EP0090268A2 - Process for anodising aluminium products and aluminised parts - Google Patents

Process for anodising aluminium products and aluminised parts Download PDF

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Publication number
EP0090268A2
EP0090268A2 EP83102616A EP83102616A EP0090268A2 EP 0090268 A2 EP0090268 A2 EP 0090268A2 EP 83102616 A EP83102616 A EP 83102616A EP 83102616 A EP83102616 A EP 83102616A EP 0090268 A2 EP0090268 A2 EP 0090268A2
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Prior art keywords
aluminum
anodizing
bath
parts
per liter
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German (de)
French (fr)
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EP0090268B1 (en
EP0090268A3 (en
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Siegfried Dr. Birkle
Klaus Stöger
Hans De Vries
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Siemens AG
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Siemens AG
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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
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • 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
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • 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

Definitions

  • the invention relates to a method for anodizing aluminum materials and aluminized parts in aqueous alkaline, phosphate-containing, anodizing electrolytes.
  • Aluminum materials and aluminum-coated parts are not yet sufficiently stable for many applications, although self-passivation takes place in air, which is stable in the pH range from 5 to 9. However, this oxide layer is still too small for many technical applications. The layer is therefore reinforced in anodizing electrolytes.
  • an alkaline bath with sodium phosphate as the main constituent is used to produce shiny aluminum oxide layers with a maximum thickness of 4 ⁇ m.
  • a bath temperature of 20 to 90 ° C and a current density of 0.5 to 80 A / dm 2 aluminum or aluminum alloys are bright-galvanized.
  • these treatments (“glossy processes”) lead to glossy films, which are often undesirable.
  • the object of the invention is to provide aluminum materials and parts coated with aluminum, in particular iron materials, with hard abrasion-resistant and dyeable thicker aluminum oxide layers, in particular those of 10 to 20 ⁇ m, while avoiding the disadvantages mentioned above, even if the aluminum coating has any defects.
  • the flaws are e.g. the uncoated contact points in question, or in the case of profiled parts, the uncoated points, which may be present due to the limited spreadability of the aluminizing process.
  • Thick aluminum oxide layers are also to be produced on partially aluminized consumer metals, such as iron, nonferrous metal, nickel and zinc die-cast materials, without destroying the base material during anodization.
  • This object is achieved by the process of the invention in that on the aluminum material and aluminized parts in an anodizing bath which does not form any forming layers and contains 10 to 200 g of trisodium phosphate or tripotassium phosphate per liter at temperatures of 0 to 15 ° C. while passing C0 2 -free or low-CO 2 air, a preferably 10 to 20 ⁇ m thick matt anodizing layer is produced.
  • aluminum materials and aluminized parts in particular also partially aluminized parts made of iron, nickel and non-ferrous metal materials as well as zinc die-cast metals, even if they have flaws, can be anodically oxidized without technical disadvantages, so that hard, abrasion-resistant and dyeable oxide layers are formed.
  • the surfaces of aluminized parts are not shiny, but retain the appearance of the deposited aluminum layers.
  • the oxide layers produced are above all thicker than 4 ⁇ m. They are characterized by exceptional hardness and abrasion resistance.
  • the method according to the invention is also particularly suitable for achieving the aforementioned layer properties in the case of aluminum materials.
  • the bath can be operated with direct current and with impulse current.
  • Baths containing 50 to 150 g / l of trisodium phosphate or tripotassium phosphate are advantageously used to carry out the process according to the invention.
  • optically most uniform anodizing layers are obtained by adding 1 to 20 g of a complexing agent per liter of anodizing bath, for example alkali metal cyanide. Preferably 1 to 6 g of sodium cyanide are added to the bath per liter.
  • the method according to the invention is suitable for anodizing aluminum materials, aluminum flame spraying layers and roll-cladding layers, fire-aluminum layers, PVD-aluminum layers and in particular IVD and galvano-aluminum layers.
  • Galvano aluminum is an aluminum of high purity (> 99.99), good electrical conductivity and high ductility ⁇ 20 HV, which is obtained by deposition from organoaluminum electrolytes.
  • hollow bodies that are aluminized on the outside as well as workpieces with partially exposed surfaces, e.g. Parts of the apparatus with movable hinges (glasses), in which, in principle, no aluminum can be deposited at all points on the hinge, are provided according to the invention with hard, abrasion-resistant and dyeable aluminum oxide layers in thicknesses of 10 to 20 ⁇ m.
  • FIG shows in section an embodiment of a hinge 1 of an eyeglass frame made of nickel silver 4, which has an aluminum layer 2.
  • the aluminum oxide layer applied to this according to the invention is designated by 3.
  • Iron sheets 50 x 100 x 1mm were first galvanically coated in an aluminum electrolyte with the following composition with a matt galvano-aluminum layer.
  • the spectacle frames 1 to 3 were treated in an anodizing bath - as described in Example 1.
  • eyeglass frames 4 to 6 were treated after pickling in an electrolyte of the following composition, the anodizing conditions being chosen from 1 to 3:
  • the eyeglass frames 1 to 3 on the hinges looked more inconsistent after coloring the anodized layer
  • the eyeglass frames 4 to 6 gave a uniform visual appearance.
  • the complexing agent contributes to a more homogeneous oxide formation at the phase boundary with aluminum.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
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Abstract

