EP1464733B1 - Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium - Google Patents

Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium Download PDF

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Publication number
EP1464733B1
EP1464733B1 EP02290376A EP02290376A EP1464733B1 EP 1464733 B1 EP1464733 B1 EP 1464733B1 EP 02290376 A EP02290376 A EP 02290376A EP 02290376 A EP02290376 A EP 02290376A EP 1464733 B1 EP1464733 B1 EP 1464733B1
Authority
EP
European Patent Office
Prior art keywords
bath
aluminium
molybdenum oxide
sealing
clogging
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
Application number
EP02290376A
Other languages
English (en)
French (fr)
Other versions
EP1464733A1 (de
Inventor
Claude Brault
Jean Pierre Richard
Jacques Pagetti
Marie Pierre Gigandet
Virginie Moutarlier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aalberts Surface Technologies SAS
Original Assignee
Societe de Galvanoplastie Industrielle SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Societe de Galvanoplastie Industrielle SAS filed Critical Societe de Galvanoplastie Industrielle SAS
Priority to AT02290376T priority Critical patent/ATE294265T1/de
Priority to EP02290376A priority patent/EP1464733B1/de
Priority to ES02290376T priority patent/ES2238058T3/es
Priority to DE60203945T priority patent/DE60203945T8/de
Publication of EP1464733A1 publication Critical patent/EP1464733A1/de
Application granted granted Critical
Publication of EP1464733B1 publication Critical patent/EP1464733B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Definitions

