EP0113862A1 - Electrolytic colouring - Google Patents
Electrolytic colouring Download PDFInfo
- Publication number
- EP0113862A1 EP0113862A1 EP83112387A EP83112387A EP0113862A1 EP 0113862 A1 EP0113862 A1 EP 0113862A1 EP 83112387 A EP83112387 A EP 83112387A EP 83112387 A EP83112387 A EP 83112387A EP 0113862 A1 EP0113862 A1 EP 0113862A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- coloring
- aluminum
- color
- dye component
- 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
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- 238000004040 coloring Methods 0.000 title claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 239000000975 dye Substances 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 9
- 239000003086 colorant Substances 0.000 claims abstract description 8
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 5
- 238000010348 incorporation Methods 0.000 claims description 4
- 239000000987 azo dye Substances 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910000906 Bronze Inorganic materials 0.000 description 4
- 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
- 239000000956 alloy Substances 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 238000007743 anodising Methods 0.000 description 1
- -1 azo compound Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 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 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- OIZJPMOIAMYNJL-UHFFFAOYSA-H gold(3+);trisulfate Chemical compound [Au+3].[Au+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OIZJPMOIAMYNJL-UHFFFAOYSA-H 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-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
- C25D11/18—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 coloring electrolyte for the electrolytic coloring of anodically produced oxide layers on aluminum and aluminum alloys in colors of different colors and brightness, in particular for use in profiles for window, door, facade elements and the like.
- Electrochemical dyebaths for coloring anodically produced oxide layers on aluminum and its alloys which contain a metal salt for coloring the oxide layer.
- a defined oxide layer is generated on the surface of the aluminum or aluminum alloys by means of direct current in, for example, sulfuric acid solution, and this is then colored by means of alternating current using a weakly acidic coloring electrolyte.
- the coloring electrolyte often contains a sulfate, for example of iron, nickel or cobalt, which produces a bronze tone with a certain color cast.
- bronze coloring can only be created by adding them in the electrochemical dyebath in the form of copper sulfate - which creates a reddish tinge to the oxide layer -, silver sulfate or gold sulfate, which results in a bluish or yellowish tint in the oxide layer comes about.
- gold and silver salts are mostly not justifiable for economic reasons, different bronze tones often result with the same dye bath composition and the same treatment sequence, which has a particularly disadvantageous effect if a larger number of aluminum profiles are colored and the profiles used next to each other visually leave an uneven color impression.
- the object of the invention is to provide a coloring electrolyte of the type mentioned at the outset, with which it is possible to color anodized layers of aluminum and aluminum alloys in an economically justifiable manner in terms of color and brightness with appropriate selection.
- the coloring electrolyte contains an organic dye component in addition to a metal salt.
- the hue produced by the metal salt can be overlaid with a suitable selection of the organic dye component such that a desired color is produced.
- an achromatic color on the surface of the aluminum or aluminum alloy In many cases, for example, it is desirable to produce an achromatic color on the surface of the aluminum or aluminum alloy.
- the laws of color mixing can be applied, the mixing of two complementary colors or the additive color mixing with a given color valence then giving rise to an achromatic color using a compensating color.
- the dye component contained in the electrolyte in addition to the metal salt contains the spectral color violet-blue. This creates the achromatic color "gray” on aluminum oxide layers, because the "bronze” color produced by electrochemical metal deposition is neutralized to a certain extent by the "violet-blue” color applied by electrosorptive.
- a metal dye-containing azo dye is preferably used as the organic dye component.
- the electrolyte is preferably adjusted to a pH of pH 4 to pH 5. Alternating current is used as the voltage source for the deposition of the metal and the incorporation of the metal complex-containing azo dye.
- a nitrogen compound is preferably added to the coloring electrolyte.
- a nitrogen compound could be, for example, a sulfate that contains nitrogen in its compound.
