US3704210A - Process for coloring aluminum objects - Google Patents
Process for coloring aluminum objects Download PDFInfo
- Publication number
- US3704210A US3704210A US55295A US3704210DA US3704210A US 3704210 A US3704210 A US 3704210A US 55295 A US55295 A US 55295A US 3704210D A US3704210D A US 3704210DA US 3704210 A US3704210 A US 3704210A
- Authority
- US
- United States
- Prior art keywords
- aluminum
- liter
- nickel
- bath
- electrode
- 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.)
- Expired - Lifetime
Links
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 21
- 238000000034 method Methods 0.000 title abstract description 11
- 238000004040 coloring Methods 0.000 title description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 abstract description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 11
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract description 9
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 239000011260 aqueous acid Substances 0.000 abstract description 2
- 239000011253 protective coating Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 229910000906 Bronze Inorganic materials 0.000 description 9
- 239000010974 bronze Substances 0.000 description 9
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 239000001166 ammonium sulphate Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000002048 anodisation reaction Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment 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
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
Definitions
- This invention relates to colored protective surface layers on aluminum or alloys of aluminum and methods and compositions for the preparation of same.
- Such coatings have been produced in various ways, one of which consists of forming a porous surface on the aluminum object by anodization, depositing metal pigments into the pores by alternating current electrolysis in an acid solution of metal salts with the object itself as one of the electrodes while the other electrode or counterelectrode is formed of stainless steel or more often of the metal of the salt dissolved in the electrolyte, and then sealing the colored layer by immersion in boiling water.
- the electrolysis bath is formulated to contain dissolved nickel chloride as a component thereof whereby crystallization in the electrolyte does not occur at ambient temperature and polarization of the counter-electrode does not take place.
- the process applies to aluminum and its alloys.
- the object can be subjected to a surface treatment beforehand, depending upon the final appearance required. For example, a mat or dull appearance is obtained by pickling the object for 10 minutes at 50 C. in a 50 g./liter soda solution. The object is rinsed, immersed in nitric acid at 36 Be and then re-rinsed. A bright appearance is obtained either by mechanical polishing or by chemical or electrolytic brightening. A porous layer of alumina 1 to 50 microns thick is then formed on the object by any known means, for example anodization in a 50 g./ liter sulphuric or chromic acid bath using direct or alternating current. This layer is then colored using alternating current.
- the operating conditions are as follows:
- C0unter-electrode Electrical conditions Alternating current; Either at a constant density of from 0.1 to 5 A. etildmfl, preferably 0.1 to 1 A.
- efiJdmfl at a constant voltage of from 5 to v., preferably 7 to 30 v.; duration from 5 seconds to 20 minutes, preferably 1 to 10 minutes.
- a sheet of 99.5% pure aluminum which has been chemically brightened and anodized to a layer thickness of 10 microns in a chromic acid bath is colored by treatment with alternating current in a bath containing: g./liter of nickel sulphate, 10 g./1iter of ammonium sulphate, 20 g./liter of boric acid, 30 g./liter of nickel chloride, with a pH value of 4.55, a resistivity of 21.5 ohms cmP/cm. and with crystals at the bottom of the cell, at 20 C.
- Treatment was carried out with a voltage of 10 volts at a temperature of 22 C. for a period of 5 minutes with a ratio of surface area of component to surface area of counter-electrode of 3.
- the stainless steel counter-electrodes retain a clean appearance and the current density varies from 0.35 to 0.4 a. eif/dm. during the treatment.
- the treatment was carried out at C. at a current density of 0.4 a. eif./dm. for a period of three minutes with a ratio of surface area of component to surface area of counter-electrode of 2.
- the nickel counter-electrodes retain a clear appearance and the electrolysis voltage varies from 9 to 9.6 volts during the treatment. It is possible in this Way to obtain a bronze color finish which, after minutes sealing in boiling distilled water, containing 1 g./1iter of nickel acetate, is resistant both to corrosion and to ultra-violet rays.