Aluminum materials and aluminized parts are oxidatively anodized at a bath temperature of 0 DEG to 15 DEG C. and preferably, 0 DEG to 10 DEG C. to produce an anodized layer of aluminum oxide more than 4 microns thick, which is hard, abrasion-proof and can be stained. The anodizing is bath used while conducting air free of or low in carbon dioxide through the bath. It is free of substances which limit the oxide layer to maximally a thickness of about 1 micron (forming layer) and contains 10 to 500 g trisodium phosphate or tripotassium phosphate per liter. In partially aluminized parts, no destruction of the base material occurs during the aluminizing.

Description

Die Erfindung betrifft ein Verfahren zum Anodisieren von Aluminiumwerkstoffen und aluminierten Teilen in wässrig alkalischen,Phosphationen enthaltenden, Anodisierelektrolyten.The invention relates to a method for anodizing aluminum materials and aluminized parts in aqueous alkaline, phosphate-containing, anodizing electrolytes.

Aluminiumwerkstoffe und aluminiumbeschichtete Teile sind für viele Anwendungszwecke noch nicht hinreichend beständig, obwohl an Luft eine Selbstpassivierung erfolgt, die im PH-Bereich von 5 bis 9 beständig ist. Diese Oxidschicht ist aber für viele Anwendungszwecke in der Technik noch zu gering. Deshalb wird die Schicht in Anodisierelektrolyten verstärkt.Aluminum materials and aluminum-coated parts are not yet sufficiently stable for many applications, although self-passivation takes place in air, which is stable in the pH range from 5 to 9. However, this oxide layer is still too small for many technical applications. The layer is therefore reinforced in anodizing electrolytes.

Es ist bekannt ("Die Praxis der anodischen Oxydation des Aluminiums" Aluminiumverlag GmbH Düsseldorf, 1961, insbesondere Seiten 37, 46 und 50) Aluminium unter Verwendung von verdünnter Schwefelsäure (Gleichstrom-Schwefelsäure-Verfahren), verdünnter Oxalsäure (Gleichstrom-Oxalsäure-Verfahren) oder auch in einem Schwefelsäure-Oxalsäure-Bad anodisch zu oxidieren.Diese Verfahren sind zwar für Aluminiumwerkstoffe einsetzbar, doch tritt bei aluminierten Teilen eine Zerstörung des Werkstoffs oder zumindest ein anwendungstechnisch nicht tolerierbares Anfressen der Materialoberfläche ein, wenn keine allseitige Aluminierbedeutung gegeben ist.It is known ("The Practice of Anodic Oxidation of Aluminum" Aluminumverlag GmbH Düsseldorf, 1961, in particular pages 37, 46 and 50) aluminum using dilute sulfuric acid (direct current sulfuric acid method), dilute oxalic acid (direct current oxalic acid method) or anodically oxidize in a sulfuric acid-oxalic acid bath.These methods can be used for aluminum materials, but in the case of aluminized parts, the material is destroyed or, at least in terms of application technology, the material surface is eroded if there is no overall importance of aluminizing.