- the objects made from aluminum or its alloys are first subjected to anodic oxidation in a known manner, using direct current in a solution suitable for electrolysis - such as sulfur, oxal or chromic acid - a defined oxide layer is generated and this is then colored in the weakly acidic coloring electrolyte with the supply of alternating current.
- a solution suitable for electrolysis - such as sulfur, oxal or chromic acid -
- the coloring electrolyte may contain cobalt sulfate as the metal salt and an azo compound containing chromium complex as the organic dye component. If an electrical alternating voltage is applied to these coloring electrolytes, the metal complex-containing dye and the cobalt ions migrate into the micropores of the aluminum oxide layer under the influence of the electrical field, the cobalt ions at the pore base being reduced to metal.
- the organic dye is deposited deeper in the pores than is the case with purely adsorptive coloring.
- the first treatment stage is the pretreatment of the objects made of aluminum or its alloys with subsequent anodic oxidation
- the second treatment stage is represented by the coloring of the oxide layer in a coloring electrolyte.
- the alloy and the condition of the anodized semi-finished products, their degree of gloss or mattness of the surface as well as the electrolyte composition and the working conditions during the anodizing process can be considered as influencing variables
- the influencing variables in the second treatment stage are the composition of the coloring electrolyte and its pH - View value, temperature, dwell time and current density.
- an extruded profile of the aluminum alloy AlMgSi o. 5 medium gray corresponding to the darkness D 4.5 of DIN sheet 6164, supplementary sheet 25, is to be colored
- the extruded profile is first degreased, pickled and anodized using known methods.
- the electrolyte causing the anodic oxidation contains 19o g sulfuric acid per 1 1 water (19o g / 1 H 2 SO 4 ) and 10 g aluminum per 1 1 electrolyte (10 g / l).
- the temperature of the electrolyte intended for anodization is 20 ° C, while the current density should be 1.5 A / dm 2 .
- the extruded profile is then immersed in the coloring electrolyte, which in this special exemplary embodiment contains 12 g cobalt 1 1 (12 g Co / 1), 8 g metal complex-containing dye 1 1 (8 g / l) and 12 g of boric acid each 1 1 (12 g / 1), wherein the pH of the electrolyte is adjusted to pH 4.3 and its temperature to 24 °.
- the extruded profile is immersed in the coloring electrolyte, then connected for 2 minutes and 30 seconds to an AC voltage of 11 volts and kept constant, after which the profile is lifted out of the coloring electrolyte.
- 1 dm 2 of profile surface should have flowed 1, o A. min of dyeing current.
- the achromatic colors i.e. produce the shades of gray from darkness level 2.5 to darkness level 8 according to DIN 6164, supplement 25 in any darkness and color tint according to DIN 55981 in the same coloring electrolyte.
- the achromatic color "gray” in the physical sense applies that the color coordination a * and b * are O.
- the color “gray” differs from the colors “white” and “black” only in the variable brightness, which is rated in the CIELAB system from 1 00 (white) to O (black).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Luminescent Compositions (AREA)
- Chemical Treatment Of Metals (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
- Cookers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
Die Erfindung betrifft einen Färbeelektrolyten zum elektrolytischen Einfärben von anodisch erzeugten Oxidschichten auf Aluminium und Aluminiumlegierungen in Farben unterschiedlicher Buntheit und Helligkeit, insbesondere zur Anwendung bei Profilen für Fenster-, Türen-, Fassadenelemente u.dgl.The invention relates to a coloring electrolyte for the electrolytic coloring of anodically produced oxide layers on aluminum and aluminum alloys in colors of different colors and brightness, in particular for use in profiles for window, door, facade elements and the like.
