EP3430185A1 - Highly reflecting anodised al surfaces with tailored diffuse and specular content - Google Patents
Highly reflecting anodised al surfaces with tailored diffuse and specular contentInfo
- Publication number
- EP3430185A1 EP3430185A1 EP16727968.6A EP16727968A EP3430185A1 EP 3430185 A1 EP3430185 A1 EP 3430185A1 EP 16727968 A EP16727968 A EP 16727968A EP 3430185 A1 EP3430185 A1 EP 3430185A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminium
- oxide
- acid
- metal
- embedded
- 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
- 238000000034 method Methods 0.000 claims abstract description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- 239000004411 aluminium Substances 0.000 claims abstract description 45
- 238000007743 anodising Methods 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000010407 anodic oxide Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000004922 lacquer Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004663 powder metallurgy Methods 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009714 stir casting Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000003466 welding Methods 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
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- 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
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- 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
-
- 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
- C25D11/14—Producing integrally coloured layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Definitions
- the present invention relates to a method to obtain a reflective anodised aluminium surface on an object.
- the present invention relates in particular to a method to obtain a reflective, anodised aluminium surface having a white appearance.
- White surfaces are ubiquitous in a huge number of applications (window frames, panels, doors, lamps, etc.), and while a white surface can be achieved using paint or even white plastics, a white wear-resistant aluminium surface would often be the number one choice if such a surface would be available.
- White aluminium surfaces can be produced by embedding titanium dioxide (Ti0 2 ) or other white pigments into an anodic film.
- the white pigments opacify the films primarily by diffusely reflecting light. This reflection occurs because the white pigment scatters or bends light strongly. If there is enough white pigment in an anodic film almost all visible light striking it will be reflected, and the anodic film will appear opaque, white, and bright.
- anodised surface is significantly higher than that of a traditional painted surface.
- anodised surfaces are usually preferred to painted surfaces when it comes to both practical applications and long-lasting decorative purposes. Therefore white anodized surfaces are preferred and have high value compared to the white painted aluminium.
- Embedding white pigments into an anodic film is not a straight-forward operation, considering that the pigments are typically magnitudes larger than the nanoscaled pores that are created in an anodizing process. It is known from EP 2 649 224 Bl to obtain a radiation scattering surface finish on an object by providing the object with a top layer, comprising aluminium or an aluminium alloy, the top layer comprising added discrete inclusions of a second material being different from aluminium and the first alloy, and subsequently anodising said top layer to form an anodic oxide layer and to generate from the inclusions discrete radiation scattering elements.
- said radiation scattering elements are selected from particles of titanium, tin, zirconium, iron, titanium oxide, tin oxide, zirconium oxide, and iron oxide.
- An anodising method using high-frequency switching anodising is disclosed in "Anodizing method for aluminum alloy by using high-frequency switching electrolysis" H.Tanaka, M. Fujita, T.Yamamoto, H. Muramatsu Suzuki Motor Corporation; H .Asoh, S.Ono, Kogakuin University.
- Multi-pass friction stir processing to impregnate Ti0 2 particles into the surface of an aluminium alloy and subsequent anodising in a sulphuric acid electrolyte is disclosed by V.C. Gudla, F. Jensen, A. Simar, R. Shabadi, R. Ambat, : Friction stir processed Al-Ti0 2 surface composites: Anodising behaviour and optical appearance, Appl . Surf. Sci . 324 (2015) 554- 562.
- FSP Multi-pass friction stir processing
- High frequency anodising of friction stir processed Al-Ti02 surface composites using a high frequency pulse and pulse reverse pulse technique at a fixed frequency in a sulfuric acid bath is disclosed by V. C. Gudla, F. Jensen, K. Bordo, A. Simar, R. Ambat, Effect of High Frequency Pulsing on the Interfacial Structure of Anodized Aluminium-Ti02, Journal of The Electrochemical Society, 162 (7) C303-C310 (2015) .
- Multi-pass friction stir processing to impregnate metal oxide (Ti0 2 , Y 2 0 3 and Ce0 2 ) particles into the surface of an aluminium alloy and subsequent anodising in a sulphuric acid electrolyte is disclosed by V. C. Gudla, F. Jensen, S. Canulescu, A. Simar, R. Ambat, Friction stir processed Al - metal oxide surface composites: anodization and optical appearance, 28th international conference on surface modification technologies, June 16 th - 18 th , 2014, Tampere University of Technology, Tampere, Finland .