Aus der DE-OS 28 42 396 ist ein "Verfahren zur Glanzanodisierung von Aluminium" bekannt, das auf einer in "Werkstoff Aluminium und seine anodische Oxydation" von Max Schenk, 1948, Seite 801 zitierten Arbeit beruht. Das alkalische 80 °C + 1 °C warme wässrige Glänzbad enthält gemäß M. Schenk Natriumcarbonat und tertiäres Natriumphosphat..From DE-OS 28 42 396 a "process for the bright anodization of aluminum" is known, which is based on a work cited in "Material aluminum and its anodic oxidation" by Max Schenk, 1948, page 801. According to M. Schenk, the alkaline 80 ° C + 1 ° C warm, aqueous gloss bath contains sodium carbonate and tertiary sodium phosphate.

Gemäß der DE-OS 28 42 396 wird zur Herstellung glänzender maximal 4 µm dicker Aluminiumoxidschichten ein alkalisches Bad mit Natriumphosphat als Hauptbestandteil verwendet. Bei einer Badtemperatur von 20 bis 90 °C und einer Stromdichte von 0,5 bis 80 A/dm2 werden Aluminium oder Aluminiumlegierungen glanzodisiert. Abgesehen davon, daß bei diesem Verfahren bei stark salzhaltigen Elektrolyten bei höheren Temperaturen gearbeitet wird, führen diese Behandlungen ("Glänzverfahren") zu glänzenden Filmen, die vielfach unerwünscht sind.According to DE-OS 28 42 396, an alkaline bath with sodium phosphate as the main constituent is used to produce shiny aluminum oxide layers with a maximum thickness of 4 μm. At a bath temperature of 20 to 90 ° C and a current density of 0.5 to 80 A / dm 2 , aluminum or aluminum alloys are bright-galvanized. In addition to the fact that this process is carried out at high temperatures in the case of strongly saline electrolytes, these treatments (“glossy processes”) lead to glossy films, which are often undesirable.

Da die Auflösung des Aluminiums schneller vonstatten geht als die Oxidbildung, kann bei dem in der DE-OS beschriebenen Verfahren selbst bei längerer Eloxierdauer nur eine Aluminiumoxidschicht von < 4 µm erzeugt werden. Außerdem entstehen bereits nach kurzer Badstandzeit wegen der zunehmenden Carbonatmenge infolge Absorption des CO2 aus der Luft nur noch sogenannte Formierschichten < 1 µm. Die Abtragsrate ist unter den hier angegebenen Eloxierbedingungen so hoch, daß bei aluminierten Teilen an dünner aluminierten Stellen das Aluminium statt anodisiert, abgelöst wird. Vor allem können keine nach DE-OS 28 42 396 beschriebenen Verfahren, Toleranzmaße des Aluminiumüberzuges, dessen Schichtdicke aus technisch wirtschaftlichen Gründen vorgegeben ist, eingehalten werden. Auch Aluminiumwerkstoffe können so nicht mit einer dickeren Oxidschicht versehen werden.Since the dissolution of the aluminum takes place faster than the oxide formation, only an aluminum oxide layer of <4 μm can be produced in the process described in DE-OS even with a longer anodizing time. In addition, after a short bath life, only so-called forming layers <1 µm are formed due to the increasing amount of carbonate due to absorption of CO 2 from the air. The removal rate is so high under the anodizing conditions specified here that the aluminum instead of anodized is replaced in the case of aluminized parts at thinner aluminized locations. Above all, no methods described according to DE-OS 28 42 396, tolerance dimensions of the aluminum coating, the layer thickness of which are possible for technical economic reasons is given. Even aluminum materials cannot be provided with a thicker oxide layer.