Es sind bereits elektrochemische Färbebäder zum Einfärben von anodisch erzeugten Oxidschichten auf Aluminium und dessen Legierungen bekannt, die ein Metallsalz zur Einfärbung der Oxidschicht enthalten. Dabei wird zunächst an der Oberfläche der Aluminium bzw. Aluminiumlegierungen mittels Gleichstrom in beispielsweise schwefelsaurer Lösung eine definierte Oxidschicht erzeugt und diese anschließend mittels Wechselstrom unter Verwendung eines schwachsauren Färbeelektrolyten eingefärbt. Dabei enthält der Färbeelektrolyt vielfach ein Sulfat, beispielsweise des Eisens, Nickels oder Cobalts, wodurch ein Bronzeton bestimmter Farbstichigkeit erzeugt wird. Ausnahmen der Bronzefärbung lassen sich nur durch einen Zusatz im elektrochemischen Färbebad in Form von Kupfersulfat - wodurch eine rötliche Färbung der Oxidschicht erzeugt wird -, Silbersulfat oder Goldsulfat erzeugen, wodurch eine bläuliche bzw. gelbliche Färbung der Oxidschicht zustande kommt. Abgesehen davon, daß die Verwendung von Gold- und Silbersalzen zumeist aus wirtschaftlichen Gründen nicht zu vertreten ist, so ergeben sich vielfach bei gleicher Färbebadzusammensetzung und gleicher Behandlungsfolge doch unterschiedliche Bronzetöne, was sich insbesondere dann sehr nachteilig auswirkt, wenn eine größere Anzahl von Aluminiumprofilen eingefärbt werden soll und die nebeneinander verwendeten Profile optisch einen ungleichmäßigen Farbeindruck hinterlassen.Electrochemical dyebaths for coloring anodically produced oxide layers on aluminum and its alloys are already known, which contain a metal salt for coloring the oxide layer. First, a defined oxide layer is generated on the surface of the aluminum or aluminum alloys by means of direct current in, for example, sulfuric acid solution, and this is then colored by means of alternating current using a weakly acidic coloring electrolyte. The coloring electrolyte often contains a sulfate, for example of iron, nickel or cobalt, which produces a bronze tone with a certain color cast. Exceptions to bronze coloring can only be created by adding them in the electrochemical dyebath in the form of copper sulfate - which creates a reddish tinge to the oxide layer -, silver sulfate or gold sulfate, which results in a bluish or yellowish tint in the oxide layer comes about. Apart from the fact that the use of gold and silver salts is mostly not justifiable for economic reasons, different bronze tones often result with the same dye bath composition and the same treatment sequence, which has a particularly disadvantageous effect if a larger number of aluminum profiles are colored and the profiles used next to each other visually leave an uneven color impression.
Die Aufgabe der Erfindung besteht darin, einen Färbeelektrolyten der eingangs genannten Art zu schaffen, mit dem es möglich ist, auf wirtschaftlich vertretbare Weise anodisch oxidierte Schichten von Aluminium und Aluminiumlegierungen in bezug auf Buntheit und Helligkeit bei entsprechender Auswahl beliebig einzufärben.The object of the invention is to provide a coloring electrolyte of the type mentioned at the outset, with which it is possible to color anodized layers of aluminum and aluminum alloys in an economically justifiable manner in terms of color and brightness with appropriate selection.
Diese Aufgabe ist erfindungsgemäß dadurch gelöst, daß der Färbeelektrolyt außer einem Metallsalz eine organische Farbstoffkomponente enthält. Dadurch läßt sich der vom Metallsalz erzeugte Farbton bei entsprechender Auswahl der organischen Farbstoffkomponente derart überlagern, daß eine gewünschte Farbe entsteht.This object is achieved in that the coloring electrolyte contains an organic dye component in addition to a metal salt. As a result, the hue produced by the metal salt can be overlaid with a suitable selection of the organic dye component such that a desired color is produced.
