EP0320952B1 - Procédé de coloration électrolytique de couches d'oxyde obtenus par voie anodique sur l'aluminium ou l'alliage de l'aluminium - Google Patents

Procédé de coloration électrolytique de couches d'oxyde obtenus par voie anodique sur l'aluminium ou l'alliage de l'aluminium Download PDF

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Publication number
EP0320952B1
EP0320952B1 EP88121038A EP88121038A EP0320952B1 EP 0320952 B1 EP0320952 B1 EP 0320952B1 EP 88121038 A EP88121038 A EP 88121038A EP 88121038 A EP88121038 A EP 88121038A EP 0320952 B1 EP0320952 B1 EP 0320952B1
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EP
European Patent Office
Prior art keywords
stage
current
alternating current
minutes
aluminium
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Expired - Lifetime
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EP88121038A
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German (de)
English (en)
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EP0320952A2 (fr
EP0320952A3 (en
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Josef Gartner and Co
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Josef Gartner and Co
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Priority to AT88121038T priority Critical patent/ATE89338T1/de
Publication of EP0320952A2 publication Critical patent/EP0320952A2/fr
Publication of EP0320952A3 publication Critical patent/EP0320952A3/de
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    • 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 anodically produced oxide layers on aluminum and aluminum alloys by means of alternating current in acidic electrolytes containing metal salt in two stages.
  • DE-B 22 08 315 shows such a method in which the direct current treatment under cathodic switching is carried out alternately at a current density of 0.2 to 2 A / dm 2 and the alternating current treatment at a voltage of 1 to 5 volts.
  • DE-C 24 44 398 shows such a method, in which pulsating direct current is applied in a sulfuric acid bath and the polarity of the pulse voltage applied to the aluminum parts is reversed after certain times which are longer than one pulse period.
  • DE-B 19 30 288 uses an asymmetrical alternating voltage composed of two half-wave trains obtained by appropriate rectification and separately regulated.
  • DE-B 26 09 146 shows the application of an anodic direct current treatment of the oxide layer in the dye bath before dyeing, whereupon the dyeing is then carried out with alternating current.
  • DE-C 25 38 622 shows dyeing with direct current, the material being anode with direct current in an anodic electrolytic bath, which is the same water-soluble, before dyeing in the electrolyte dye bath Metal ion as the electrolyte dye bath contains, is treated electrolytically.
  • DE-B 20 34 950 shows dyeing by means of alternating current superimposed on direct current at special temperatures and current densities, the direct current density being between 1/10 and 1/2 of the alternating current density, and circuit arrangements or systems for electrolytically coloring anodized aluminum, for example, show DE-B 26 07 543 and DE-C 29 41 191.
  • EP-A 0239 944 A1 uses an essentially positive voltage in the first stage and an asymmetrical alternating current in the second stage, the positive component now being smaller than the negative component.
  • US 44 21 610 also shows a two-stage process, in which two stages work with alternating current with a peak voltage between 55 and 85 volts and a current density of less than 0.3 A / dm 2, but the first stage is not in the dye bath but in a sulfuric acid bath of less than 4 g / l and then the workpiece is transferred to the dye bath.
  • the object of the invention is therefore a method by which the coloring over the entire workpiece, in particular in the case of irregularly shaped workpieces, becomes more uniform, which therefore brings about better scattering.
  • Such dyeings which are carried out with various metal salts that can be separated in the strongly acidic range, in particular tin and copper, are used particularly frequently in facade construction, where very irregularly shaped profiles of sometimes considerable length and large areas are to be colored very uniformly. above all, there are still considerable problems with the uniformity of the color.
  • the invention thus relates to a process for the electrolytic coloring of anodic oxide layers on aluminum or its alloys by means of alternating current in acidic electrolytes containing metal salt in two stages, a modified alternating current being applied in the first stage, in which the ratio of the anodic portion to the cathodic portion 10 : 1 to 50: 1 and alternating current is applied in the second stage, and a pause of 10 to 60 seconds is taken between the two treatment stages, in the second stage a longer time and / or at a higher voltage than in the first stage is worked.
  • the first stage 0.5 to 5 minutes with voltages of 5 to 20 V and current densities of 0.2 to 2 A / dm 2 and in the second stage 0.5 to 15 minutes at a voltage of 15 to 25 V, an initial current density of 0.2 to 1.2 A / dm2 and a final current density of 0.05 to 0.5 A / dm2 and a break of 20 to 50 seconds.
  • the ratio of the initial current density to the final current density is preferably 4: 1 to 8: 1.
  • the duration of the first stage is 1 to 4 minutes at voltages from 6 to 20, in particular 8 to 18 volts and current densities from 0.4 to 1.2 A / dm 2.
  • the pause can be 10 to 60 seconds, but the above 20 to 50 seconds are preferred.
  • the AC treatment lasts in particular 1 to 12 minutes, with a voltage of in particular 16-22 volts at the initial and final current densities already mentioned.
  • the ratio between the initial current density and the final current density in the second step can also be higher than the preferred ratio of 4: 1 to 8: 1 mentioned.
  • the modified alternating current is such that the ratio of the anodic component to the cathodic component (i.e. the integral of the wave above the zero line or below the zero line) is approximately 10: 1 to 50: 1, in particular 20-40: 1.
  • Such alternating currents can be obtained technically via a thyristor with a suitable circuit.
  • the treatment times depend on the desired shade, whereby the times for the modified AC treatment hardly change, but those for the AC treatment do.
  • tin staining with 2 minutes of modified AC treatment and 0.5 minutes of AC treatment results in champagne staining, while with 12 minutes of AC treatment, it turns black.
  • the pause between treatments is 40 seconds.
  • the pretreatment with the modified alternating current has no significant oxidation effect. Obviously, it causes an activation of the surface to be colored, but only a very limited oxidation, which is particularly evident when coloring with tin, where hardly any tin dioxide is formed. It is also unclear why there should be a break between the two treatment stages, but the results will be significantly worse without this break.
  • the experimental set-up according to the attached FIG. 6 was used to measure the effect.
  • One of the profile developments shown in FIGS. 7a and 7b was placed in the middle of the circuit.
  • Profile processing 7a had a processing length of 230 mm and an area of 9.1 dm 2 at a length of 400 mm
  • profile processing 7b had a processing length of 145 mm and an area of 5.8 dm 2 at a length of 400 mm.
  • the counter electrode was made of 4301 stainless steel and dipped into the bathroom at one end.
  • the composition of the dye bath was as follows: 8.5 g / l Sn (approx. 16 g / l SnSo4) 24 g / l H2SO4 conc.
  • the bath also contained the stabilizers customary for such baths (in the present case, the products from Bihlmaier, which are well known under the order numbers KBEL2 and KBEL3) in the usual quantities, which are also well known (10 ml / l KBEL3 and 20 ml / l KBEL2).
  • the bath temperature was around 20 ° C.
  • the piece was colored under the conditions given in the following examples using the current curves shown in the accompanying figures. After dyeing, a reflection measurement was carried out using three measuring points according to the experimental setup.
  • the reflectometer (TYPUME1 from Dr. Lange, Berlin) was set to 100 at measuring point 2, which was closest to the power supply, and then the two ends, measuring points 1 and 3, were measured.
  • the difference between the final measuring points and the O point (measuring point 2) or, if this value was larger, between measuring points 1 and 3 was expressed in points. The smaller the difference, the more uniform the coloring and thus the better the scatter.
  • a scatter value of at most 10 points was considered to be still satisfactory for this test arrangement.
  • a scatter value of less than 5 points can no longer be distinguished with the unarmed eye.
  • Example 1 a (Fig. 1a) profile a
  • the example was repeated with profile 1b, working for 16 minutes at 16 V and 2 A in the first stage and after a break of 40 seconds in the second stage for 4 minutes at 19 V and an initial current of 2 A and a final current of 0 , 5 A was worked.
  • the reflection measurement gave a value of 107 for point 1 and a value of 101 for point 3, i.e. a scatter of 7 points.
  • the example was repeated with profile 1b, working in step 1 for 2 minutes at 12.5 V and 2.5 A and after a break of 40 seconds for 4 minutes at 19 V with an initial current of 2 A and a final current of 0. 5 A was worked.
  • the reflection measurement gave a value of 103 for point 1 and a value for 101 for point 3, i.e. a scatter of 3 points.
  • the example was repeated with profile 1b, working in the first stage for 2 minutes at 9 V and 2A and after a 40 second pause in the second stage for 4 minutes at 19 V with an initial current of 2A and a final current of 0.5 A was worked on.
  • the result was 103 points for measuring point 1 and 102 for measuring point 3, ie a scatter of 3 points.
  • the reflection measurement in which measuring point 2 was set to 100, gave a value of 92 for point 1 and for point 3 a value of 115, so that the scatter is 15 points to the O value, but a total of 23 points, which gives a clear difference in color between the beginning and end of the sheet.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Spectrometry And Color Measurement (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Drawing Aids And Blackboards (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (3)

