EP3652363A1 - An aluminium alloy rolled product with intense iridiscent colors - Google Patents
An aluminium alloy rolled product with intense iridiscent colorsInfo
- Publication number
- EP3652363A1 EP3652363A1 EP18735324.8A EP18735324A EP3652363A1 EP 3652363 A1 EP3652363 A1 EP 3652363A1 EP 18735324 A EP18735324 A EP 18735324A EP 3652363 A1 EP3652363 A1 EP 3652363A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide film
- anodic oxide
- porous anodic
- rolled product
- solution
- 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
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 11
- 239000003086 colorant Substances 0.000 title description 17
- 239000010407 anodic oxide Substances 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004411 aluminium Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000007743 anodising Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000004040 coloring Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012703 sol-gel precursor Substances 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000987 azo dye Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005098 hot rolling Methods 0.000 claims description 6
- -1 polysiloxane Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000001000 anthraquinone dye Substances 0.000 claims description 5
- 239000008119 colloidal silica Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 claims description 4
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 3
- 238000005097 cold rolling Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000003303 reheating Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims 1
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 25
- 229910045601 alloy Inorganic materials 0.000 description 21
- 239000000956 alloy Substances 0.000 description 21
- 239000011777 magnesium Substances 0.000 description 13
- 239000010949 copper Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- QWYBGPXCNWEGHC-UHFFFAOYSA-N gold Chemical compound [Au].[Au].[Au] QWYBGPXCNWEGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/243—Chemical after-treatment using organic dyestuffs
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
Definitions
- the present invention relates to decorative aluminium rolled products having iridescent colors.
- aluminium alloys are used in the form of rolled products for decorative applications such as cosmetic packaging, automotive trims (exterior and interior) , interior design, sound system and consumer electronics.
- iridescent colors on aluminium rolled products is known.
- iridescent colors it is meant that the color changes as a function of the incident angle.
- it may be obtained on anodized aluminium having porous anodic oxide films obtained in various electrolytes (sulfuric, phosphoric, oxalic acid etc.) .
- porous anodic oxide films consist of two layers, a porous thick outer layer 22 and an inner layer which is dense and dielectrically compact called the barrier layer 21.
- the iridescent phenomenon is due to interference between the light reflected on the oxide surface and the light reflected on a metal/oxide interface.
- incident angles V as illustrated in Figure 1, different wavelengths of light have either positive or negative interference resulting in different colors being perceived.
- Iridiscent colors may be observed on porous anodic oxide films.
- Optical properties and color generation mechanism of porous anodic alumina films are provided of iridescent anodic aluminum oxide films obtained on high purity aluminum foils by phosphoric acid anodizing. The phenomenon appears to be enhanced if the porous anodic oxide film is colored.
- the patent application WO2017/013607 relates to a structural colouration method for colouring an aluminium substrate, exemplified by alloy 6061, which comprises forming a nano structure of one-dimensional photonic crystals by means of a process of periodic current pulse anodisation, the colour obtained depending on the application time of the maximum and/or minimum current density of the pulse, and the colour varying with the angle of observation.
- Patent application US2016/0362808 describes a formed aluminum article, exemplified by alloys 6061 and 6063, in which pores formed by anodic oxidation are filled with a pigment, the formed aluminum article having an adequately colored film.
- the colors can be adjusted by modifying the anodizing and coloring parameters, but for typical anodizing quality, e.g. high purity foils such as those described in the mentioned articles or more generally on 1XXX series alloys, the overall coloring effect remains light.
- An object of the invention is an anodized decorative rolled product made of an aluminum alloy consisting of, in weight %, Mg : 0 - 1.5,
- the rolled product has a porous anodic oxide film which is colored electrochemically or chemically and wherein the color of the decorative sheet is different if viewed at an incidence angle 0° and at an incidence angle of 45° .