In vielen Fällen ist es beispielsweise wünschenswert, eine unbunte Farbe an-der Oberfläche des Aluminiums bzw. der Aluminiumlegierung zu erzeugen. Es lassen sich die Gesetze der Farbmischung anwenden, wobei die Mischung von zwei Komplementärfarben bzw. die additive Farbmischung mit einer gegebenen Farbvalenz durch eine kompensative Farbe dann eine unbunte Farbe entstehen läßt. Um nun eine derartige unbunte Farbe der Qxidschicht des Aluminiums bzw. der Aluminiumlegierung zu erzeugen, enthält die neben dem Metallsalz im Elektrolyten enthaltene Farbstoffkomponente die Spektralfarbe Violett-Blau. Damit kommt die unbunte Farbe "grau" an Aluminium-Oxidschichten zustande, weil der über die elektrochemische Metallabscheidung anfallende Farbton "Bronze" durch den elektroadsorptiv angelagerten Farbton "Violett-Blau" gewissermaßen neutralisiert wird. Dabei kommt vorzugsweise als organische Farbstoffkomponente ein metallkomplexhaltiger Azofarbstoff zur Anwendung.In many cases, for example, it is desirable to produce an achromatic color on the surface of the aluminum or aluminum alloy. The laws of color mixing can be applied, the mixing of two complementary colors or the additive color mixing with a given color valence then giving rise to an achromatic color using a compensating color. In order to produce such a achromatic color for the oxide layer of the aluminum or the aluminum alloy, the dye component contained in the electrolyte in addition to the metal salt contains the spectral color violet-blue. This creates the achromatic color "gray" on aluminum oxide layers, because the "bronze" color produced by electrochemical metal deposition is neutralized to a certain extent by the "violet-blue" color applied by electrosorptive. A metal dye-containing azo dye is preferably used as the organic dye component.
Zur gemeinsamen Einlagerung der Farbstoffkomponente und des Metalls in die Oxidschicht ist der Elektrolyt vorzugsweise auf einen pH-Wert von pH 4 bis pH 5 eingestellt. Dabei wird als Spannungsquelle Wechselstrom für die Abscheidung des Metalls und die Einlagerung des metallkomplexhaltigen Azofarbstoffes benutzt.For the joint incorporation of the dye component and the metal into the oxide layer, the electrolyte is preferably adjusted to a pH of pH 4 to pH 5. Alternating current is used as the voltage source for the deposition of the metal and the incorporation of the metal complex-containing azo dye.
Um die Einlagerung der Farbstoffkomponente in die Oxidschicht zu stabilisieren, ist dem Färbeelektrolyt vorzugsweise eine Stickstoffverbindung zugesetzt. Eine derartige Stickstoffverbindung könnte beispielsweise ein Sulfat sein, das in seiner Verbindung Stickstoff enthält.In order to stabilize the incorporation of the dye component in the oxide layer, a nitrogen compound is preferably added to the coloring electrolyte. Such a nitrogen compound could be, for example, a sulfate that contains nitrogen in its compound.
Die Erfindung ist nachfolgend näher beschrieben und wird anhand eines Ausführungsbeispieles erläutert.The invention is described in more detail below and is explained using an exemplary embodiment.
Zur Herstellung einer elektrolytisch und elektroadsorptiv eingefärbten Oxidschicht von Aluminium und Aluminiumlegierungen werden die aus dem Aluminium bzw. dessen Legierungen hergestellten Gegenstände zunächst einer in bekannter Weise durchgeführten anodischen Oxidation unterzogen, wobei mittels Gleichstom in einer zur Elektrolyse geeigneten Lösung - wie beispielsweise Schwefel-, Oxal-oder Chromsäure - eine definierte Oxidschicht erzeugt wird und diese anschließend in dem schwachsauren Färbeelektrolyten unter Zuführung von Wechselstrom eingefärbt wird.To produce an electrolytically and electrophoretically colored oxide layer of aluminum and aluminum alloys, the objects made from aluminum or its alloys are first subjected to anodic oxidation in a known manner, using direct current in a solution suitable for electrolysis - such as sulfur, oxal or chromic acid - a defined oxide layer is generated and this is then colored in the weakly acidic coloring electrolyte with the supply of alternating current.