  • the present invention relates to a method of clogging by hydration of the obtained oxide layer by anodizing aluminum or an aluminum alloy, devoid of hexavalent chromium.
  • Aluminum alloys are, despite the development of composites, the most used on aircraft and helicopter cells. Protection against corrosion and assembly by collage of these materials therefore remain the concerns main.
  • chromates to the clogging water allows enhance the corrosion resistance of the film.
  • the chromate ion is one of the most important corrosion inhibitors more efficient for aluminum. Inhibition is due to the formation on the surface of the metal of a protective film formed by the reduction of the chromate ion.
  • the inventors have given themselves as their goal to find a non-harmful substitute for hexavalent chromium, while maintaining the resistance properties in corrosion of the material and its adhesion properties vis-à-vis paint systems.
  • JP-A-02 025592 describes a process for clogging an aluminum oxide layer obtained by anodization.
  • the sealing bath is an aqueous solution of molybdate containing a benzotriazole or a tolytriazole and the molybdate used can be Na 2 MoO 4 or K 2 MoO 4 at a concentration of preferably between 500 and 5000 ppm, that is to say ie 0.5 and 5 g / l. No pH value or immersion time or hydration rate is specified.
  • molybdenum oxide could be used as a substitute for chromium hexavalent in the clogging process.
  • the of hydration represents in mass the quantity of fixed water when clogging compared to the total mass of the coating (alumina + water).
  • the molybdenum oxide is present in the form of salt, preferably in the form of sodium molybdate, potassium or ammonium, or in the form of a complex, of preferably in the form of an amine and acid complex molybdic.
  • the molybdenum oxide is present in the form of ammonium molybdate.
  • Ammonium molybdate can be used directly as a salt containing 85% MoO 3 or can be used in the form of pure molybdenum oxide with added ammonia according to the following equation: 7 MoO 3 + 6 NH 4 OH ⁇ (NH 4 ) 6 Mo 7 O 24 + 3H 2 O
  • the pH of the clogging baths used in the according to the invention is stabilized at 6 +/- 1 by addition of a buffer salt such as, for example, acetate ammonium.
  • the sealing method according to the invention can be used on pure aluminum or alloys aluminum type 2024 T3, 5086 or 7075 T73 previously anodized according to anodizing method conventional methods, such as of sulfuric, chromic, alkaline or sulfoborique.
  • Parts obtained after clogging according to the present invention have very good resistance to corrosion, between 500 and 750 hours and the hydration levels correspond to those observed with a classic clogging in the presence of chromium Hexavalent.
  • the paint system offers perfect adhesion, as well as excellent performance at salt spray corresponding to that which we obtain with chromic oxidation followed by clogging with hexavalent chromium.
  • the measurement of the hydration rate is carried out by a gravimetric measurement of the hydration of the coating.
  • the thickness of the layer is measured by a test according to the ISO 2360 standard; the clogging is measured by the method dye absorption system, referenced NF A 91408, and the continuity of the layer is measured by the test ISO 2085 standard.
  • the adhesion of the paint was measured according to described by the company PRC-De Soto which includes the successive application of a layer of primer P99, based on phenolic butyral, then deposit of an anticorrosion primer PAC 33, then a layer polyurethane-based PU 66 finishes, the above designations being registered trademarks of the PRC-De Soto company.
  • the first layer has a thickness of 4 to 11 ⁇ m, the total of the first two layers a thickness of 14 to 29 ⁇ m, and the total of the three layers a thickness of 39 to 64 ⁇ m.
  • test pieces are anodized for about 40 minutes to one hour in a bath containing 35 to 60 g / l of chromic acid at a voltage of between 5 and 90 volts and a density of the electric current of 0.5 to 50 amperes / cm 2 .
  • the anodized part is rinsed for about 2 minutes and immersed in a clogging bath containing either 85% MoO 3 ammonium molybdate added directly to the bath or ammonium molybdate prepared by adding ammonia to MoO. 3 according to the equation 7 MoO 3 + 6 NH 4 OH ⁇ (NH 4 ) 6 Mo 7 O 24 + 3H 2 O
  • the duration of immersion in the clogging bath is 20 minutes and the bath temperature is 97 ° C.
  • the clogging bath comprises 3.6 g / l MoO 3 to which NH 4 OH ammonia and ammonium acetate have been added.
  • the bath temperature is 97 ° C and the immersion time is 40 minutes.
  • the test pieces used are 2024 T3 and 7075 T7 test pieces.
  • a series of test pieces is used to measure the adhesion of painting, the other series is used to evaluate the resistance corrosion.
  • the hydration rate, the layer thickness, the layer continuity and absorption tests of dye are compliant.
  • the paint system offers perfect adhesion before and after immersion in the water, as well as an excellent held in salt spray.
  • Parts processed by the process of the invention have a thickness, a continuity of layer, a absorption of dyes identical to those gets after chromic anodizing and clogging with hexavalent chromium.
  • the corrosion resistance measured by the holding of the salt spray is quite satisfactory and well over 500 hours of exposure.
  • the paint system offers a perfect adhesion and excellent hold salt mist also corresponding to that which one gets after chromic oxyanodization and clogging with hexavalent chromium.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (5)