- Another object of the invention is a method to make an anodized decorative rolled product according to the invention comprising the steps of
- porous anodic oxide film by electrochemical deposition preferably of at least one of Zn, Ni, Sn, Co,
- Cu Ag of or chemical deposition preferably of at least one dye among an azo dye, an anthraquinone dye, an indigo dye,
- Figure 1 Interference between the light reflected on the oxide surface and the light reflected on a metal/oxide interface, for an anodic porous alumina on an aluminium surface.
- Metallurgical tempers referred to are designated using the European standard EN-515.
- EN-515 European standard EN-515.
- the inventors have found that by using alloys having a specific composition, and in particular including additions of Mg and/or Mn it is possible to obtain decorative aluminium rolled products with strong iridescent colors
- an anodized decorative rolled product with strong iridescent colors can be obtained with rolled product made of an aluminum alloy consisting of, in weight %,
- the rolled product has a porous anodic oxide film which is colored electrochemically or chemically and wherein the color of the decorative sheet is different if viewed at an incidence angle 0° and at an incidence angle of 45° .
- the Si content is at least 0.03 wt . % . Excessive Si content can however be detrimental to formability.
- the Si content is at most 0.3 wt . % and preferably at most 0.25 wt . % and more preferably at most 0.2 wt . % .
- the Fe content is at least 0.02 wt . % .
- Excessive Fe content can however be detrimental to formability.
- the Fe content is at most 0.5 wt . ⁇ 6 , more preferably at most 0.4 wt . % and preferentially at most 0.2 wt . % .
- Fe is at most 0.5 wt . % and Si is at most 0.3 wt . % .
- the other elements which have a content of ⁇ 0.05 wt.% each and ⁇ 0.15 wt.% in total, are undesirable impurities.
- the alloy contains from 0.8 to 1.5 wt.% Mn and is preferably an alloy from the 3XXX series.
- Preferred alloys in this first embodiment are AA3103, AA3104 and AA3005.
- the Mg content is at most 1.3 wt.% and preferably at most 0.6 wt.%
- the Mn content is at most 0.2 wt.% and the Mg content is from 0.5 to 1.1 wt.%.
- the alloy is preferably an alloy from the 5XXX series.
- This second embodiment is advantageously also combined with a Si content of at most 0.2 wt.%, preferably at most 0.1 wt.% and most preferably at most 0.04 wt.%.
- This second embodiment is advantageously also combined with a Fe content of at most 0.2 wt.%, preferably at most 0.1 wt.% and most preferably at most 0.06 wt .%.
- Preferred alloys in this second embodiment are AA5005, AA5505 and AA5657.
- the method to make an anodized decorative rolled product according according to the invention comprises the steps of
- a matt or bright aspect for example by satin matt etching or by chemical/electrochemical brightening
- porous anodic oxide film by electrochemical deposition preferably of at least one of Zn, Ni, Sn, Co, Cu, Ag of or chemical deposition preferably of at least one dye among an azo dye, an anthraquinone dye, an indigo dye,
- porous anodic oxide film by depositing a sol-gel precursor followed by evaporation and/or curing.
- Typical surfactants are anionic such as carboxylates or sulphonates, nonionic such as ethoxylated aliphatic alcohols, cationic such as quaternary ammonium salts or amphoteric such as aliphatic aminocarboxylic acid salts.
- the porous outer layer obtained from acid anodizing can be schematically represented as a closed-packed array of hexagonally arranged cells containing pores in each cell-center.
- Figure 1 illustrates a cross section of a porous anodic oxide film 2 on aluminium an aluminium substrate 1, comprising a barrier layer 21 and a porous outer layer 22.
- the porous anodic oxide film is characterized by given parameters such as a pore diameter, interpore distance (cell diameter) of the porous outer layer and the barrier layer thickness.
- the porous anodic oxide film of the products according to the invention exhibit a barrier layer with a thickness advantageously from 15 to 25 nm, in order to obtain the desired iridiscent colors.
- the porous anodic oxide film total thickness is advantageously between 1 and 10 ym.
