EP1464733B1 - Use of molybdate in a process for sealing anodic oxide films formed on aluminium - Google Patents

Use of molybdate in a process for sealing anodic oxide films formed on 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
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EP
European Patent Office
Prior art keywords
bath
aluminium
molybdenum oxide
sealing
clogging
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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.)
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EP02290376A
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German (de)
French (fr)
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EP1464733A1 (en
Inventor
Claude Brault
Jean Pierre Richard
Jacques Pagetti
Marie Pierre Gigandet
Virginie Moutarlier
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Aalberts Surface Technologies SAS
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Societe de Galvanoplastie Industrielle SAS
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Priority to DE60203945T priority Critical patent/DE60203945T8/en
Priority to AT02290376T priority patent/ATE294265T1/en
Priority to ES02290376T priority patent/ES2238058T3/en
Priority to EP02290376A priority patent/EP1464733B1/en
Publication of EP1464733A1 publication Critical patent/EP1464733A1/en
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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
    • C25D11/24—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.

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

Abstract

The consolidation by hydration of the oxide layer obtained by anodization of aluminium or aluminium alloy is carried out in bath under the following conditions: (a) base of the bath: dematerialized water containing 1 to 5 g/l of an anti-corrosion agent with a molybdenum oxide (MoO3) base; (b) bath temperature: 90 - 100[deg]C; (c) duration of immersion: 20 - 60 minutes; (d) pH of the bath: 6 +- 1; (e) the time and the temperature being in inverse relation; (f) the method allowing a rate of hydration of between 10 and 30%, preferably between 15 and 25%. An independent claim is also included for the preparation of anodized and consolidated aluminium or aluminium alloy components in which the consolidation is carried out by the inventive method.

Description

La présente invention concerne un procédé de colmatage par hydratation de la couche d'oxyde obtenue par anodisation d'aluminium ou d'un alliage d'aluminium, dépourvu de chrome hexavalent.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.

Les alliages d'aluminium sont, malgré le développement des composites, les matériaux les plus utilisés sur les cellules des avions et des hélicoptères. La protection contre la corrosion et l'assemblage par collage de ces matériaux restent donc les préoccupations principales.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.

Les traitements de surface par voie humide tels que l'anodisation sont actuellement les plus répandus pour répondre à ces besoins. Pour améliorer la résistance en corrosion des alliages d'aluminium anodisés, une étape appelée "colmatage" est nécessaire. Cette opération consiste à transformer les cellules d'alumine anhydre en alumine monohydratée de formule Al2O3, nH2O par simple immersion dans l'eau pure à 100°C. L'alumine hydratée a alors un volume de 33% supérieur à celui de l'alumine anhydre entraínant un "bouchage" des pores.Wet surface treatments such as anodizing are currently the most common to meet these needs. To improve the corrosion resistance of anodized aluminum alloys, a step called "clogging" is necessary. This operation consists in transforming the cells of anhydrous alumina into alumina monohydrate of formula Al 2 O 3 , nH 2 O by simple immersion in pure water at 100 ° C. The hydrated alumina then has a volume 33% greater than that of the anhydrous alumina resulting in a "clogging" of the pores.

L'ajout de chromates à l'eau de colmatage permet de renforcer la résistance en corrosion du film. En effet, l'ion chromate est un des inhibiteurs de corrosion les plus efficaces pour l'aluminium. L'inhibition est due à la formation à la surface du métal d'un film protecteur formé par la réduction de l'ion chromate. The addition of chromates to the clogging water allows enhance the corrosion resistance of the film. Indeed, 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.

Mais il est avancé que l'ion chromate pourrait être à la fois toxique et cancérigène. Compte-tenu de ces risques éventuels vis-à-vis de l'environnement et de la santé, des restrictions quant à l'utilisation de ce composé sont nécessaires.But it is argued that the chromate ion could be both toxic and carcinogenic. Given these possible risks to the environment and to the health, restrictions on the use of this compound are necessary.