- FSP Multi-pass friction stir processing
- US 2009/0236228 Al relates to an anodizing method and apparatus.
- US 2006/0037866 relates to an anodic oxide film and anodizing method .
- US 2008/0087551 relates to a method for anodizing aluminum alloy and power supply for anodizing aluminum alloy.
- JP2004-035930 relates to an aluminum alloy material and anodization treatment method therefor.
- JP2008-0085574 relates to a method for anodizing an aluminum member.
- JP2007-154301 relates to an aluminum alloy anodic oxidation method and power source for aluminum alloy anodic oxidation.
- the present invention relates to a method to obtain a reflective anodised aluminium surface on an object, comprising the steps: a Providing the object with a top layer comprising aluminium or an aluminium alloy, the top layer comprising embedded discrete particles of a metal or metal oxide, said metal being different from aluminium; b Subsequently anodising said top layer to form an anodic oxide layer; wherein said anodising of step b. takes place in an aqueous solution of an organic acid applying a time varying signal.
- Fig. 1 (a) shows almost parallel growth of DC formed anodic pores, making it hard to reach the regions underneath particles;
- Fig. 1 (b) shows branched pores formed during high frequency anodising; and Fig. 2 illustrates the process disclosed in example 1.
- Fig. 1 (b) shows branched pores formed during high frequency anodising; and Fig. 2 illustrates the process disclosed in example 1.
- the embedded discrete particles are selected from the group consisting of titanium, tin, zirconium, iron, titanium oxide, tin oxide, zirconium oxide, lead oxide, yttrium oxide, and iron oxide, preferably titanium oxide.
- Titanium dioxide exhibits a light refractive index much different than sealed anodic alumina, making it an ideal pigment for obtaining good light scattering.
- pigments with other chemical compositions can be used, if they possess properties similar to those of titanium dioxide.
- the particle size of the embedded discrete particles is in the range 100-500 nm, preferably in the range 150-400 nm, such as 200-300 nm.
- the size of Ti0 2 particles should preferably be 200-300 nm to secure light scattering of all visible wavelengths, making the surface perceived as white.
- the aluminium or aluminium alloy comprises at least 95% by weight of aluminium, preferably at least 96% by weight of aluminium, such as at least 97% by weight of aluminium, such as at least 98% by weight of aluminium, more preferably at least 99% by weight of aluminium.
- a pure alumininum alloy is required for the anodic film to become as optically transparent as possible. Alloying elements such as Fe, Mn and Cu must be kept to an absolute minimum, knowing that these elements will give rise to a certain degree of light absorption, which will compromise the anodic film whiteness. Using an alloy with a composition equivalent to a 6060 (or even purer), has proven to give good results.
- the discrete particles of a metal or metal oxide are embedded by a solid state process.
- solid state processes include a solid state process selected from the group consisting of friction stir processing (FSP), additive friction stir processing (AFSP), and powder metallurgy.
- Friction stir processing is a solid state process known for its ability to modify
- FSP friction stir processing
- FSW friction stir welding
- FSP has emerged as an advanced tool to produce surface composites by embedding second phase particles into the matrix. It is exactly this feature that is utilized in this patent application as to embed white pigments into the aluminium bulk, considering that the FSP process has the required advantages of: i) Maintaining a sufficiently low temperature to avoid a critical reaction between pigment and aluminium; ii) Being able to remove excess heat via a Heat Sink, again to avoid a reaction between pigment and aluminium; iii) Securing a homogenous and individual distribution of pigments within the aluminium matrix; and iv) Leaving the pigments in a functional state.
- Friction Stir Processing is a very time-consuming batch process
- Additive Friction Stir Processing has emerged to create a continuous process, where particles are fed to the material through a hollow spinning tool. Not only is this a much faster (and non-batch) process, it also allows for much higher particle loadings.
- AFSP is the preferred technique for embedding white pigments into an aluminium matrix
- An further example of solid state processing is powder metallurgy, where pigments are mechanically alloyed into the aluminium powder. The composite powder is subsequently compressed and shaped in a normal powder metal route such as forging, cold isostatic pressing (CIP), hot isostatic pressing (HIP), direct profile extrusion, direct rolling of sheets, cold spraying, thermal spraying etc.