- a sulfuric anodizing can be achieved at l-l,5A/dm 2 at 20°C, providing an approximately 21 nm thick barrier layer, the anodizing time being adjusted to vary the coloring effect,
- the coloring dyestuff concentration may vary from 0.1 to lOg/L, depending on the color and the required darkness.
- the temperature is usually in the range of 50 to 60°C, with some exceptions working at lower temperature.
- the porous anodic oxide film is coated by depositing a sol-gel precursor followed by evaporation and/or curing to obtain a sol-gel coating.
- a sol-gel precursor followed by evaporation and/or curing to obtain a sol-gel coating.
- the present inventors observed that surprisingly the sol-gel coating does not alter the iridescent appearance, probably because of its specific optical properties.
- the sol-gel coating protects the porous anodic film from scratches, fingerprints, and other surface deffects.
- conventional coatings such as clear lacquer does not allow not to keep the iridescent aspect.
- the sol-gel precursor is made from a mixture of a polysiloxane, preferably prepared from an alcoholic solution of silane, preferably of an alkoxysilane solution, and an aqueous solution of colloidal silica.
- the sol-gel precursor is advantageously prepared from two solutions A and B, solution A being an alcoholic solution of one or more alkoxysilanes , the alcohol used as solvent being methanol, ethanol, propanol, preferably isopropanol, butanol or a combination thereof, the alkoxysilanes being described by the general formula XnSi (OR) 4- n wherein "R” is a simple alkyl, preferably chosen in the group consisting of methyl, ethyl, propyl and butyl and "X" is also an alkyl, preferably selected from the group consisting of methyl, ethyl, propyl and butyl; solution B being a solution of colloidal silica dissolved in water.
- solution A contains 25 - 35 wt% TEOS and 15 - 25 wt% MTMOS, both dissolved in 40 - 60 wt% isopropyl alcohol.
- Advantageously solution B is set with an acid, preferably with nitric acid (HN03) , to a pH value between 2.0 and 4, preferably between 2.5 and 3.0 and more preferably close to 2.7.
- Advantgeously the alkali content of the silica is less than 0.04 wt % Na 2 0.
- the deposition of the sol-gel precursor is carried out by immersion.
- the sol-gel coating thickness is comprised between 2 and 4 ym.
- the sol-gel coating contains a small quantity of organic compounds, for example the carbon content of the coating as measured by XPS (X-Ray Photoelectron Spectrometry) is less than 10 atomic % as measured by concentration profile through the sol-gel coating.
- curing of the sol-gel is done at a temperature comprised between 150 and 250 °C during 30 to 60 seconds.
- the product of the invention is particularly useful for decorative applications such as cosmetic packaging, automotive trims (exterior and interior) , interior design, sound system and consumer electronics.
- composition of the alloys is provided in Table 1
- Electrolytic coloring with nickel sulphate 30g/L, boric acid 30g/L, ammonium sulphate 15g/L, 35°C, 2 min 19V AC current or chemical coloring with an azo dye chromium complex : Sanodal® Black 2LW (lg/L), with an azo dye copper complex : Sanodure® Fast Gold L (3g/L) , and with an anthraquinone dye :Sanodye® Blue 2LW (3g/L) at 60°C during 2 min,
- the resulting samples were observed at different incident angles.
- the intensity of colors was classified through comparison with reference samples and scaled from 1 : light to 3 : strong.
- Coloring with alloys according to the invention enables obtention of strong iridescent colors, ranging from 2 to 3.
- the sample of example 1 made of alloy 5657 is protected by a sol-gel coating.
- the sol-gel solution applied by immersion consists of the mixture of a solution A and a solution B.
- Anhydrous solution A comprises a mixture of unhydrolyzed siloxanes and alcohols:
- TEOS tetraethylorthosilicate
- trimethoxymethylsilane (MTMOS)
- the aqueous solution B comprises: 25% by weight of colloidal silica and 75% by weight of water.
- the pH of solution B is modified to reach 2.5 by addition of acid such as, for example, HN03.
- the silica must have the lowest possible alkaline content, preferably less than 0.04 m.cL S S "6 of Na20.