Ein besonderes Problem - bei der Kombination von metallischen Werkstoffen mit Aluminium in Form eines schützenden Überzuges - ergibt sich insofern, weil in sauren den bekannten/Anodisierelektrolyten (bei anodischer Polung) an den ungenügend beschichteten Substratoberflächen, beispielsweise bei Eisen, Kupfer, Nickel und Zink und deren Legierungen diese sich anodisch auflösen. Bei solchen Materialien kommt es daher zu derart starken Korrosionserscheinungen, daß aluminiumbeschichtete Teile sowohl in dekorativer Hinsicht als auch in ihrer Funktion unbrauchbar bzw. zerstört werden.A particular problem - with the combination of metallic materials with aluminum in the form of a protective coating - arises because in acidic the known / anodizing electrolytes (with anodic polarity) on the insufficiently coated substrate surfaces, for example with iron, copper, nickel and zinc and the alloys of which dissolve anodically. With such materials, the corrosion phenomena are so severe that aluminum-coated parts are unusable or destroyed both in decorative terms and in their function.

Diese Tatsache schränkt die Anwendung der Aluminierung im dekorativen funktionellen Oberflächensektor stark ein, so daß beispielsweise die Applikation der einfärbbaren Galvano-Aluminium-Eloxal O -schichten, z.B. auf Brillengestellen, Feuerzeughülsen, Schreibgeräten usw. technisch gesehen bisher nur schwer oder überhaupt nicht realisiert werden konnte.This fact severely limits the use of aluminizing in the decorative functional surface sector, so that, for example, the application of the dyeable galvano-aluminum-anodized O layers, for example on spectacle frames, lighter sleeves, writing utensils, has so far been difficult or impossible to achieve from a technical point of view .

Zur Anodisierung von aluminierten Teilen mit ungenügender Bedeckung, die in sauren Eloxierbädern durchgeführt wird, ist es erforderlich, die freien Stellen vor dem Eloxieren mit einem sogenannten Abdecklack zu versehen. Nach dem Eloxieren sind derartige Lacke zu entfernen, indem man diese entweder abzieht oder mit einem geeigneten Lösungsmittel ablöst. Bei Hohlräumen oder Bohrungen, in denen sich kein Aluminium befindet, kann man sich dadurch helfen, indem diese mit Stopfen oder dergleichen abgedichtet werden. Diese prinzipiell zwar mögliche Verfahrensweise ist technisch aufwendig und unwirtschaftlich. Bei diversen Teilen, z.B. solchen mit Scharnieren (Brillen) , ist das genannte Abdeckverfahren jedoch aus dekorativen Gründen (Einfärben der Eloxal®-Schichten) unbrauchbar und damit ein Anodisieren prinzipiell nicht möglich.To anodize aluminized parts with insufficient coverage, which is carried out in acidic anodizing baths, it is necessary to provide the free areas with a so-called masking lacquer before anodizing. After anodizing, such varnishes must be removed by either peeling them off or removing them with a suitable solvent. Cavities or bores in which there is no aluminum can be helped by sealing them with plugs or the like. This in principle The possible procedure is technically complex and uneconomical. In the case of various parts, such as those with hinges (glasses), the covering method mentioned is unusable for decorative reasons (coloring of the Eloxal® layers) and anodizing is therefore not possible in principle.