  1. Procédé de coloration électrolytique de couches d'oxyde anodiques sur l'aluminium ou des alliages de ce dernier au moyen de courant alternatif dans des électrolytes acides contenant du sel métallique en deux étapes, où durant la première étape un courant alternatif modifié est appliqué, pour lequel le rapport de la part anodique par rapport à la part cathodique varie de 10 : 1 à 50 : 1 et où durant la seconde étape un courant alternatif est appliqué et une pause de 10 à 60 secondes est respectée entre les deux étapes de traitement, où durant la seconde étape le traitement se fait pendant un temps plus long et/ou sous une tension plus élevée que durant la première étape.
  2. Procédé selon la revendication 1, caractérisé en ce que le traitement se fait durant la première étape pendant 0,5 à 5 minutes avec des tensions de 5 à 20V et des densités de courant de 0,2 à 2 A/dm² et durant la seconde étape pendant 0,5 à 15 minutes sous une tension de 15 à 25V, une densité initiale de courant de 0,2 à 1,2 A/dm² et une densité finale de courant de 0,05 à 0,5 A/dm² et avec une pause de 20 à 50 secondes.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que durant la première étape le rapport entre la densité initiale de courant et la densité finale de courant varie de 4 : 1 à 8 : 1.
EP88121038A 1987-12-18 1988-12-15 Procédé de coloration électrolytique de couches d'oxyde obtenus par voie anodique sur l'aluminium ou l'alliage de l'aluminium Expired - Lifetime EP0320952B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88121038T ATE89338T1 (de) 1987-12-18 1988-12-15 Verfahren zum elektrolytischen faerben von anodisch erzeugten oxidschichten auf aluminium und aluminiumlegierungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873743113 DE3743113A1 (de) 1987-12-18 1987-12-18 Verfahren zum elektrolytischen faerben von anodisch erzeugten oxidschichten auf aluminium und aluminiumlegierungen
DE3743113 1987-12-18