Zur Erzielung eines beispielsweise unbunten Farbtones - d.h. eines Grautones - mag der Färbeelektrolyt als Metallsalz Cobaltsulfat sowie als organische Farbstoffkomponente eine chromkomplexhaltige Azoverbindung enthalten. Legt man an diesen Färbeelektrolyten eine elektrische Wechselspannung an, so wandern unter dem Einfluß des elektrischen Feldes der metallkomplexhaltige Farbstoff und die Cobalt-Ionen in die Mikroporen der Aluminiumoxidschicht ein, wobei die Cobalt-Ionen am Porengrund zu Metall reduziert werden. Der organische Farbstoff lagert sich tiefer in die Poren ein, als dies bei einer rein adsorptiven Einfärbung der Fall ist. Infolge dieser tieferen Einlagerung in den Poren sowie der Rekomplexierung des Farbstoffes mit den in den Poren verbleibenden Schwermetallsalzen während der hydro-thermalen Behandlung - dem sogenannten Sealen -, gelingt es in wirtschaftlicher Weise sogenannte licht- und wetterfeste Grautöne auf anodisiertem Aluminium zu erhalten.To achieve a achromatic color tone - i.e. a shade of gray - the coloring electrolyte may contain cobalt sulfate as the metal salt and an azo compound containing chromium complex as the organic dye component. If an electrical alternating voltage is applied to these coloring electrolytes, the metal complex-containing dye and the cobalt ions migrate into the micropores of the aluminum oxide layer under the influence of the electrical field, the cobalt ions at the pore base being reduced to metal. The organic dye is deposited deeper in the pores than is the case with purely adsorptive coloring. As a result of this deeper storage in the pores and the recomplexing of the dye with the heavy metal salts remaining in the pores during the hydro-thermal treatment - the so-called Sealen - it is possible to obtain so-called light and weatherproof shades of gray on anodized aluminum in an economical manner.
Dabei lassen sich unterschiedliche Farbnuancen der definierten Aluminiumoxidschichten durch gezieltes Abstimmen der Einflußgrößen in zwei aufeinander folgenden Behandlungsstufen erzielen. Als erste Behandlungsstufe ist die Vorbehandlung der aus Aluminium bzw. dessen Legierungen hergestellten Gegenstände mit nachfolgender anodischer Oxidation anzusehen, während die zweite Behandlungsstufe durch das Einfärben der Oxidschicht in einem Färbeelektrolyten dargestellt ist. Während bei der ersten Behandlungsstufe die Legierung und der Zustand der anodisierten Halbzeuge, deren Glanz- bzw. Mattheitsgrad der Oberfläche sowie die Elektrolytzusammensetzung und die Arbeitsbedingungen während des Anodisiervorganges als Einflußgrößen in Frage kommen, sind als Einflußgrößen der zweiten Behandlungsstufe die Zusammensetzung des Färbeelektrolyten, deren pH-Wert, Temperatur, Verweilzeit und Stromdichte anzusehen.Different color shades of the defined aluminum oxide layers can be achieved by specifically coordinating the influencing variables in two successive treatment stages. The first treatment stage is the pretreatment of the objects made of aluminum or its alloys with subsequent anodic oxidation, while the second treatment stage is represented by the coloring of the oxide layer in a coloring electrolyte. While in the first treatment stage the alloy and the condition of the anodized semi-finished products, their degree of gloss or mattness of the surface as well as the electrolyte composition and the working conditions during the anodizing process can be considered as influencing variables, the influencing variables in the second treatment stage are the composition of the coloring electrolyte and its pH - View value, temperature, dwell time and current density.