Aussi, les inventeurs se sont-ils donnés pour but de trouver un substitut non nocif au chrome hexavalent, tout en maintenant les propriétés de résistance en corrosion du matériau et ses capacités d'adhérence vis-à-vis des systèmes de peinture.Also, 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.

De nombreuses études ont déjà été réalisées pour tenter de remplacer le chrome hexavalent. Ainsi, l'utilisation des sels de terres rares (Shih H. et al., ASTM Spec. Tech. Publ. (1992), 1134, 180-195) a-t-elle été évoquée, de même que l'utilisation de solutions diluées de vanadate ou la formation d'un oxyde de zirconium à la surface du matériau (Hinton B.R.W., Metal Finishing (1991), 9, 55-61)Many studies have already been done to try to replace hexavalent chromium. Thus, the use of rare earth salts (Shih H. et al ., ASTM Spec Tech Publ (1992), 1134, 180-195) has been discussed, as has the use of dilute solutions of vanadate or the formation of a zirconium oxide on the surface of the material (Hinton BRW, Metal Finishing (1991), 9, 55-61)

Beaucoup de ces différents composés sont utilisés en présence d'un polymère pour former en surface une résine capable d'avoir de bonnes propriétés protectrices (Hinton B.R.W., Metal Finishing (1991), 10, 15-20).Many of these different compounds are used in the presence of a polymer to form on the surface a resin capable of having good protective properties (Hinton BRW, Metal Finishing (1991), 10, 15-20).

JP-A-02 025592 décrit un procédé de colmatage d'une couche d'oxyde d'aluminium obtenue par anodisation. Le bain de colmatage est une solution aqueuse de molybdate contenant un benzotriazole ou un tolytriazole et le molybdate utilisé peut être du Na2MoO4 ou K2MoO4 à une concentration comprise de préférence entre 500 et 5 000 ppm, c'est-à-dire 0,5 et 5 g/l. Aucune valeur de pH ni de durée d'immersion ou de taux d'hydratation n'est précisée.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.

Or, les inventeurs ont trouvé, de manière surprenante, que l'oxyde de molybdène pouvait être utilisé comme produit de remplacement du chrome hexavalent dans le procédé de colmatage.Now, the inventors have found, so surprisingly, that molybdenum oxide could be used as a substitute for chromium hexavalent in the clogging process.

Aussi, l'invention a-t-elle pour objet un procédé de colmatage par hydratation de la couche d'oxyde obtenue par anodisation d'aluminium ou d'un alliage d'aluminium, le bain de colmatage étant réalisé dans les conditions suivantes:

  • base du bain: eau déminéralisée contenant un agent anticorrosion à base d'oxyde de molybdène (MoO3) à raison de 1 à 5 g/l d'oxyde de molybdène,
  • température du bain: 90-100 °C,
  • durée d'immersion: 20-60 minutes, et
  • pH du bain: 6 +/- 1,
le temps et la température étant en relation inverse et ledit procédé permettant un taux d'hydratation compris entre 10 et 30%, de préférence entre 15 et 25%.Also, the subject of the invention is a process for clogging by hydration of the oxide layer obtained by anodizing aluminum or an aluminum alloy, the clogging bath being produced under the following conditions:
  • base of the bath: demineralized water containing an anticorrosion agent based on molybdenum oxide (MoO 3 ) at a rate of 1 to 5 g / l of molybdenum oxide,
  • bath temperature: 90-100 ° C,
  • immersion time: 20-60 minutes, and
  • pH of the bath: 6 +/- 1,
the time and the temperature being in inverse relation and said method allowing a hydration rate of between 10 and 30%, preferably between 15 and 25%.

Au sens de la présente invention, le taux d'hydratation représente en masse la quantité d'eau fixée lors du colmatage par rapport à la masse totale du revêtement (alumine + eau).For the purposes of the present invention, the of hydration represents in mass the quantity of fixed water when clogging compared to the total mass of the coating (alumina + water).