Aufgabe der Erfindung ist es, Aluminiumwerkstoffe sowie mit Aluminium beschichtete Teile,insbesondere Eisen- werkstoffe,unter Vermeidung der oben angeführten Nachteile mit harten abriebfesten und einfärbbaren dickeren Aluminiumoxidschichten, insbesondere solchen von 10 bis 20 µm zu versehen, und zwar auch dann, wenn der Aluminiumüberzug irgendwelche Fehlstellen aufweist. Als Fehlstellen kommen z.B. die nicht beschichteten Kontaktstellen infrage, oder bei profilierten Teilen, die nicht überzogenen Stellen, die aufgrund der begrenzten Streufähigkeit Aluminierverfahren vorhanden sein können. Es sollen auch auf partiell aluminierten Gebrauchsmetallen, wie Eisen-, Buntmetall-, Nickel-und Zinkdruckgußwerkstoffen ohne Zerstörung des Grundwerkstoffes bei der Anodisierung dicke Aluminiumoxidschichten erzeugt werden.The object of the invention is to provide aluminum materials and parts coated with aluminum, in particular iron materials, with hard abrasion-resistant and dyeable thicker aluminum oxide layers, in particular those of 10 to 20 μm, while avoiding the disadvantages mentioned above, even if the aluminum coating has any defects. The flaws are e.g. the uncoated contact points in question, or in the case of profiled parts, the uncoated points, which may be present due to the limited spreadability of the aluminizing process. Thick aluminum oxide layers are also to be produced on partially aluminized consumer metals, such as iron, nonferrous metal, nickel and zinc die-cast materials, without destroying the base material during anodization.

Diese Aufgabe wird durch das Verfahren der Erfindung dadurch gelöst, daß auf dem Aluminiumwerkstoff und aluminierten Teilen in einem keine Formierschichten bildenden Anodisierbad, enthaltend pro Liter 10 bis 200g Trinatriumphosphat oder Trikaliumphosphat, bei Temperaturen von 0 bis 15 °C unter Durchleiten von C02-freier oder C02-armer Luft eine vorzugsweise 10 bis 20 um dicke matte Anodisierschicht erzeugt wird.This object is achieved by the process of the invention in that on the aluminum material and aluminized parts in an anodizing bath which does not form any forming layers and contains 10 to 200 g of trisodium phosphate or tripotassium phosphate per liter at temperatures of 0 to 15 ° C. while passing C0 2 -free or low-CO 2 air, a preferably 10 to 20 μm thick matt anodizing layer is produced.

Mit dem erfindungsgemäßen Verfahren können Aluminiumwerkstoffe und aluminierte Teile, insbesondere auch partiell aluminierte Teile aus Eisen-, Nickel- und Buntmetallwerkstoffen sowie Zinkdruckgußmetalle, auch wenn sie Fehlstellen aufweisen, ohne anwendungstechnische Nachteile anodisch oxidiert werden, so daß und harte,abriebfeste und einfärbbare Oxidschichten entstehen. Die Oberflächen aluminierter Teile sind nicht glänzend, sondern behalten das Aussehen der abgeschiedenen Aluminiumschichten bei. Die erzeugten Oxidschichten sind vor allem dicker als 4 µm. Sie zeichnen sich durch außergewöhnliche Härte und Abriebfestigkeit aus. Das erfindungsgemäße Verfahren eignet sich insbesondere auch für die Erzielung vorgenannter Schichteigenschaften bei Aluminium-Werkstoffen.With the method according to the invention, aluminum materials and aluminized parts, in particular also partially aluminized parts made of iron, nickel and non-ferrous metal materials as well as zinc die-cast metals, even if they have flaws, can be anodically oxidized without technical disadvantages, so that hard, abrasion-resistant and dyeable oxide layers are formed. The surfaces of aluminized parts are not shiny, but retain the appearance of the deposited aluminum layers. The oxide layers produced are above all thicker than 4 µm. They are characterized by exceptional hardness and abrasion resistance. The method according to the invention is also particularly suitable for achieving the aforementioned layer properties in the case of aluminum materials.

Besonders günstige Effekte werden bei einem Badbetrieb von 0 bis 10 °C erreicht. Das Bad kann mit Gleichstrom und mit Impulsstrom betrieben werden.Particularly favorable effects are achieved with bath operation from 0 to 10 ° C. The bath can be operated with direct current and with impulse current.

Zur Durchführung des erfindungsgemäßen Verfahrens werden mit Vorteil Bäder, enthaltend 50 bis 150g/1 Trinatriumphosphat oder Trikaliumphosphat, eingesetzt.Baths containing 50 to 150 g / l of trisodium phosphate or tripotassium phosphate are advantageously used to carry out the process according to the invention.