Wenn nun beispielsweise ein Strangpreßprofil der Aluminiumlegierung AlMgSi o,5 Mittelgrau entsprechend der Dunkelstufe D 4,5 des DIN-Blattes 6164, Beiblatt 25, eingefärbt werden soll, so wird das Strangpreßprofil zunächst nach bekannten Verfahren entfettet, gebeizt und anodisiert. Der die anodische Oxidation bewirkende Elektrolyt enthält 19o g Schwefelsäure je 1 1 Wasser (19o g/1 H2S04) und 1o g Aluminium pro 1 1 Elektrolyt (1o g/l). Die Temperatur des zur Anodisation vorgesehenen Elektrolyten beträgt 20°C, während die Stromdichte 1,5 A/dm2 betragen soll. Um die im Anodisations-Elektrolyten erzeugte Oxidschicht mittelgrau einzufärben, wird das Strangpreßprofil anschließend in den Färbeelektrolyten eingetaucht, der bei diesem speziellen Ausführungsbeispiel 12 g Cobalt je 1 1 (12 g Co/1), 8 g metallkomplexhaltiger Farbstoff je 1 1 (8 g/l) und 12 g Borsäure je 1 1 (12 g/1) enthält, wobei der pH-Wert des Elektrolyten auf pH 4,3 und dessen Temperatur auf 24° eingestellt ist.If, for example, an extruded profile of the aluminum alloy AlMgSi o. 5 medium gray corresponding to the darkness D 4.5 of DIN sheet 6164, supplementary sheet 25, is to be colored, the extruded profile is first degreased, pickled and anodized using known methods. The electrolyte causing the anodic oxidation contains 19o g sulfuric acid per 1 1 water (19o g / 1 H 2 SO 4 ) and 10 g aluminum per 1 1 electrolyte (10 g / l). The temperature of the electrolyte intended for anodization is 20 ° C, while the current density should be 1.5 A / dm 2 . In order to color the oxide layer produced in the anodization electrolyte medium gray, the extruded profile is then immersed in the coloring electrolyte, which in this special exemplary embodiment contains 12 g cobalt 1 1 (12 g Co / 1), 8 g metal complex-containing dye 1 1 (8 g / l) and 12 g of boric acid each 1 1 (12 g / 1), wherein the pH of the electrolyte is adjusted to pH 4.3 and its temperature to 24 °.
Das Strangpreßprofil wird in den Färbeelektrolyten eingetaucht, anschließend für 2 Minuten und 3o Sekunden an eine Wechselspannung von 11 Volt angeschlossen und konstant gehalten, wonach das Profil aus dem Färbeelektrolyt gehoben wird. Je 1 dm2 Profiloberfläche sollen 1,o A.min Färbestrom geflossen sein.The extruded profile is immersed in the coloring electrolyte, then connected for 2 minutes and 30 seconds to an AC voltage of 11 volts and kept constant, after which the profile is lifted out of the coloring electrolyte. 1 dm 2 of profile surface should have flowed 1, o A. min of dyeing current.
Durch die Wahl der Abscheidungs- und Arbeitsbedingungen lassen sich beispielsweise die unbunten Farben, d.h. die Grautöne, ab der Dunkelstufe 2,5 bis Dunkelstufe 8 gemäß DIN 6164, Beiblatt 25 in beliebiger Dunkelheit und Farbstichigkeit nach DIN 55981 in demselben Färbeelektrolyten herstellen.By choosing the deposition and working conditions, for example, the achromatic colors, i.e. produce the shades of gray from darkness level 2.5 to darkness level 8 according to DIN 6164, supplement 25 in any darkness and color tint according to DIN 55981 in the same coloring electrolyte.
In Anlehnung an das Farbkoordinatensystem nach CIELAB 1976 gilt für die unbunte Farbe "Grau" im physikalischen Sinne, daß die Farbkoordination a* und b* gleich O sind. Die Farbe "Grau" unterscheidet sich von den Farben "Weiß" und "Schwarz" nur durch die variable Helligkeit, die im CIELAB-System von 100 (Weiß) bis O (Schwarz) bewertet ist.Based on the color coordinate system according to CIELAB 1976, the achromatic color "gray" in the physical sense applies that the color coordination a * and b * are O. The color "gray" differs from the colors "white" and "black" only in the variable brightness, which is rated in the CIELAB system from 1 00 (white) to O (black).