- EXAMPLE 3 A piece of aluminum alloy section containing 0.5% of silicon and 0.5 of magnesium, which has been mechanically polished and anodized to a layer thickness of 12 microns in a sulphuric acid bath, is colored by treatment with alternating current in a bath containing: 100 g./liter of nickel sulphate, 30 g./liter of ammonium sulphate, 25 g./liter of boric acid and 200 g./liter of nickel chloride, with a pH value of 3.99 and a resistivity of 15.2 ohms cmF/cm. At 20 C. there are no crystals at the bottom of the cell.
- the treatment was carried out at 30 C. at a current density of 0.4 a. e1T./dm. for a period of 10 minutes with a ratio of surface area of component to surface area of counter-electrode of 2.
- the nickel counter-electrodes retain a clear appearance and the electrolysis voltage varies from 9 to 9.7 volts during the treatment. It is possible in this way to obtain a very deep bronze color finish which, after 30 minutes sealing in boiling distilled water, is resistant both to corrosion and to ultra-violet rays.
- EXAMPLE 4 A piece of a section of aluminum alloy containing 1% of silicon, 1% of magnesium and 1% of manganese, which has been satinized and anodized to a layer thickness of 5 microns in an alternating current sulphuric acid bath, is colored by treatment with alternating current in a bath containing: 75 g./liter of nickel sulphate, 20 g./liter of ammonium sulphate, g./liter of boric acid and 350 g./liter of nickel chloride, with a pH value of 3.6 and a resistivity of 14.8 ohms cmF/cm. At 20 C., there are no crystals at the bottom of the cell.
- the treatment was carried out for 10 minutes at 22 C. with a current density of 0.4 a. elf./dm. and a ratio of surface area of component to surface area of counterelectrode of 4.
- the stainless steel counter-electrodes retain a clean appearance and the electrolysis voltage remains constant at 9.6 volts, during the treatment. It is possible in this way to obtain a very deep bronze color finish which, after 30 minutes sealing in boiling distilled water, is resistant both to corrosion and to ultra-violet rays.
- this invention provides a new and improved electrolysis bath for the production of uniform bronze colors on aluminum and alloys of aluminum in a simple, efficient and reproducible manner.
- a process for producing colored surfaces of aluminum and alloys of aluminum comprising contacting an anodized surface of aluminum or alloy of aluminum as one of the electrodes with an electrolysis bath comprising an acidic solution of 5 to grams per liter hydrated nickel sulfate, 10 to 50 grams per liter ammonium sulfate and 50 to 250 grams per liter hydrated nickel chloride, and passing an alternating current between the electrodes.
- a process as claimed in claim 1 which includes the step of sealing the colored surface by immersion in boiling water.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR6924728A FR2052132A5 (enrdf_load_stackoverflow) | 1969-07-21 | 1969-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3704210A true US3704210A (en) | 1972-11-28 |
Family
ID=9037743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US55295A Expired - Lifetime US3704210A (en) | 1969-07-21 | 1970-07-15 | Process for coloring aluminum objects |
Country Status (12)
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3849264A (en) * | 1972-09-05 | 1974-11-19 | Lockheed Aircraft Corp | Production of stain resistant, clear, sealed anodized films |
| US3929593A (en) * | 1973-09-21 | 1975-12-30 | Riken Light Metal Ind Company | Method of forming colored oxide film on aluminum or aluminum alloy material |