Die optisch einheitlichsten Anodisierschichten werden bei Zugabe von 1 bis 20g eines Komplexbildners pro Liter Anodisierbad, beispielsweise Alkalicyanid, erhalten. Vorzugsweise werden dem Bad pro Liter 1 bis 6g Natriumcyanid zugesetzt.The optically most uniform anodizing layers are obtained by adding 1 to 20 g of a complexing agent per liter of anodizing bath, for example alkali metal cyanide. Preferably 1 to 6 g of sodium cyanide are added to the bath per liter.

Das erfindungsgemäße Verfahren eignet sich zum Anodisieren von Aluminium-Werkstoffen, Aluminium-Flammspritzschichten und -Walzplattierschichten, Feuer-Aluminium- Schichten, PVD-Aluminium-Schichten und insbesondere IVD- und Galvano-Aluminium-Schichten.The method according to the invention is suitable for anodizing aluminum materials, aluminum flame spraying layers and roll-cladding layers, fire-aluminum layers, PVD-aluminum layers and in particular IVD and galvano-aluminum layers.

"Galvano-Aluminium" ist ein Aluminium hoher Reinheit ( >99.99), guter elektrischer Leitfähigkeit und hoher Duktilität < 20 HV, das durch Abscheidung aus aluminiumorganischen Elektrolyten erhalten wird."Galvano aluminum" is an aluminum of high purity (> 99.99), good electrical conductivity and high ductility <20 HV, which is obtained by deposition from organoaluminum electrolytes.

Es können mit Vorteil beispielsweise nur außen aluminierte Hohlkörper sowie Werkstücke mit partiell freigelassenen Flächen, z.B. Apparateteile mit beweglichen Scharnieren (Brillen), bei denen prinzipiell kein Aluminium an allen Stellen des Scharniers abgeschieden werden kann, erfindungsgemäß mit harten abriebfesten und einfärbbaren Aluminiumoxidschichten in Dicken von 10 bis 20 µm versehen werden.For example, hollow bodies that are aluminized on the outside as well as workpieces with partially exposed surfaces, e.g. Parts of the apparatus with movable hinges (glasses), in which, in principle, no aluminum can be deposited at all points on the hinge, are provided according to the invention with hard, abrasion-resistant and dyeable aluminum oxide layers in thicknesses of 10 to 20 μm.

Die Erfindung wird anhand der Beispiele und der FIG näher erläutert.The invention is illustrated by the examples and the FIG.

Die FIG zeigt im Schnitt ein Ausführungsbeispiel eines Scharniers 1 eines Brillengestells aus Neusilber 4, das eine Aluminiumschicht 2 aufweist. Die auf dieser gemäß der Erfindung aufgebrachte Aluminium-oxid-Schicht ist mit 3 bezeichnet.The FIG shows in section an embodiment of a hinge 1 of an eyeglass frame made of nickel silver 4, which has an aluminum layer 2. The aluminum oxide layer applied to this according to the invention is designated by 3.

Beispiel 1example 1

Es wurden zuerst Eisenbleche (50 x 100 x 1mm) in einem Aluminiumelektrolyten nach folgender Zusammensetzung galvanisch mit einer matten Galvano-Aluminiumschicht versehen.Iron sheets (50 x 100 x 1mm) were first galvanically coated in an aluminum electrolyte with the following composition with a matt galvano-aluminum layer.

Figure imgb0001
Nach kurzem Beizen werden sie in verdünnter Natronlauge in einen Eloxierelektrolyten zusammengesetzt aus
Figure imgb0001
 After brief pickling, they are put together in an anodizing electrolyte in dilute sodium hydroxide solution

30 1 entionisiertem Wasser30 1 deionized water

1,5 kg Na3PO4 12 H2 0 1.5 kg Na 3 PO 4 1 2 H 2 0

getaucht und wie folgt anodisiert:

Figure imgb0002
dipped and anodized as follows:
Figure imgb0002

Elektrolytumwälzung mit CO2-freier Preßluft.Electrolyte circulation with CO 2 -free compressed air.