Dans un mode préféré de réalisation de l'invention, l'oxyde de molybdène est présent sous forme de sel, de préférence sous forme de molybdate de sodium, de potassium ou d'ammonium, ou sous forme d'un complexe, de préférence sous forme d'un complexe d'amine et d'acide molybdique.In a preferred embodiment of the invention, 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.

Dans un mode encore plus avantageux de réalisation de l'invention, l'oxyde de molybdène est présent sous forme de molybdate d'ammonium. Le molybdate d'ammonium peut être utilisé directement sous forme d'un sel contenant 85% de MoO3 ou peut être utilisé sous forme d'oxyde de molybdène pur additionné d'ammoniaque selon l'équation suivante: 7 MoO3 + 6 NH4OH → (NH4)6Mo7O24 + 3 H2O In an even more advantageous embodiment of the invention, 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

De manière particulièrement avantageuse, le procédé de colmatage est réalisé dans les conditions suivantes:

  • base du bain: eau déminéralisée contenant un agent anticorrosion à base d'oxyde de molybdène (MoO3) à raison de 3,6 g/l d'oxyde de molybdène, 0,75 g/l d'ammoniaque et 3 g/l d'acétate d'ammonium,
  • température du bain: 97°C, et
  • durée d'immersion: 40 minutes.
In a particularly advantageous manner, the clogging process is carried out under the following conditions:
  • base of the bath: demineralized water containing an anticorrosion agent based on molybdenum oxide (MoO 3 ) at a rate of 3.6 g / l of molybdenum oxide, 0.75 g / l of ammonia and 3 g / l ammonium acetate,
  • bath temperature: 97 ° C, and
  • immersion time: 40 minutes.

Le pH des bains de colmatage utilisé dans le procédé selon l'invention est stabilisé à 6 +/- 1 par ajout d'un sel tampon tel que par exemple l'acétate d'ammonium.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.

Le procédé de colmatage selon l'invention peut être utilisé sur de l'aluminium pur ou des alliages d'aluminium du type 2024 T3, 5086 ou 7075 T73 préalablement anodisé selon une méthode d'anodisation conventionnelle, comme par exemple les méthodes d'anodisation sulfurique, chromique, alcaline ou sulfoborique.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.

Aussi, l'invention a-t-elle pour objet un procédé de fabrication de pièces d'aluminium ou d'alliage d'aluminium anodisé et colmaté caractérisé en ce que le bain de colmatage est réalisé dans les conditions suivantes:

  • base du bain: eau déminéralisée contenant un agent anticorrosion à base d'oxyde de molybdène (MoO3) à raison de 1 à 5 g/l d'oxyde de molybdène,
  • température du bain: 90-100 °C,
  • durée d'immersion: 20-60 minutes, et
  • pH du bain: 6 +/- 1,
le temps et la température étant en relation inverse et ledit procédé permettant un taux d'hydratation compris entre 10 et 30%, de préférence entre 15 et 25%. Also, the subject of the invention is a process for manufacturing anodized and clogged aluminum or aluminum alloy parts, characterized in that the clogging bath is produced under the following conditions:
  • base of the bath: demineralized water containing a molybdenum oxide (M oO 3 ) anticorrosion agent at a rate of 1 to 5 g / l of molybdenum oxide,
  • bath temperature: 90-100 ° C,
  • immersion time: 20-60 minutes, and
  • pH of the bath: 6 +/- 1,
the time and the temperature being in inverse relation and said method allowing a hydration rate of between 10 and 30%, preferably between 15 and 25%.

Les pièces obtenues après colmatage selon la présente invention présentent une très bonne résistance à la corrosion, comprise entre 500 et 750 heures et les taux d'hydratation correspondent à ceux que l'on observe avec un colmatage classique en présence de chrome hexavalent. Par ailleurs, le système de peinture offre une adhérence parfaite, ainsi qu'une excellente tenue au brouillard salin correspondant à celle que l'on obtient avec l'oxydation chromique suivie d'un colmatage avec du chrome hexavalent.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. Moreover, 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.

