EP0011097B1 - Verfahren zur elektrolytischen Färbung von auf Aluminium erzeugten anodischen Oxidschichten - Google Patents
Verfahren zur elektrolytischen Färbung von auf Aluminium erzeugten anodischen Oxidschichten Download PDFInfo
- Publication number
- EP0011097B1 EP0011097B1 EP79103288A EP79103288A EP0011097B1 EP 0011097 B1 EP0011097 B1 EP 0011097B1 EP 79103288 A EP79103288 A EP 79103288A EP 79103288 A EP79103288 A EP 79103288A EP 0011097 B1 EP0011097 B1 EP 0011097B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- tin
- iron
- sulfuric acid
- electrolyte
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000010407 anodic oxide Substances 0.000 title claims description 3
- 239000004411 aluminium Substances 0.000 title claims 2
- 238000004040 coloring Methods 0.000 title abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 7
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 7
- GVOUROSDBUODMG-UHFFFAOYSA-L iron(2+);3-sulfophthalate Chemical compound [Fe+2].OS(=O)(=O)C1=CC=CC(C([O-])=O)=C1C([O-])=O GVOUROSDBUODMG-UHFFFAOYSA-L 0.000 claims description 3
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 claims 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 40
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003929 acidic solution Substances 0.000 abstract description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 14
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 6
- 229940044654 phenolsulfonic acid Drugs 0.000 description 6
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- LPARUNFRVILVRU-UHFFFAOYSA-L iron(2+);2-sulfooxybenzoate Chemical compound [Fe+2].OS(=O)(=O)OC1=CC=CC=C1C([O-])=O.OS(=O)(=O)OC1=CC=CC=C1C([O-])=O LPARUNFRVILVRU-UHFFFAOYSA-L 0.000 description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXPDAXLODHMVDJ-UHFFFAOYSA-L sulfuric acid tin(2+) sulfate Chemical compound [Sn+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O VXPDAXLODHMVDJ-UHFFFAOYSA-L 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical class [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- RAZPXVHCSOQXHL-UHFFFAOYSA-J sulfuric acid;tin(4+);disulfate Chemical compound [Sn+4].OS(O)(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RAZPXVHCSOQXHL-UHFFFAOYSA-J 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 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
- the invention relates to a process for the electrolytic coloring of anodic oxide layers produced on aluminum by means of direct current in acidic solution by means of alternating current using an acid electrolyte containing tin (II) salts and iron (II) salts.
- the so-called electrolytic metal salt coloring a defined oxide layer is generated in the first process step using direct current with sulfuric acid or sulfuric acid and oxalic acid as the electrolytic liquid.
- the aluminum thus anodized is then electrolytically colored in a second process step using alternating current and using solutions of certain metal salts or metal salt mixtures, tin (II) and iron (II) sulfate-containing solutions preferably being used here.
- the invention has for its object to prevent the formation of precipitates when standing in the electrolytes used for coloring, which contain tin (II) salts, and at the same time to find electrolytes which enable the coloring to be obtained with the highest possible color intensity.
- the hydrocarbon radical connected to the sulfur atom which may contain up to 8 carbon atoms, inclusive, does not play a decisive role.
- the hydrocarbon radical can be an optionally substituted alkyl, aryl or alkaryl radical.
- Example 2 The procedure was analogous to Example 1, with a solution containing 14 g of tin (II) sulfate, 16 g of conc. Contained sulfuric acid and 10 g of aminoethylethanolamine / I was used.
- Example 2 The procedure was analogous to Example 1, with a solution containing 14 g of tin (II) sulfate, 16 g of conc. Containing sulfuric acid, 10 g phenolsulfonic acid and 5 g iron (II) sulfamate / I was used.
- the brightness determined using the colorimeter was 15.8.
- the amount of precipitation of 200 ml of this solution was 66 mg after standing for 1 week.
- the brightness determined using the colorimeter was 16.5.
- the amount of precipitation of 200 ml of this solution was 420 mg after standing for 1 week.
- the brightness determined using the colorimeter was 13.8.
- the amount of precipitation of 200 ml of this solution was 8 mg after standing for 1 week.
