en composé de molybdène se situant dans la plage de 40 à 150 mg/l calculée en tant que métal, et la composition aqueuse présentant une valeur de pH à température ambiante dans la plage de 2,0 à 5,0.
- Composition aqueuse selon la revendication 1, caractérisée en ce que la teneur en composé de phosphore se situe dans la plage de 25 à 40 mg/l, préférablement dans la plage de 30 à 38 mg/l calculée en tant que phosphore, la teneur en composé de zirconium se situe dans la plage de 450 à 540 mg/l, préférablement dans la plage de 470 à 520 mg/l calculée en tant que métal, la teneur en composé de titane se situe dans la plage de 200 à 400 mg/l, préférablement dans la plage de 350 à 380 mg/l calculée en tant que métal et la teneur en composé de molybdène se situe dans la plage de 60 à 130 mg/l, préférablement dans la plage de 80 à 125 mg/l calculée en tant que métal.
- Composition aqueuse selon la revendication 1 ou 2, caractérisée en ce que les rapports des teneurs individuelles en composé de phosphore, en composé de zirconium, en composé de titane et en composé de molybdène se situent dans la plage de 0,04 à 0,40 sur 1,4 à 5,8 sur 1,0 sur 0,10 à 1,4, préférablement dans la plage de 0,06 à 0,25 sur 1,4 à 3,5 sur 1,0 sur 0,15 à 0,9 et particulièrement préférablement dans la plage de 0,08 à 0,12 sur 1,4 à 1,5 sur 1,0 sur 0,20 à 0,40, normé sur la teneur en composé de titane.
- Composition aqueuse selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient du fluorure libre, la teneur en fluorure libre se situant dans la plage de 40 à 100 mg/l, préférablement dans la plage de 60 à 80 mg/l, la teneur totale en fluor se situant dans la plage de 1 à 2 g/l, préférablement dans la plage de 1,4 à 1,8 g/l, l'au moins un composé de zirconium comprenant de, préférablement étant l'acide hexafluorozirconique, et l'au moins un composé de titane comprenant de, préférablement étant l'acide hexafluorotitanique.
- Composition aqueuse selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition aqueuse présente une valeur de pH dans la plage de 3,0 à 4,0, des points d'acide libre dans la plage de 3,9 à 4,5 et des points d'acides totaux de pas plus de 25.
- Composition aqueuse selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle ne contient au total pas plus de 1 mg/l, préférablement pas plus de 0,5 mg/l et particulièrement préférablement pas plus de 0,1 mg/l de polymère organique.
- Composition aqueuse selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle ne contient pas plus de 300 mg/l, préférablement pas plus de 100 mg/l d'aluminium.
- Composition aqueuse selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle ne contient au total pas plus de 20 mg/l, préférablement pas plus de 10 mg/l des éléments As, Ba, Cd, Co, Cu, Mn, Ni, Pb, Sb, Sn, Sr, V et Ce.
- Concentré caractérisé en ce qu'à partir de celui-ci, par dilution avec un solvant approprié, préférablement avec de l'eau, et éventuellement par ajustement de la valeur du pH avec un acide ou une base approprié(e), une composition aqueuse selon l'une quelconque des revendications 1 à 8 peut être obtenue.
- Procédé pour le prétraitement essentiellement sans chrome de surfaces d'aluminium, caractérisé en ce qu'une surface éventuellement nettoyée et rincée qui est constituée au moins partiellement d'aluminium ou d'un alliage d'aluminium est mise en contact avec une composition aqueuse selon l'une quelconque des revendications 1 à 8 et ensuite éventuellement rincée et/ou séchée.
- Procédé selon la revendication 10, caractérisé en ce que la surface est mise en contact avec la composition aqueuse de telle manière qu'un dépôt de phosphore calculé en tant que P2O5 dans la plage de 8 à 17 mg/m2, préférablement dans la plage de 10 à 15 mg/m2, qu'un dépôt de zirconium dans la plage de 1 à 6 mg/m2, préférablement dans la plage de 1 à 2 mg/m2, qu'un dépôt de titane dans la plage de 7 à 19 mg/m2, préférablement dans la plage de 11 à 16 mg/m2 et qu'un dépôt de molybdène dans la plage de 6 à 18 mg/m2, préférablement dans la plage de 9 à 14 mg/m2, sur la surface en résulte.
- Procédé selon la revendication 10 ou 11, caractérisé en ce que la surface est la surface d'un ruban et la surface est trempée dans la composition aqueuse pendant 5 à 10 secondes à une température de 50 à 55 °C.
- Procédé selon l'une quelconque des revendications 10 à 12, caractérisé en ce que la surface est nettoyée tout d'abord de manière alcaline ou de manière alcaline et acide, ensuite rincée soigneusement, préférablement en plusieurs étapes, avec de l'eau et est trempée dans la composition aqueuse.
- Pièce ou ruban doté(e) d'une surface qui est constituée au moins partiellement d'aluminium ou d'un alliage d'aluminium, caractérisé(e) en ce qu'elle/il peut être obtenu(e) avec un procédé selon l'une quelconque des revendications 10 à 13 et a été éventuellement peint(e).
