EP0351680B1 - Verwendung von p-Toluolsulfonsäure zum elektrolytischen Färben anodisch erzeugter Oberflächen von Aluminium - Google Patents
Verwendung von p-Toluolsulfonsäure zum elektrolytischen Färben anodisch erzeugter Oberflächen von Aluminium Download PDFInfo
- Publication number
- EP0351680B1 EP0351680B1 EP89112555A EP89112555A EP0351680B1 EP 0351680 B1 EP0351680 B1 EP 0351680B1 EP 89112555 A EP89112555 A EP 89112555A EP 89112555 A EP89112555 A EP 89112555A EP 0351680 B1 EP0351680 B1 EP 0351680B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ammonium
- alkaline earth
- salts
- alkali metal
- earth metal
- 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004040 coloring Methods 0.000 title claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000004411 aluminium Substances 0.000 title claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 alkaline earth metal salts Chemical class 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 229940021013 electrolyte solution Drugs 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 11
- 229910000367 silver sulfate Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000010930 yellow gold Substances 0.000 description 6
- 229910001097 yellow gold Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- 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 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000012928 buffer substance Substances 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 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
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 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
- C25D11/14—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
- 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 the electrolytic coloring of anodically produced surfaces of aluminum and / or aluminum alloys in aqueous electrolytes containing silver salt by means of alternating current and using p-toluenesulfonic acid.
- Chemical Abstracts 105 (10), Unit 87 431z, discloses the electrolytic coloring of aluminum using an electrolyte containing silver nitrate and sulfuric acid. The coloring process was used for the surface treatment of lamps and aluminum workpieces. It is described that the problems that usually arise from dyeing with organic dyes are solved.
- JP-A 55-131195 describes the electrolytic coloring of aluminum with a number of metal salts.
- said electrolytic coloring is carried out.
- Metal Finishing Abstracts, Vol 23 (1981), No. 1, page 25 F also describes a process for the electrolytic coloring of anodized aluminum, in which an electrolysis bath, the salts of nickel Contains cobalt, tin or copper in the form of sulfate, sulphamate, oxalate, tartrate or phosphate.
- the bath also contains 5 to 100 g / l p-toluenesulfonate sodium salt or similar compounds and unsaturated compounds, for example formaldehyde, benzylidene acetone, pyridine, quinoline, butynediol, ethylene cyanohydrin, thiourea or azo dyes.
- the coloring tape contains a silver salt, for example 0.5 g / l silver sulfate and 1 g / l tin sulfate, 20 g / l sulfosalicylic acid, 20 g / l magnesium sulfate and 10 g / l sulfuric acid.
- a silver salt for example 0.5 g / l silver sulfate and 1 g / l tin sulfate, 20 g / l sulfosalicylic acid, 20 g / l magnesium sulfate and 10 g / l sulfuric acid.
- the aluminum treated in this way is then immersed in an acidic bath containing, for example, sulfuric acid or nitric acid, or in a neutral bath containing, for example, thiosulfate or thiogluconate. This results in permanent and light-colored layers, for example light-orange colored layers.
- the invention thus relates to the use of p-toluenesulfonic acid and / or its water-soluble alkali metal, ammonium and / or alkaline earth metal salts for the electrolytic coloring of anodized surfaces of aluminum and / or aluminum alloys, which is characterized in that aqueous electrolyte solutions are used, the 0 , Contain 1 to 10 g / l silver in the form of water-soluble salts, and apply alternating current or alternating current superimposed on direct current.
- the electrolytic coloring according to the invention also has the decorative effect has the advantage that it can be easily and permanently over-dyed with organic dyes and so, for example, with dyes such as Sanodalblau R from Sandoz AG, Basel, Switzerland, a lightfast green can also be achieved as a combination dyeing.
- p-toluenesulfonic acid also includes their water-soluble alkali metal salts and / or their water-soluble alkaline earth metal salts.
- p-toluenesulfonic acid is used in the form of the monohydrate because of its better solubility in water.
- p-toluenesulfonic acid is used in an amount of 3 to 100 g / l electrolytic solution, while a preferred embodiment of the present invention consists in using 5 to 25 g / l p-toluenesulfonic acid.
- the electrolytic solution contains the silver in the form of nitrate, acetate and / or sulfate.