Man erhielt eine ca. 10 µm dicke, transparente Eloxalschicht. Die nicht aluminierten Kontaktstellen waren praktisch nicht angegriffen.An approximately 10 μm thick, transparent anodized layer was obtained. The non-aluminized contact points were practically not attacked.

Ein im Vergleich hierzu gemäß der DE-OS 28 42 396 bei 20 °C eloxierte vorher matte Aluminiumoberfläche hatte ein glänzendes Aussehen. Die nicht aluminierten Kontaktstellen zeigen eine für die Anwendung nicht tolerierbare Korrosion. Außerdem konnten selbst bei dicken Aluminium-Schichten nur max. 3 bis 4 µm dicke Eloxalschichten erzeugt werden.A previously matt aluminum surface, anodized in comparison with this in DE-OS 28 42 396 at 20 ° C., had a shiny appearance. The non-aluminized contact points show corrosion that is not tolerable for the application. In addition, even with thick aluminum layers, only max. 3 to 4 µm thick anodized layers can be created.

Beispiel 2Example 2

6 Brillengestelle aus Neusilber wurden in einem Aluminier-Elektrolyten - wie in Beispiel 1 angegeben - ca. 1 1/2 Stunden aluminiert. Die mittlere Al-Schichtdicke am Brillenbügel und an der Brillenfassung betrug ca. 20 µm, dagegen im Zwickel an den Scharnieren 1 bis 3 µm.6 glasses frames made of nickel silver were aluminized in an aluminizing electrolyte - as indicated in Example 1 - for about 1 1/2 hours. The average Al layer thickness on the temple and on the frame was approx. 20 µm, but in the gusset on the hinges 1 to 3 µm.

Nach kurzem Beizen in verdünnter Natronlauge wurden die Brillengestelle 1 bis 3 in einem Anodisierbad - wie in Beispiel 1 beschrieben - behandelt.After briefly pickling in dilute sodium hydroxide solution, the spectacle frames 1 to 3 were treated in an anodizing bath - as described in Example 1.

Im Gegensatz dazu wurden die Brillengestelle 4 bis 6 nach dem Beizen in einem Elektrolyten folgender Zusammensetzung behandelt, wobei die Anodisierbedingungen von 1 bis 3 gewählt wurden:

Figure imgb0003
In contrast, the eyeglass frames 4 to 6 were treated after pickling in an electrolyte of the following composition, the anodizing conditions being chosen from 1 to 3:
Figure imgb0003

In beiden Fällen wurde eine Eloxalschichtdicke von ca. 10 µm erreicht; die Brillen waren bis auf das Aussehen der Zwickel an den Scharnieren gleich.In both cases an anodized layer thickness of approx. 10 µm was achieved; the glasses were the same except for the appearance of the gusset on the hinges.

Während die Brillengestelle 1 bis 3 an den Scharnieren nach dem Einfärben der Eloxalschicht uneinheitlicher aussahen, vermittelten die Brillengestelle 4 bis 6 ein einheitliches optisches Aussehen. Daraus resultiert, daß der Komplexbildner an der Phasengrenze zum Aluminium zu einer homogeneren Oxidbildung beiträgt.While the eyeglass frames 1 to 3 on the hinges looked more inconsistent after coloring the anodized layer, the eyeglass frames 4 to 6 gave a uniform visual appearance. As a result, the complexing agent contributes to a more homogeneous oxide formation at the phase boundary with aluminum.