- Example 2 The procedure was analogous to Example 1, with a solution containing 14 g of tin (11) sulfate, 16 g of conc. Contains sulfuric acid and 10 g cresolsulfonic acid / I was used.
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)
- Electrolytic Production Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Secondary Cells (AREA)
- Electroplating Methods And Accessories (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT79103288T ATE87T1 (de) | 1978-11-18 | 1979-09-05 | Verfahren zur elektrolytischen faerbung von auf aluminium erzeugten anodischen oxidschichten. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2850136 | 1978-11-18 | ||
| DE2850136A DE2850136B2 (de) | 1978-11-18 | 1978-11-18 | Verfahren zur elektrolytischen Färbung von auf Aluminium erzeugten anodischen Oxidschichten |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0011097A2 EP0011097A2 (de) | 1980-05-28 |
| EP0011097A3 EP0011097A3 (en) | 1980-06-11 |
| EP0011097B1 true EP0011097B1 (de) | 1981-06-17 |
Family
ID=6055052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79103288A Expired EP0011097B1 (de) | 1978-11-18 | 1979-09-05 | Verfahren zur elektrolytischen Färbung von auf Aluminium erzeugten anodischen Oxidschichten |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4401525A (da) |
| EP (1) | EP0011097B1 (da) |
| AT (1) | ATE87T1 (da) |
| BR (1) | BR7906756A (da) |
| DE (1) | DE2850136B2 (da) |
| DK (1) | DK486579A (da) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3718849A1 (de) * | 1987-06-05 | 1988-12-15 | Henkel Kgaa | Elektrolytisches einfaerben von anodisiertem aluminium |
| DE3824403A1 (de) * | 1988-07-19 | 1990-01-25 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur elektrolytischen metallsalzeinfaerbung von anodisierten aluminiumoberflaechen |
| GB9825043D0 (en) * | 1998-11-16 | 1999-01-13 | Agfa Gevaert Ltd | Production of support for lithographic printing plate |
| EP3553208A1 (de) * | 2018-04-09 | 2019-10-16 | DURA Operating, LLC | Verfahren zum herstellen eines aluminiumbauteils mit einer farbigen oberfläche |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5423662B2 (en) * | 1975-03-05 | 1979-08-15 | Yoshida Kogyo Kk | Aruminiumu mataha aruminiumugokinno goorudoshokuhenodenkaichakushokuho |
| JPS5423663B2 (da) * | 1975-03-06 | 1979-08-15 | ||
| JPS5296940A (en) * | 1976-02-10 | 1977-08-15 | Mitsui Keikinzoku Kako | Electrolytic pigmentation process for aluminum or its alloy |
| JPS5318438A (en) * | 1976-08-04 | 1978-02-20 | Mitsui Keikinzoku Kako | Process for forming electrolytic pigmentation coatings on aluminum and aluminum alloy |
| FR2384037A1 (fr) * | 1977-03-17 | 1978-10-13 | Nice Anodisation Sa | Perfectionnement au procede de coloration electrolytique de l'aluminium et de ses alliages |
-
1978
- 1978-11-18 DE DE2850136A patent/DE2850136B2/de not_active Ceased
-
1979
- 1979-09-05 AT AT79103288T patent/ATE87T1/de active
- 1979-09-05 EP EP79103288A patent/EP0011097B1/de not_active Expired
- 1979-10-19 BR BR7906756A patent/BR7906756A/pt not_active IP Right Cessation
- 1979-11-14 US US06/093,990 patent/US4401525A/en not_active Expired - Lifetime
- 1979-11-16 DK DK486579A patent/DK486579A/da not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US4401525A (en) | 1983-08-30 |
| EP0011097A2 (de) | 1980-05-28 |
| DE2850136A1 (de) | 1980-05-22 |
| DK486579A (da) | 1980-05-19 |
| DE2850136B2 (de) | 1981-01-22 |
| BR7906756A (pt) | 1980-06-03 |
| EP0011097A3 (en) | 1980-06-11 |
| ATE87T1 (de) | 1981-07-15 |
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