- the electrolyte solution contains 0.3 to 1.2 g / l of silver in the form of water-soluble salts, preferably in the form of nitrate, acetate and / or sulfate.
- the use of silver sulfate is preferred.
- a further embodiment of the present invention consists in that the electrolyte solution, if desired, 2.5 to 100 g / l sulfuric acid and / or its alkali metal, ammonium and / or contains alkaline earth metal salts.
- a particular embodiment of the present invention is that an electrolyte solution is used which contains 2.5 to 25 g / l sulfuric acid.
- the alkali metal, ammonium and / or alkaline earth metal salts which can be used instead of or together with this are those of sodium, potassium, ammonium, magnesium or mixtures thereof, preferably in the form of the sulfates and / or the acetates.
- magnesium sulfate together with or instead of the sulfuric acid is particularly preferred.
- a terminal voltage of 4 to 20 V is set according to the invention.
- a preferred embodiment of the present invention is to set the terminal voltage in the range from 8 to 16 V.
- Alternating current or alternating current superimposed with direct current is used.
- the "alternating current superimposed with direct current” is equivalent to "direct current superimposed with alternating current”.
- the voltage applied to the bath is defined as the terminal voltage.
- the generation of gold tones is preferred within the scope of the invention. These preferably result in a voltage range of 8 to 16 V, the treatment times should be shorter the higher the voltage is selected. In this sense, the treatment times are usually in the range of 0.5 to 3 minutes.
- brown tones result in dyeing times of more than 3 min and higher voltage values, i.e. especially more than 10 V.
- Voltage values of more than 16 V should generally be avoided with dyeing times of more than 3 minutes, since otherwise the oxide layer may flake off.
- Electrolyte solutions which contain further cations can also be used within the scope of the invention. Preferred as such are: Cu (II), Ni (II) and Co (II). This results in a wide range of other warm colors.
- test sheets (dimension 50 mm x 40 mm x 1 mm) made of the material Almg 1 (DIN material no. 3.3315) were used.
- the sheets were degreased, pickled and pickled using conventional methods.
- the degreasing was carried out with an alkaline cleaner containing borates, carbonates, phosphates and nonionic surfactants (P3-almeco R 18, Henkel KGaA, Düsseldorf), bath concentration 5% by weight at 70 ° C. in the course of 15 minutes.
- a mixture (3: 1) of sodium hydroxide and a pickling agent containing alkali, alcohols and salts of inorganic acids (P3-almeco R 46, Henkel KGaA, Duesseldorf) was used.
- the pickling was carried out using an acidic pickling agent containing salts of inorganic acids and inorganic acids (P3-almeco R 90, Henkel KGaA, Düsseldorf), in a concentration of 15% by weight, at a temperature of 20 ° C. in the course of 3 minutes .
- P3-almeco R 90 Henkel KGaA, Düsseldorf
- the subsequent anodization was carried out using the direct current sulfuric acid method; Bath composition: 180 g / l sulfuric acid, 10 g / l aluminum, air injection: 8 m3 / m2h, temperature: 20 ° C, DC voltage 15 V, current density 1.4 A / dm2, anodizing time: 2700 to 3600 sec, depending on the requirements for the production of a constant oxide layer of 20 ⁇ m.
- the sheets were then rinsed again and subjected to a compression process. At a temperature of about 98 ° C in the course of 60 min. (corresponding to 3 min./ ⁇ m) the compression.
- a sealing coating inhibitor based on polycarboxylic acids and ammonium acetate was used as a buffer substance (P3-almeco R seal SL, Henkel KGaA, Düsseldorf).