Publications (3)

Publication Number Publication Date
EP0320952A2 EP0320952A2 (fr) 1989-06-21
EP0320952A3 EP0320952A3 (en) 1990-01-31
EP0320952B1 true EP0320952B1 (fr) 1993-05-12

Family

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EP88121038A Expired - Lifetime EP0320952B1 (fr) 1987-12-18 1988-12-15 Procédé de coloration électrolytique de couches d'oxyde obtenus par voie anodique sur l'aluminium ou l'alliage de l'aluminium

Country Status (3)

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EP (1) EP0320952B1 (fr)
AT (1) ATE89338T1 (fr)
DE (2) DE3743113A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0487754A1 (fr) * 1990-11-25 1992-06-03 BEFELD SYSTEME GmbH Procédé de coloration électrolytique de couches d'oxyde obtenues par voie anodique sur l'aluminium et d'alliages de l'aluminium
ES2052455B1 (es) * 1992-12-31 1994-12-01 Novamax Tech Holdings Procedimiento para la obtencion por via electrolitica sobre aluminio anodizado de una gama de colores del espectro visible.

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1902983C3 (de) * 1968-06-21 1978-06-22 Keller, Eberhard, 7121 Freudental Verfahren zum elektrolytischen Färben von anodischen Oxidschichten auf Aluminium oder Aluminiumlegierungen
FR2052100A5 (fr) * 1969-07-16 1971-04-09 Cegedur Gp
JPS5014623B1 (fr) * 1971-02-22 1975-05-29
JPS547267B2 (fr) * 1973-09-21 1979-04-05
JPS5423664B2 (fr) * 1975-03-06 1979-08-15
ES437604A1 (es) * 1975-05-12 1977-01-16 Empresa Nacional Aluminio Sistema de autocontrol y regulacion del valor medio de la tension aplicada en procesos de coloracion electrolitica de aluminio anodizado.
ES474736A1 (es) * 1978-10-31 1979-04-01 Empresa Nacional Aluminio Sistema de generacion y autocontrol de la forma de onda y - tension o corriente aplicable a procesos de coloracion elec-trolitica del aluminio anodizado.
ES8205885A2 (es) * 1979-07-04 1982-08-01 Empresa Nacional Aluminio Mejoras introducidas en el objeto de la patente principal por proceso para la coloracion electrolitica del aluminio a-nodizado.
ES8201232A1 (es) * 1981-01-16 1981-12-01 Ronain Sa Procedimiento de coloracion por via electrolitica de una pieza de aluminio o de aleacion de aluminio
US4808280A (en) * 1986-04-01 1989-02-28 Fujisash Company Method for electrolytic coloring of aluminim or aluminum alloys
DE3777806D1 (de) * 1987-01-16 1992-04-30 Alusuisse Lonza Services Ag Verfahren zum elektrolytischen faerben einer anodischen oxidschicht auf aluminium oder aluminiumlegierungen.

Also Published As

Publication number Publication date
DE3743113A1 (de) 1989-06-29
ATE89338T1 (de) 1993-05-15
EP0320952A2 (fr) 1989-06-21
DE3743113C2 (fr) 1992-05-07
DE3880990D1 (de) 1993-06-17
EP0320952A3 (en) 1990-01-31

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