- Solution A is mixed with solution B in the presence of nitric acid with continuous stirring and leads to a hydrolysis and condensation reaction bringing the mixture to a gel state.
- Solutions A and B are mixed with a weight ratio of preferably 7 : 3.
- the mixture is preferably maintained at a pH value of between 2 and 4, preferably 2.5 to 3.0, and most preferably 2.7.
- the pH value is corrected by addition of acid, preferably nitric acid.
- the resulting solution is filtered.
- the filtration may, for example, be carried out using polypropylene filters with a mesh size of 1 micron. Before use, the solution is left standing for 12 to 22 hours before being applied to the substrate to form the protective deposit.
- the baking of the deposit is carried out at a temperature of 150 to 250 ° C for 30s to 60s.
- the thickness of the deposit is preferably 2 to 4 ⁇ and contains only very few organic compounds (less than 10 at%, measured by depth profile in XPS) .
- the strong iridescent coloring of the alloy according to the invention is not modified by the sol-gel coating, which is suprising because irridescence is based on interference phenomena and the addition of a thin coating is expected to affect coloring. Moreover the surface is well protected mechanically by the sol-gel coating.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1756527A FR3068712B1 (en) | 2017-07-10 | 2017-07-10 | ALUMINUM ALLOY LAMINATED PRODUCT WITH INTENSE IRIDESCENT COLORS |
PCT/EP2018/068242 WO2019011778A1 (en) | 2017-07-10 | 2018-07-05 | An aluminium alloy rolled product with intense iridiscent colors |
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EP3652363A1 true EP3652363A1 (en) | 2020-05-20 |
EP3652363B1 EP3652363B1 (en) | 2021-06-23 |
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EP (1) | EP3652363B1 (en) |
ES (1) | ES2882886T3 (en) |
FR (1) | FR3068712B1 (en) |
WO (1) | WO2019011778A1 (en) |
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EP3553208A1 (en) * | 2018-04-09 | 2019-10-16 | DURA Operating, LLC | Method of manufacturing an aluminium component having a coloured surface |
CN112973677A (en) * | 2019-12-13 | 2021-06-18 | 山西潞安矿业(集团)有限责任公司 | Preparation method and application of hydrophobic noble metal catalyst |
CN111206275B (en) * | 2020-02-17 | 2021-04-06 | 王勇 | Strong acid and strong basicity resistant hole sealing treatment method for aluminum alloy anodic oxide film |
CN112501461B (en) * | 2020-10-23 | 2022-05-31 | 福耀汽车铝件(福建)有限公司 | Preparation method of automotive high-gloss aluminum alloy exterior trim plate |
CN117778822A (en) * | 2024-01-03 | 2024-03-29 | 广东融盈铝业科技有限公司 | High-performance aluminum alloy capable of being anodized, preparation method thereof and anodizing method |
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DE102008011296A1 (en) * | 2007-03-16 | 2008-09-18 | Süddeutsche Aluminium Manufaktur GmbH | Motor vehicle component with sol-gel coating |
EP2904132A1 (en) * | 2012-10-08 | 2015-08-12 | Süddeutsche Aluminium Manufaktur GmbH | Process for producing a sol-gel coating on a surface to be coated of a component and also corresponding component |
CN106068338A (en) * | 2014-02-28 | 2016-11-02 | 株式会社樱花彩色笔 | Coloring aluminium formed body and manufacture method thereof |
AR102806A1 (en) * | 2015-07-21 | 2017-03-29 | Consejo Nac De Investig Científicas Y Técnicas (Conicet) | METHOD OF STRUCTURAL COLORATION OF ALUMINUM ANODIZED BY FORMATION OF PHOTONIC CRYSTALS THROUGH CURRENT PULSES |
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EP3652363B1 (en) | 2021-06-23 |
FR3068712B1 (en) | 2021-10-01 |
WO2019011778A1 (en) | 2019-01-17 |
ES2882886T3 (en) | 2021-12-03 |
FR3068712A1 (en) | 2019-01-11 |
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