Les exemples qui suivent illustrent l'invention.The following examples illustrate the invention.

1. Caractéristiques mesurées.1. Measured characteristics. 1.1. Résistance à la corrosion.1.1. Corrosion resistance.

Elle est mesurée par le test du brouillard salin selon la norme ISO 9227 - NSS.It is measured by the salt spray test according to ISO 9227 - NSS.

1.2. Taux d'hydratation.1.2. Hydration rate.

La mesure du taux d'hydratation est réalisée par une mesure gravimétrique de l'hydratation du revêtement.The measurement of the hydration rate is carried out by a gravimetric measurement of the hydration of the coating.

1.3. Tests non destructifs sur l'anodisation chromique.1.3. Non-destructive tests on anodizing Chromic.

L'épaisseur de la couche est mesurée par un test selon la norme ISO 2360; le colmatage est mesuré par la méthode d'absorption de colorants référencé NF A 91408, et la continuité de la couche est mesurée par le test référentiel ISO 2085.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.

1.4. Adhérence d'un système de peinture polyuréthane souple.1.4. Adhesion of a paint system soft polyurethane.

L'adhérence de la peinture a été mesurée suivant la technique décrite par la société PRC-De Soto qui comprend l'application successive d'une couche de primaire d'accrochage P99, à base de butyral phénolique, puis le dépôt d'un primaire anticorrosion PAC 33, puis une couche de finition PU 66 à base de polyuréthane, les désignations ci-dessus étant des marques déposées de la société PRC-De Soto.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.

La première couche a une épaisseur de 4 à 11 µm, le total des deux premières couches une épaisseur de 14 à 29 µm, et le total des trois couches une épaisseur de 39 à 64 µm.The first layer has a thickness of 4 to 11 μm, the total of the first two layers a thickness of 14 to 29 μm, and the total of the three layers a thickness of 39 to 64 μm.

Un essai d'adhérence "Q + S" selon la norme ISO 2409-1976 est mesuré après 14 jours d'immersion dans l'eau.ISO "Q + S" adhesion test according to ISO standard 2409-1976 is measured after 14 days of immersion in the water.

1.5. Résistance à la corrosion du système oxydation anodique chromique (OAC) + peinture.1.5. Corrosion resistance of the system chromic anodic oxidation (OAC) + painting.

On réalise une rayure en croix sur la protection et on laisse la pièce exposée pendant 3 000 heures.We make a cross stripe on the protection and we leave the piece exposed for 3,000 hours.

2. Essais.2. Tests. Premier essai:First try:

On utilise une ligne pilote avec des cuves de 250 1 de volume; l'alliage utilisé est de l'alliage 2024 T3 sous forme d'éprouvette de dimension 120 x 60 x 08 mm, brut de laminage. Après dégraissage-rinçage, les éprouvettes sont anodisées pendant environ 40 minutes à une heure dans un bain contenant 35 à 60 g/l d'acide chromique sous une tension comprise entre 5 et 90 volts et une densité du courant électrique de 0,5 à 50 ampères/cm2. La pièce anodisée est rincée pendant environ 2 minutes et immergée dans un bain de colmatage contenant soit du molybdate d'ammonium à 85% en MoO3 ajouté directement dans le bain, soit du molybdate d'ammonium préparé par ajout d'ammoniaque sur du MoO3 selon l'équation 7 MoO3 + 6 NH4OH → (NH4)6Mo7O24 + 3 H2O A pilot line is used with tanks of 250 liters of volume; the alloy used is alloy 2024 T3 in the form of a specimen of dimension 120 x 60 x 08 mm, gross rolling. After degreasing and rinsing, the 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

La durée d'immersion dans le bain de colmatage est de 20 minutes et la température du bain est de 97°C.The duration of immersion in the clogging bath is 20 minutes and the bath temperature is 97 ° C.