- the discrete particles of a metal or metal oxide are embedded by a liquid state process, such as e.g. Stir Casting or Investment Casting.
- the discrete particles of a metal or metal oxide are embedded by a vapour state process such as e.g. Physical Vapour Deposition (PVD) or Chemical Vapour Deposition (CVD).
- any of the above major processing routes can be used, as long as they fulfill the considerations mentioned above.
- Anodizing secures the conversion of aluminium into aluminium oxide.
- the pigments which were embedded into the top aluminium layer will become embedded into the aluminium oxide after anodizing.
- the difference in refractive index between the anodic oxide and the white pigments secures scattering of all visible wavelengths that finally makes the anodized surface appear white.
- Anodic films are traditionally formed by passing a direct current (DC) through an electrolyte, with the aluminium part working as the anode and a suitable material serving as the cathode.
- DC anodizing has proven problematic in anodizing the aforementioned composite alloy, due to the regions that are underneath each individual pigment. Anodic pores formed through a DC process are almost completely parallel and do not reach the regions underneath the pigments. This leaves an anodic film with embedded pigments that have a small area of non-anodized aluminium underneath them. In turn this is a very unfortunate situation, considering the light absorption properties of metallic aluminium, which finally makes the entire anodic film be perceived as dark rather than white.
- the white anodizing must be carried out at low temperature and in low-aggressive electrolyte to decrease the degree of pore wall attack.
- the electrolyte used in an anodising process is traditionally water based and has an active content of acid. Almost all weak and strong organic acids can function as an electrolyte in the anodizing step of the process according to the invention.
- the anodising of step b. takes place in an aqueous solution of an organic acid selected from the group consisting of oxalic acid, succinic acid, tartaric acid, malic acid, maleic acid, formic acid, citric acid and acetic acid.
- the anodising of step b. takes place in an aqueous solution of an organic acid selected from the group consisting of oxalic acid, formic acid and citric acid, preferably oxalic acid.
- the high frequency signal which is a time varying signal, may comprise a square wave signal having pulses with amplitudes between between -5 V and +5 V in the low period and between + 15 V and 100 V in the high period. Moreover, the voltage ramp up/down times of the pulses may be in the range between 0 and 15% of the ideal square wave pulse duration.
- the frequency of the square wave signal may typically be around 1 kHz.
- the thickness of the anodized film determines how white the surface appears. To secure a total white light scattering effect in the visible spectrum - normally about ⁇ oxide is necessary. Thus in an embodiment of the invention the thickness of the anodized film is in the range 50-300 ⁇ , such as about 75-200 ⁇ , preferably in the range 100-150 ⁇ , such as in the range 80-130 ⁇ .
- the pigment concentration determines how white the surface appears. Thus in an embodiment of the invention the pigment concentration is in the range 2-25 wt%, such as about 5-20 wt%, preferably in the range 10-15 wt%.
- optical properties can be characterized by a standard spectrophotometer, where the degree of reflected light is measured.
- Hardness can be measured with a standard microhardness testing unit, where a diamond indenter is pressed into the surface. The diagonal (in case of Vickers hardness testing) of the resulting indentation gives a figure for the surface hardness.
- Tribological properties can be found by a standardised wear tester such as a ball-on-disc setup.
- the thick anodic film obtained above may be slightly dissolved in the upper part because of the prolonged exposure to the acid electrolyte, a phenomenon known as "pore wall attack".
- the porous oxide can be stabilized by impregnating it with an agent that fills the anodic pores.
- the method comprises a further step of impregnating the anodised aluminium oxide layer.
- said impregnation is performed by means of an impregnating substance selected from the group consisting of a silicate, a lacquer, and a sol- gel substance.
- an impregnating substance selected from the group consisting of a silicate, a lacquer, and a sol- gel substance.
- lacquers and sol-gel substances include acrylics, silanes and silane based sol-gels.
- Aluminium plates with dimensions 200 mm x 60 mm x 6 mm were used for the FSP trials.
- Commercial Ti0 2 powder in rutile phase was used.
- the median diameter of the powder particles was 210 nm.
- Processing the FSP process was performed using a hermle milling machine equipped with a steel tool having 20 mm shoulder diameter, 1.5 mm pin length with a m6 thread.
- the backwards tilt angle of the tool was maintained at 1°.