- Pièce ou ruban selon la revendication 14, caractérisé(e) en ce que sa surface présente un dépôt de phosphore calculé en tant que P2O5 dans la plage de 8 à 17 mg/m2, préférablement dans la plage de 10 à 15 mg/m2, un dépôt de zirconium dans la plage de 1 à 6 mg/m2, préférablement dans la plage de 1 à 2 mg/m2, un dépôt de titane dans la plage de 7 à 19 mg/m2, préférablement dans la plage de 11 à 16 mg/m2 et un dépôt de molybdène dans la plage de 6 à 18 mg/m2, préférablement dans la plage de 9 à 14 mg/m2.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL17792018T PL3545118T3 (pl) | 2016-11-23 | 2017-10-25 | Kompozycja i sposób bezchromowej obróbki wstępnej powierzchni aluminiowych |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102016223170 | 2016-11-23 | ||
PCT/EP2017/077308 WO2018095684A1 (fr) | 2016-11-23 | 2017-10-25 | Composition et procédé de prétraitement sans chrome de surfaces d'aluminium |
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EP3545118A1 EP3545118A1 (fr) | 2019-10-02 |
EP3545118B1 true EP3545118B1 (fr) | 2020-08-19 |
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EP17792018.8A Active EP3545118B1 (fr) | 2016-11-23 | 2017-10-25 | Composition et procédé de prétraitement sans chrome de surfaces d'aluminium |
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Country | Link |
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US (1) | US11686000B2 (fr) |
EP (1) | EP3545118B1 (fr) |
CN (1) | CN109983160B (fr) |
CA (1) | CA3041934A1 (fr) |
ES (1) | ES2832656T3 (fr) |
PL (1) | PL3545118T3 (fr) |
RU (1) | RU2754069C2 (fr) |
WO (1) | WO2018095684A1 (fr) |
ZA (1) | ZA201903869B (fr) |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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US5143562A (en) * | 1991-11-01 | 1992-09-01 | Henkel Corporation | Broadly applicable phosphate conversion coating composition and process |
MY130189A (en) * | 1994-03-24 | 2007-06-29 | Nihon Parkerizing | Aqueous composition and solution and process for metallic surface-treating an aluminum-containing metal material |
DE4417965A1 (de) * | 1994-05-21 | 1995-11-23 | Henkel Kgaa | Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren |
US6706123B2 (en) * | 2000-08-01 | 2004-03-16 | Henkel Kommanditgesellschaft Auf Aktien | Phosphate conversion coating concentrate |
US7947333B2 (en) * | 2006-03-31 | 2011-05-24 | Chemetall Gmbh | Method for coating of metallic coil or sheets for producing hollow articles |
DE102006039633A1 (de) * | 2006-08-24 | 2008-03-13 | Henkel Kgaa | Chromfreies, thermisch härtbares Korrosionsschutzmittel |
DE102009047522A1 (de) * | 2009-12-04 | 2011-06-09 | Henkel Ag & Co. Kgaa | Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zink- und Eisenoberflächen |
IT1397902B1 (it) * | 2010-01-26 | 2013-02-04 | Np Coil Dexter Ind Srl | Processi di pretrattamento alla verniciatura, a basso impatto ambientale, alternativi ai trattamenti tradizionali di fosfatazione. |
CN103276384B (zh) * | 2013-05-06 | 2015-12-09 | 大庆宝丰科技有限公司 | 通用型金属陶化皮膜处理剂及制备方法 |
CN104561975A (zh) * | 2014-12-30 | 2015-04-29 | 广州市泓硕环保科技有限公司 | 一种铝合金免水洗彩色无铬钝化膜及钝化液和使用方法 |
WO2017046139A1 (fr) | 2015-09-15 | 2017-03-23 | Chemetall Gmbh | Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène |
-
2017
- 2017-10-25 PL PL17792018T patent/PL3545118T3/pl unknown
- 2017-10-25 CA CA3041934A patent/CA3041934A1/fr active Pending
- 2017-10-25 ES ES17792018T patent/ES2832656T3/es active Active
- 2017-10-25 US US16/463,196 patent/US11686000B2/en active Active
- 2017-10-25 WO PCT/EP2017/077308 patent/WO2018095684A1/fr unknown
- 2017-10-25 RU RU2019118432A patent/RU2754069C2/ru active
- 2017-10-25 CN CN201780071845.1A patent/CN109983160B/zh active Active
- 2017-10-25 EP EP17792018.8A patent/EP3545118B1/fr active Active
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Also Published As
Publication number | Publication date |
---|---|
EP3545118A1 (fr) | 2019-10-02 |
PL3545118T3 (pl) | 2021-02-08 |
BR112019010258A2 (pt) | 2019-09-03 |
CA3041934A1 (fr) | 2018-05-31 |
ZA201903869B (en) | 2022-12-21 |
CN109983160B (zh) | 2022-05-31 |
RU2019118432A3 (fr) | 2021-03-19 |
WO2018095684A1 (fr) | 2018-05-31 |
RU2019118432A (ru) | 2020-12-24 |
CN109983160A (zh) | 2019-07-05 |
RU2754069C2 (ru) | 2021-08-25 |
US20200063267A1 (en) | 2020-02-27 |
ES2832656T3 (es) | 2021-06-10 |
US11686000B2 (en) | 2023-06-27 |
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