Les résultats sont donnés dans le tableau 1 suivant. [ ] du bain Température Temps de colmatage % hydratation Tenue brouillard salin Epaisseur courant de Foucault Test d'absorp -tion de colorant Molybdate d'ammonium 1 g/l 97°C 20 min 29,7 550 h 3,2 0 oxyde de molybdène 1 g/l + ammoniaque 97°C 20 min 30 600 h 3,5 0 Molybdate d'ammonium 1 g/l 97°C 20 min 29,5 600 h 3 0 oxyde de molybdène + ammoniaque 1 g/l 97°C 20 min 28,7 650 h 3,3 0 The results are given in Table 1 below. [] bath Temperature Clogging time % hydration Salt mist holding Eddy Current Thickness Dye absorbtion test Ammonium molybdate 1 g / l 97 ° C 20 min 29.7 550 h 3.2 0 molybdenum oxide 1 g / l + ammonia 97 ° C 20 min 30 600 h 3.5 0 Ammonium molybdate 1 g / l 97 ° C 20 min 29.5 600 h 3 0 Molybdenum oxide + ammonia 1 g / l 97 ° C 20 min 28.7 650 h 3.3 0

On observe une bonne tenue à la corrosion prise entre 550 et 650 heures avec les deux types de dérivés d'oxyde de molybdène et une hydratation d'environ 30%. Le test d'absorption de colorant montre que le colmatage est complet.Good corrosion resistance is observed between 550 and 650 hours with both types of oxide derivatives of molybdenum and a hydration of about 30%. The test dye absorption shows that clogging is full.

Deuxième essai:Second trial:

Les conditions sont les mêmes que pour le premier essai, mais le pH est tamponné à 6 avec de l'acétate d'ammonium. Cet essai a été réalisé comme dans le premier essai en utilisant MoO3 + NH4OH avec une concentration en MoO3 de 1 g/l ou de 3,6 g/l, la température du bain étant de 85 ou 97°C. Les résultats sont exprimés dans le tableau 2 ci-dessous. [ ] du bain Température Temps de colmatage % hydratation Tenue brouillard salin Epaisseur courant de Foucault Test d'absorption de colorant 1 g/l 85 °C 5 2,5 288 2,8 5 10 2,5 288 2,9 5 15 2,1 288 2,8 5 20 3,0 288 2,8 5 30 3,6 288 2,9 5 40 2,7 288 2,9 5 1 g/l 97°C 5 5,1 450 2,9 5 10 6,7 450 3,0 5 15 6,7 450 3,0 5 20 6,3 450 3,0 5 30 10,2 450 3,2 2-3 40 20,6 450 3,0 1-2 3,6 g/l 85°C 5 4,8 450 3,0 5 10 5,2 450 3,0 5 15 5,8 450 3,0 5 20 6,1 450 3,0 5 30 5,7 450 3,0 5 40 6,0 450 3,0 5 3,6 g/l 97°C 5 5,7 556 3,0 5 10 5,9 556 3,0 5 15 10,7 556 3,2 2-3 20 12,0 556 3,2 2 30 13,1 700 3,3 2 40 19,9 700 3,0 1-2 The conditions are the same as for the first test, but the pH is buffered to 6 with ammonium acetate. This test was carried out as in the first test using MoO 3 + NH 4 OH with a concentration of MoO 3 of 1 g / l or 3.6 g / l, the temperature of the bath being 85 or 97 ° C. The results are shown in Table 2 below. [] bath Temperature Clogging time % hydration Salt mist holding Eddy Current Thickness Dye absorption test 1 g / l 85 ° C 5 2.5 288 2.8 5 10 2.5 288 2.9 5 15 2.1 288 2.8 5 20 3.0 288 2.8 5 30 3.6 288 2.9 5 40 2.7 288 2.9 5 1 g / l 97 ° C 5 5.1 450 2.9 5 10 6.7 450 3.0 5 15 6.7 450 3.0 5 20 6.3 450 3.0 5 30 10.2 450 3.2 2-3 40 20.6 450 3.0 1-2 3.6 g / l 85 ° C 5 4.8 450 3.0 5 10 5.2 450 3.0 5 15 5.8 450 3.0 5 20 6.1 450 3.0 5 30 5.7 450 3.0 5 40 6.0 450 3.0 5 3.6 g / l 97 ° C 5 5.7 556 3.0 5 10 5.9 556 3.0 5 15 10.7 556 3.2 2-3 20 12.0 556 3.2 2 30 13.1 700 3.3 2 40 19.9 700 3.0 1-2