Wie bereits erwähnt, gibt das vorbeschriebene Anwendungsbeispiel die Erfindung lediglich beispielsweise wieder und ist keinesfalls allein darauf beschränkt. Es sind vielmehr noch mancherlei Änderungen der Anwendung möglich. Wenn beispielsweise das Strangpreßprofil eine Farbstichigkeit nach Blau aufweisen soll und nach dem CIELAB-Farbkoordinatensystem die Farbkoordinaten a* = 1,3 und b* = 3,o aufweisen soll, so kann entweder der pH-Wert des Färbeelektrolyten angehoben oder aber die Tauchzeit verlängert werden.As already mentioned, the above-described example of use only reproduces the invention by way of example and is in no way limited to it. Rather, there are still many changes to the application. If, for example, the extruded profile is to have a color cast to blue and the color coordinates a * = 1.3 and b * = 3.0 according to the CIELAB color coordinate system, then either the pH value of the coloring electrolyte can be increased or the immersion time can be extended .
Claims (5)
dadurch gekennzeichnet ,
daß der Färbeelektrolyt außer einem Metallsalz eine organische Farbstoffkomponente enthält.1.) Coloring electrolyte for the electrolytic coloring of anodically produced oxide layers on aluminum and aluminum alloys in colors of different colors and brightness, in particular for use in profiles for window, door, facade elements and the like.
characterized ,
that the coloring electrolyte contains an organic dye component in addition to a metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83112387T ATE36356T1 (en) | 1982-12-29 | 1983-12-09 | DYE ELECTROLYTE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3248472 | 1982-12-29 | ||
| DE3248472A DE3248472C1 (en) | 1982-12-29 | 1982-12-29 | Coloring electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0113862A1 true EP0113862A1 (en) | 1984-07-25 |
| EP0113862B1 EP0113862B1 (en) | 1988-08-10 |
Family
ID=6182048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83112387A Expired EP0113862B1 (en) | 1982-12-29 | 1983-12-09 | Electrolytic colouring |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0113862B1 (en) |
| AT (1) | ATE36356T1 (en) |
| DE (1) | DE3248472C1 (en) |
| DK (1) | DK591783A (en) |
| ES (1) | ES8407526A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB359495A (en) * | 1930-07-23 | 1931-10-23 | Sidney Rowland Sheppard | Improvements in and relating to the production of coloured aluminium, aluminium alloys and aluminium coated articles |
-
1982
- 1982-12-29 DE DE3248472A patent/DE3248472C1/en not_active Expired
-
1983
- 1983-12-09 AT AT83112387T patent/ATE36356T1/en not_active IP Right Cessation
- 1983-12-09 EP EP83112387A patent/EP0113862B1/en not_active Expired
- 1983-12-22 DK DK591783A patent/DK591783A/en not_active Application Discontinuation
- 1983-12-28 ES ES528468A patent/ES8407526A1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB359495A (en) * | 1930-07-23 | 1931-10-23 | Sidney Rowland Sheppard | Improvements in and relating to the production of coloured aluminium, aluminium alloys and aluminium coated articles |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 82, Nr. 24, 16. Juni 1975, Seite 390, Nr. 161818f, Columbus, Ohio, US & JP - A - 74 115 942 (ONTA, TOSHIYUKI) 06-11-1974 * |
| CHEMICAL ABSTRACTS, Band 93, Nr. 3, August 1980, Seite 672, Nr. 56908q, Columbus, Ohio, US & JP - A -80 28 324 (NIHON KAGAKU KIZAI K.K.) 28-02-1980 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DK591783A (en) | 1984-06-30 |
| ES528468A0 (en) | 1984-09-16 |
| ATE36356T1 (en) | 1988-08-15 |
| EP0113862B1 (en) | 1988-08-10 |
| DE3248472C1 (en) | 1984-02-16 |
| ES8407526A1 (en) | 1984-09-16 |
| DK591783D0 (en) | 1983-12-22 |
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