Claims (6)

1. Verfahren zum Anodisieren von Aluminiumwerkstoffen und aluminierten Teilen in wässrig, alkalischen Phosphationen enthaltenden, Anodisierelektrolyten, pdadurch gekennzeichnet , daß auf den Aluminiumwerkstoff und aluminierten Teilen in einem keine Formierschichten bildenden Anodisierbad,enthaltend pro Liter 10 bis 200g Trinatriumphosphat oder Trikaliumphosphat,bei Temperaturen von 0 bis 15 °C unter Durchleiten von CO2-freier oder CO2-armer Luft eine 10 bis 20 µm dicke Aluminiumoxidschicht ohne Glanzeffekt erzeugt wird.1. A method for anodizing aluminum materials and aluminized parts in aqueous, alkaline phosphate ions, anodizing electrolytes, pd characterized in that on the aluminum material and aluminized parts in an anodizing bath not forming forming layers, containing 10 to 200 g trisodium phosphate or tripotassium phosphate per liter at temperatures of 0 up to 15 ° C while passing through CO 2 -free or CO 2 -free air, a 10 to 20 µm thick aluminum oxide layer is produced without a gloss effect. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet , daß das Anodisierbad mit Gleichstrom oder Impulsstrom betrieben wird.2. The method according to claim 1, characterized in that the anodizing bath is operated with direct current or pulse current. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet , daß bei 0 bis 10 °C anodisiert wird.3. The method according to claim 1 and 2, characterized in that is anodized at 0 to 10 ° C. 4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet , daß das Anodisierbad pro Liter 50 bis 150g Na3PO4 . 12 H20 oder K3PO4 . 7 H 2 0 enthält.4. The method according to claim 1 to 3, characterized in that the anodizing bath per liter 50 to 150g Na 3 PO 4th 12 H 2 0 or K 3 PO 4 . 7 H 2 0 contains. 5. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet , daß das Bad außerdem pro Liter 1 bis 20g eines Komplexbildners enthält.5. The method according to claim 1 to 4, characterized in that the bath also contains 1 to 20 g of a complexing agent per liter. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet , daß das Bad pro Liter 1 bis 6g Natriumcyanid enthält.6. The method according to claim 5, characterized in that the bath contains 1 to 6 g of sodium cyanide per liter.
EP83102616A 1982-03-30 1983-03-16 Process for anodising aluminium products and aluminised parts Expired EP0090268B1 (en)

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AT83102616T ATE28760T1 (en) 1982-03-30 1983-03-16 PROCESS FOR ANODISING ALUMINUM MATERIALS AND ALUMINATED PARTS.

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DE19823211759 DE3211759A1 (en) 1982-03-30 1982-03-30 METHOD FOR ANODIZING ALUMINUM MATERIALS AND ALUMINUM PARTS
DE3211759 1982-03-30

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EP0090268A2 true EP0090268A2 (en) 1983-10-05
EP0090268A3 EP0090268A3 (en) 1985-05-15
EP0090268B1 EP0090268B1 (en) 1987-08-05

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EP (1) EP0090268B1 (en)
JP (1) JPS58177493A (en)
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DE (2) DE3211759A1 (en)

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US5097109A (en) * 1990-02-20 1992-03-17 General Motors Corporation Insulated aluminum weld fixture and a method of making same
CN1306071C (en) * 2001-08-14 2007-03-21 镁技术有限公司 Magnesium anodisation system and methods
US6591954B2 (en) 2001-09-28 2003-07-15 Eaton Corporation Clutch brake
US7569132B2 (en) * 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
US7820300B2 (en) * 2001-10-02 2010-10-26 Henkel Ag & Co. Kgaa Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to organic or inorganic coating
US7452454B2 (en) * 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
US7578921B2 (en) * 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
US6916414B2 (en) * 2001-10-02 2005-07-12 Henkel Kommanditgesellschaft Auf Aktien Light metal anodization
JP5334445B2 (en) * 2008-04-07 2013-11-06 本田技研工業株式会社 Aluminum alloy member and manufacturing method thereof
US9701177B2 (en) 2009-04-02 2017-07-11 Henkel Ag & Co. Kgaa Ceramic coated automotive heat exchanger components
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Also Published As

Publication number Publication date
EP0090268B1 (en) 1987-08-05
US4439287A (en) 1984-03-27
ATE28760T1 (en) 1987-08-15
JPH0359149B2 (en) 1991-09-09
DE3211759A1 (en) 1983-10-06
EP0090268A3 (en) 1985-05-15
DE3372871D1 (en) 1987-09-10
JPS58177493A (en) 1983-10-18

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