On observe une très bonne tenue au brouillard salin comprise entre 500 et 700 heures et des taux d'hydratation supérieurs à 20% qui correspondent à ceux que l'on observe avec les colmatages classiques.We observe a very good resistance to salt spray between 500 and 700 hours and rates hydration levels greater than 20% which correspond to those that we observe with classical blockages.

Troisième essai:Third test:

Le bain de colmatage comprend 3,6 g/l de MoO3 auquel on a ajouté NH4OH ammoniaque et de l'acétate d'ammonium. La température du bain est de 97°C et le temps d'immersion est de 40 minutes. Les éprouvettes utilisées sont des éprouvettes 2024 T3 et 7075 T7.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.

Un système de peinture a été appliqué sur deux séries d'éprouvettes: P99 + PAC 33 x 2 + PU66 (réf. 5440/2047) A paint system was applied to two sets of test pieces: P99 + PAC 33 x 2 + PU66 (ref 5440/2047)

Une série d'éprouvettes sert à mesurer l'adhérence de la peinture, l'autre série sert à évaluer la résistance de la corrosion.A series of test pieces is used to measure the adhesion of painting, the other series is used to evaluate the resistance corrosion.

Les résultats sont regroupés dans les deux tableaux 3 et 4 qui suivent: Alliages [ ] du bain (g/l) Température Temps de Colmatage % hydratation Tenue Brouillard salin Epaisseur courant de Foucault Test d'absorption de colorant 2024 T3 3,6 97°C 40 min 21,1 670 h 4,0 0-1 7075 T7 3,6 97°C 40 min 22,4 540 h 3,1 0-1 Alliages Q+S Q+S+H2O Tenue brouillard salin 2024 T3 0 0 3 000 heures RAS 7075 T7 0 0 3 000 heures RAS The results are grouped in the following two tables 3 and 4: alloys [] bath (g / l) Temperature Clogging time % hydration Salt spray holding Eddy Current Thickness Dye absorption test 2024 T3 3.6 97 ° C 40 min 21.1 670 h 4.0 0-1 7075 T7 3.6 97 ° C 40 min 22.4 540 h 3.1 0-1 alloys Q + S Q + S + H2O Salt mist holding 2024 T3 0 0 3000 hours RAS 7075 T7 0 0 3000 hours RAS

On observe une bonne tenue au brouillard salin avec l'alliage 2024 T3 et des performances satisfaisantes avec l'alliage 7075 T7 qui est par nature très sensible à la corrosion.We observe a good resistance to salt spray with 2024 T3 alloy and satisfactory performance with 7075 T7 alloy which is inherently very sensitive to corrosion.

Le taux d'hydratation, l'épaisseur de couche, la continuité de couche et les tests d'absorption de colorant sont conformes.The hydration rate, the layer thickness, the layer continuity and absorption tests of dye are compliant.

Le système peinture offre une adhérence parfaite avant et après immersion dans l'eau, ainsi qu'une excellente tenue au brouillard salin.The paint system offers perfect adhesion before and after immersion in the water, as well as an excellent held in salt spray.

Les résultats ci-dessus montrent que le molybdène peut être utilisé comme élément de remplacement du chrome hexavalent dans des bains de colmatage.The results above show that molybdenum can to be used as a substitute for chromium hexavalent in clogging baths.

Les pièces traitées par le procédé de l'invention présentent une épaisseur, une continuité de couche, une absorption de colorants identiques à ceux que l'on obtient après anodisation chromique et colmatage avec du chrome hexavalent.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.