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)
- Electrochemical Coating By Surface Reaction (AREA)
- Electrolytic Production Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Detergent Compositions (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT89112555T ATE82022T1 (de) | 1988-07-19 | 1989-07-10 | Verwendung von p-toluolsulfonsaeure zum elektrolytischen faerben anodisch erzeugter oberflaechen von aluminium. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3824402 | 1988-07-19 | ||
| DE3824402A DE3824402A1 (de) | 1988-07-19 | 1988-07-19 | Verwendung von p-toluolsulfonsaeure zum elektrolytischen faerben anodisch erzeugter oberflaechen von aluminium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0351680A1 EP0351680A1 (de) | 1990-01-24 |
| EP0351680B1 true EP0351680B1 (de) | 1992-11-04 |
Family
ID=6358983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89112555A Expired - Lifetime EP0351680B1 (de) | 1988-07-19 | 1989-07-10 | Verwendung von p-Toluolsulfonsäure zum elektrolytischen Färben anodisch erzeugter Oberflächen von Aluminium |
Country Status (12)
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4244021A1 (de) * | 1992-12-24 | 1994-06-30 | Henkel Kgaa | Verfahren zur elektrolytischen Wechselstromeinfärbung von Aluminiumoberflächen |
| DE10033434A1 (de) | 2000-07-10 | 2002-01-24 | Basf Ag | Verfahren zur Herstellung von goldfarbenen Oberflächen von Aluminium oder Aluminium-Legierungen mittels silbersalzhaltigen Formulierungen |
| CN102808208B (zh) * | 2012-08-29 | 2013-07-24 | 广东豪美铝业股份有限公司 | 一种铝材着金色的方法 |
| KR101890681B1 (ko) | 2016-12-27 | 2018-09-28 | 엘에스산전 주식회사 | 기중 차단기의 위치표시장치 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5249408B2 (enrdf_load_stackoverflow) * | 1972-11-21 | 1977-12-17 | ||
| JPS547267B2 (enrdf_load_stackoverflow) * | 1973-09-21 | 1979-04-05 | ||
| US4128460A (en) * | 1976-09-13 | 1978-12-05 | Daiwa Kasei Kenkyujo Kabushiki Kaisha | Coloring by electrolysis of aluminum or aluminum alloys |
| FR2380357A1 (fr) * | 1977-02-11 | 1978-09-08 | Pechiney Aluminium | Procede de coloration electrolytique de l'aluminium et de ses alliages non anodises |
| US4226680A (en) * | 1977-06-06 | 1980-10-07 | Alcan Research And Development Limited | Process for electrolytic coloration of anodized aluminium |
| JPS55131195A (en) * | 1979-03-30 | 1980-10-11 | Sumitomo Light Metal Ind Ltd | Electrolytic coloring method for aluminum |
| US4430169A (en) * | 1982-03-04 | 1984-02-07 | Woods Jack L | Method of producing green coatings on aluminum and aluminum alloys |
-
1988
- 1988-07-19 DE DE3824402A patent/DE3824402A1/de not_active Withdrawn
-
1989
- 1989-07-10 AT AT89112555T patent/ATE82022T1/de not_active IP Right Cessation
- 1989-07-10 DE DE8989112555T patent/DE58902601D1/de not_active Expired - Fee Related
- 1989-07-10 ES ES198989112555T patent/ES2035994T3/es not_active Expired - Lifetime
- 1989-07-10 EP EP89112555A patent/EP0351680B1/de not_active Expired - Lifetime
- 1989-07-18 BR BR898903540A patent/BR8903540A/pt unknown
- 1989-07-18 NZ NZ229977A patent/NZ229977A/en unknown
- 1989-07-18 AU AU38244/89A patent/AU609320B2/en not_active Ceased
- 1989-07-18 KR KR1019890010185A patent/KR900001886A/ko not_active Ceased
- 1989-07-18 ZA ZA895471A patent/ZA895471B/xx unknown
- 1989-07-19 JP JP1187235A patent/JPH0273993A/ja active Pending
- 1989-07-19 US US07/382,611 patent/US4917780A/en not_active Expired - Fee Related
-
1992
- 1992-11-05 GR GR920402464T patent/GR3006151T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA895471B (en) | 1990-03-28 |
| ATE82022T1 (de) | 1992-11-15 |
| ES2035994T3 (es) | 1993-05-01 |
| EP0351680A1 (de) | 1990-01-24 |
| DE58902601D1 (de) | 1992-12-10 |
| AU609320B2 (en) | 1991-04-26 |
| BR8903540A (pt) | 1990-03-13 |
| US4917780A (en) | 1990-04-17 |
| KR900001886A (ko) | 1990-02-27 |
| JPH0273993A (ja) | 1990-03-13 |
| DE3824402A1 (de) | 1990-01-25 |
| GR3006151T3 (enrdf_load_stackoverflow) | 1993-06-21 |
| AU3824489A (en) | 1990-01-25 |
| NZ229977A (en) | 1990-08-28 |
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