- a groove 0.5 mm deep, 10 mm wide, and 180 mm long in the Al plates which was compactly filled with Ti0 2 powder.
- the filled plates were then covered by the same Al sheet rolled down to a thickness of 0.25mm to prevent loss of Ti0 2 powder during the initial FSP pass.
- Rotational speed of the tool was 1000 rpm and the advancing speed was 200 mm/min for the first pass to insure correct closure of the groove and 1000 mm/min for the next six passes.
- a surface of 175 mm long x 20 mm wide was processed for each pass with a total processing time of roughly 2 min. All seven passes were performed one over the other without any shift.
- the samples were then mechanically polished, buffed to a mirror finish and then degreased in a mild alkaline solution at 60°C.
- the samples were subsequently desmutted by immersing in diluted HNCh followed by demineralized water rinsing. Anodising was carried out in a saturated oxalic acid bath maintained at 10°C.
- a square wave high frequency signal of 1 kHz from 0 to 40V was applied, with a controlled ramp up/down duration which corresponds to 10% of the pulse duration.
- the process continues until the film thickness has grown to approximately ⁇ . After anodising the surface appears white, with both specular and diffuse reflections.
- the sample is rinsed and transferred to a hot water sealing tank for closing the open-pored anodic structure. The process is illustrated in Fig. 2.
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DKPA201600250 | 2016-04-27 | ||
PCT/EP2016/061383 WO2017186315A1 (en) | 2016-04-27 | 2016-05-20 | Highly reflecting anodised al surfaces with tailored diffuse and specular content |
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US (1) | US20190136399A1 (en) |
EP (1) | EP3430185B1 (en) |
CN (1) | CN109072473B (en) |
DK (1) | DK3430185T3 (en) |
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JP2004035930A (en) | 2002-07-02 | 2004-02-05 | Suzuki Motor Corp | Aluminum alloy material and anodization treatment method therefor |
US7838120B2 (en) | 2004-08-20 | 2010-11-23 | Suzuki Motor Corporation | Anodic oxide film |
CN100383292C (en) * | 2004-12-29 | 2008-04-23 | 湖南大学 | Anodizing method for generating ceramic film on aluminium and its alloy material surface |
JP2007154301A (en) | 2005-11-30 | 2007-06-21 | Idx Corp | Aluminum alloy anodic oxidation method and power source for aluminum alloy anodic oxidation |
TW200804629A (en) | 2006-07-05 | 2008-01-16 | Idx Corp | Power supply for anodizing |
JP5207124B2 (en) | 2008-03-24 | 2013-06-12 | スズキ株式会社 | Anodizing method |
CN101392397B (en) * | 2008-10-21 | 2011-04-20 | 湖南大学 | Electrochemistry processing method for generating oxide film on surface of aluminium or aluminium alloy material |
WO2012076467A2 (en) * | 2010-12-06 | 2012-06-14 | Bang & Olufsen A/S | A method to obtain a radiation scattering surface finish on an object |
CN102834551B (en) * | 2011-03-08 | 2015-07-01 | 纳米及先进材料研发院有限公司 | Method for producing white anodized aluminum oxide |
JP5986308B2 (en) * | 2012-06-22 | 2016-09-06 | アップル インコーポレイテッド | White-like anodic oxide film and method for forming the same |
CN103014808B (en) * | 2012-12-14 | 2015-07-29 | 中国计量学院 | The method of aluminium alloy anode oxide film is prepared with tartrate anodic oxidation |
US9512536B2 (en) * | 2013-09-27 | 2016-12-06 | Apple Inc. | Methods for forming white anodized films by metal complex infusion |
CN105705681B (en) * | 2013-10-30 | 2021-03-26 | 苹果公司 | Method for producing white appearing metal oxide films by locating reflective particles prior to or during an anodization process |
US9181629B2 (en) * | 2013-10-30 | 2015-11-10 | Apple Inc. | Methods for producing white appearing metal oxide films by positioning reflective particles prior to or during anodizing processes |
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DK3430185T3 (en) | 2023-04-24 |
CN109072473A (en) | 2018-12-21 |
HK1259273A1 (en) | 2019-11-29 |
EP3430185B1 (en) | 2023-02-22 |
WO2017186315A1 (en) | 2017-11-02 |
CN109072473B (en) | 2021-03-30 |
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