La résistance à la corrosion mesurée par la tenue du brouillard salin est tout à fait satisfaisante et largement supérieure à 500 heures d'exposition.The corrosion resistance measured by the holding of the salt spray is quite satisfactory and well over 500 hours of exposure.

Par ailleurs, le système de peinture offre une adhérence parfaite ainsi qu'une excellente tenue au brouillard salin correspondant également à celle que l'on obtient après oxyanodisation chromique et colmatage avec du chrome hexavalent.Moreover, 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.

Claims (5)

  1. Process of sealing by hydrating the oxide layer obtained by anodizing aluminium or an aluminium alloy, characterized in that the sealing bath is realized under the following conditions:
    bath base: demineralized water comprising an anti-corrosion agent based on molybdenum oxide (MoO3) in a proportion of from 1 to 5 g/l of molybdenum oxide,
    bath temperature: 90-100°C,
    immersion time: 20-60 minutes,
    bath pH: 6 +/- 1,
    the time and the temperature being in inverse relation and the said process allowing a degree of hydration of between 10% and 30%, preferably between 15% and 25%.
  2. Process of sealing according to Claim 1, characterized in that the molybdenum oxide is present in salt form, preferably in the form of sodium, potassium or ammonium molybdate or in the form of a complex, preferably in the form of a complex of amine and molybdic acid.
  3. Process of sealing according to Claim 1, characterized in that the molybdenum oxide is present in the form of ammonium molybdate.
  4. Process of sealing according to Claim 1, characterized in that the sealing bath is realized under the following conditions:
    bath base: demineralized water comprising an anti-corrosion agent based on molybdenum oxide (MoO3) in a proportion of from 3.6 g/l of molybdenum oxide, 0.75 g/l of ammonia and 3 g/l of ammonium acetate,
    bath temperature: 97°C, and
    immersion time: 40 minutes.
  5. Process for producing anodized and sealed aluminium or aluminium-alloy parts, characterized in that the sealing is realized according to any one of Claims 1 to 4.
EP02290376A 2002-02-15 2002-02-15 Use of molybdate in a process for sealing anodic oxide films formed on aluminium Expired - Lifetime EP1464733B1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE60203945T DE60203945T8 (en) 2002-02-15 2002-02-15 Use of a molybdate in a process for sealing anodic oxide layers on aluminum
AT02290376T ATE294265T1 (en) 2002-02-15 2002-02-15 USE OF A MOLYBDATE IN A PROCESS FOR SEALING ANODIC OXIDE LAYERS ON ALUMINUM
ES02290376T ES2238058T3 (en) 2002-02-15 2002-02-15 USE OF MOLIBDATE IN A COLMATATE PROCEDURE OF AN OXIDE LAYER OBTAINED BY ALUMINUM ANODIZATION.
EP02290376A EP1464733B1 (en) 2002-02-15 2002-02-15 Use of molybdate in a process for sealing anodic oxide films formed on aluminium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP02290376A EP1464733B1 (en) 2002-02-15 2002-02-15 Use of molybdate in a process for sealing anodic oxide films formed on aluminium

Publications (2)

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EP1464733A1 EP1464733A1 (en) 2004-10-06
EP1464733B1 true EP1464733B1 (en) 2005-04-27

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AT (1) ATE294265T1 (en)
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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2812116C2 (en) * 1977-03-30 1982-06-03 Yoshida Kogyo K.K., Tokyo Method of applying a curable coating to a sealed anodic oxide layer on aluminum
US4515919A (en) * 1983-05-09 1985-05-07 Lockheed Corporation Protective coating composition and process for aluminum and aluminum alloys
JPH0225592A (en) * 1988-07-14 1990-01-29 Fujitsu Ltd Pore sealing treatment of anodic oxide film
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

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DE60203945D1 (en) 2005-06-02
DE60203945T2 (en) 2006-02-23
DE60203945T8 (en) 2006-07-27
ATE294265T1 (en) 2005-05-15
EP1464733A1 (en) 2004-10-06
ES2238058T3 (en) 2005-08-16

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