  1. Verfahren zum Abdichten der Mikroporen durch Hydratisierung der Oxidschicht, erhalten durch Eloxierung von Aluminium oder einer Aluminiumlegierung, dadurch gekennzeichnet, dass das Abdichtungsbad ausgeführt wird unter den folgenden Bedingungen:
    Basis des Bads: entmineralisiertes Wasser, welches ein Korrosionsschutzmittel auf der Grundlage von Molybdänoxid (MoO3) in einer Menge von 1 bis 5 g/l Molybdänoxid enthält,
    Temperatur des Bads: 90-100°C,
    Eintauchdauer: 20-60 min,
    pH des Bads: 6 +/- 1,
    wobei die Dauer und die Temperatur in umgekehrter Beziehung zueinander stehen und das Verfahren einen Hydratisierungsgrad zwischen 10 und 30%, vorzugsweise zwischen 15 und 25% ermöglicht.
  2. Verfahren zum Abdichten der Mikroporen nach Anspruch 1, dadurch gekennzeichnet, dass das Molybdänoxid in Salzform, vorzugsweise in Form von Natrium-, Kalium- oder Ammoniummolybdat, oder in Form eines Komplexes, vorzugsweise in Form eines Komplexes von einem oder mehreren Amin(en) und von Molybdänsäure vorliegt.
  3. Verfahren zum Abdichten der Mikroporen nach Anspruch 1, dadurch gekennzeichnet, dass das Molybdänoxid in Form von Ammoniummolybdat vorliegt.
  4. Verfahren zum Abdichten der Mikroporen nach Anspruch 1, dadurch gekennzeichnet, dass das Abdichtungsbad ausgeführt wird unter den folgenden Bedingungen:
    Basis des Bads: entmineralisiertes Wasser, welches ein Korrosionsschutzmittel auf der Grundlage von Molybdänoxid (MoO3) in einer Menge von 3,6 g/l Molybdänoxid, 0,75 g/l Ammoniak und 3 g/l Ammoniumacetat enthält,
    Temperatur des Bads: 97°C und
    Eintauchdauer: 40 min.
  5. Verfahren zur Herstellung von Teilen aus Aluminium oder einer Aluminiumlegierung, die eloxiert und deren Mikroporen abgedichtet sind, dadurch gekennzeichnet, dass das Abdichten der Mikroporen gemäß einem der Ansprüche 1 bis 4 ausgeführt wird.
EP02290376A 2002-02-15 2002-02-15 Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium Expired - Lifetime EP1464733B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AT02290376T ATE294265T1 (de) 2002-02-15 2002-02-15 Verwendung eines molybdats in einem verfahren zur versieglung von anodischen oxidschichten auf aluminium
EP02290376A EP1464733B1 (de) 2002-02-15 2002-02-15 Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium
ES02290376T ES2238058T3 (es) 2002-02-15 2002-02-15 Utilizacion de molibdato en un procedimiento de colmatado de una capa de oxido obtenida por anodizacion de aluminio.
DE60203945T DE60203945T8 (de) 2002-02-15 2002-02-15 Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP02290376A EP1464733B1 (de) 2002-02-15 2002-02-15 Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium

Publications (2)

Publication Number Publication Date
EP1464733A1 EP1464733A1 (de) 2004-10-06
EP1464733B1 true EP1464733B1 (de) 2005-04-27

Family

ID=32842681

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02290376A Expired - Lifetime EP1464733B1 (de) 2002-02-15 2002-02-15 Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium

Country Status (4)

Country Link
EP (1) EP1464733B1 (de)
AT (1) ATE294265T1 (de)
DE (1) DE60203945T8 (de)
ES (1) ES2238058T3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12560092B2 (en) 2021-10-29 2026-02-24 Rtx Corporation Coating for aluminum alloy aerostructures

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2812116C2 (de) * 1977-03-30 1982-06-03 Yoshida Kogyo K.K., Tokyo Verfahren zum Aufbringen eines härtbaren Überzugs auf eine gedichtete anodische Oxidschicht auf Aluminium
US4515919A (en) * 1983-05-09 1985-05-07 Lockheed Corporation Protective coating composition and process for aluminum and aluminum alloys
JPH0225592A (ja) * 1988-07-14 1990-01-29 Fujitsu Ltd 陽極酸化皮膜の封孔処理方法
US5205922A (en) * 1990-11-20 1993-04-27 The United States Of America As Represented By The Secretary Of The Navy Formation of pitting resistant anodized films on aluminum

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12560092B2 (en) 2021-10-29 2026-02-24 Rtx Corporation Coating for aluminum alloy aerostructures

Also Published As

Publication number Publication date
ATE294265T1 (de) 2005-05-15
ES2238058T3 (es) 2005-08-16
DE60203945D1 (de) 2005-06-02
DE60203945T8 (de) 2006-07-27
DE60203945T2 (de) 2006-02-23
EP1464733A1 (de) 2004-10-06

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