| US4147598A (en) * | 1975-08-27 | 1979-04-03 | Riken Keikinzoku Kogyo Kabushiki Kaisha | Method for producing colored anodic oxide films on aluminum based alloy materials |
| US4179342A (en) * | 1978-06-28 | 1979-12-18 | Reynolds Metals Company | Coating system method for coloring aluminum |
| US4180443A (en) * | 1978-06-28 | 1979-12-25 | Reynolds Metals Company | Method for coloring aluminum |
| US20100183869A1 (en) * | 2009-01-16 | 2010-07-22 | Alcoa Inc. | Aluminum alloys, aluminum alloy products and methods for making the same |
| CN102304743A (zh) * | 2011-09-16 | 2012-01-04 | 南南铝业股份有限公司 | 一种铝及铝合金表面电化学氧化膜封孔方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5255601A (en) * | 1975-11-01 | 1977-05-07 | Sony Corp | Driving device for tone arm |
-
1969
- 1969-07-21 FR FR6924728A patent/FR2052132A5/fr not_active Expired
-
1970
- 1970-07-15 US US55295A patent/US3704210A/en not_active Expired - Lifetime
- 1970-07-16 NL NL7010552A patent/NL7010552A/xx unknown
- 1970-07-16 GB GB34473/70A patent/GB1292699A/en not_active Expired
- 1970-07-17 DE DE2035599A patent/DE2035599C3/de not_active Expired
- 1970-07-17 ES ES381942A patent/ES381942A1/es not_active Expired
- 1970-07-17 LU LU61358D patent/LU61358A1/xx unknown
- 1970-07-20 BE BE753706D patent/BE753706A/xx unknown
- 1970-07-20 CH CH1100470A patent/CH515338A/fr not_active IP Right Cessation
- 1970-07-20 CA CA088629A patent/CA926337A/en not_active Expired
- 1970-07-20 JP JP45062918A patent/JPS5015216B1/ja active Pending
- 1970-07-21 SE SE10074/70A patent/SE351441B/xx unknown
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3849264A (en) * | 1972-09-05 | 1974-11-19 | Lockheed Aircraft Corp | Production of stain resistant, clear, sealed anodized films |
| US3929593A (en) * | 1973-09-21 | 1975-12-30 | Riken Light Metal Ind Company | Method of forming colored oxide film on aluminum or aluminum alloy material |
| US4147598A (en) * | 1975-08-27 | 1979-04-03 | Riken Keikinzoku Kogyo Kabushiki Kaisha | Method for producing colored anodic oxide films on aluminum based alloy materials |
| US4179342A (en) * | 1978-06-28 | 1979-12-18 | Reynolds Metals Company | Coating system method for coloring aluminum |
| US4180443A (en) * | 1978-06-28 | 1979-12-25 | Reynolds Metals Company | Method for coloring aluminum |
| US20100183869A1 (en) * | 2009-01-16 | 2010-07-22 | Alcoa Inc. | Aluminum alloys, aluminum alloy products and methods for making the same |
| US8349462B2 (en) * | 2009-01-16 | 2013-01-08 | Alcoa Inc. | Aluminum alloys, aluminum alloy products and methods for making the same |
| US8950465B2 (en) | 2009-01-16 | 2015-02-10 | Alcoa Inc. | Aluminum alloys, aluminum alloy products and methods for making the same |
| CN102304743A (zh) * | 2011-09-16 | 2012-01-04 | 南南铝业股份有限公司 | 一种铝及铝合金表面电化学氧化膜封孔方法 |
| CN102304743B (zh) * | 2011-09-16 | 2014-04-02 | 南南铝业股份有限公司 | 一种铝及铝合金表面电化学氧化膜封孔方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5015216B1 (enrdf_load_stackoverflow) | 1975-06-03 |
| CH515338A (fr) | 1971-11-15 |
| CA926337A (en) | 1973-05-15 |
| DE2035599C3 (de) | 1973-12-13 |
| LU61358A1 (enrdf_load_stackoverflow) | 1971-07-13 |
| NL7010552A (enrdf_load_stackoverflow) | 1971-01-25 |
| GB1292699A (en) | 1972-10-11 |
| DE2035599A1 (de) | 1971-02-11 |
| BE753706A (fr) | 1971-01-20 |
| FR2052132A5 (enrdf_load_stackoverflow) | 1971-04-09 |
| DE2035599B2 (de) | 1973-05-24 |
| SE351441B (enrdf_load_stackoverflow) | 1972-11-27 |
| ES381942A1 (es) | 1973-04-01 |
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