EP0103234B1 - Procédé de colmatage de couches d'oxyde obtenues par voie anodique sur de l'aluminium ou des alliages d'aluminium - Google Patents

Procédé de colmatage de couches d'oxyde obtenues par voie anodique sur de l'aluminium ou des alliages d'aluminium Download PDF

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Publication number
EP0103234B1
EP0103234B1 EP83108560A EP83108560A EP0103234B1 EP 0103234 B1 EP0103234 B1 EP 0103234B1 EP 83108560 A EP83108560 A EP 83108560A EP 83108560 A EP83108560 A EP 83108560A EP 0103234 B1 EP0103234 B1 EP 0103234B1
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European Patent Office
Prior art keywords
acid
sealing
water
reaction
soluble salts
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
Application number
EP83108560A
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German (de)
English (en)
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EP0103234A3 (en
EP0103234A2 (fr
Inventor
Hans Jürgen Dr. Göhausen
Winfried Kirchhoff
Jürgen Lindener
Harald Wennemann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT83108560T priority Critical patent/ATE28218T1/de
Publication of EP0103234A2 publication Critical patent/EP0103234A2/fr
Publication of EP0103234A3 publication Critical patent/EP0103234A3/de
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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 invention relates to a method for compacting anodically produced oxide layers on aluminum or aluminum alloys by treatment with aqueous solutions at elevated temperatures, the occurrence of disruptive aluminum hydroxide coatings (sealing coatings) on the surfaces being prevented.
  • Anodically produced oxide layers are often applied to aluminum surfaces for the purpose of corrosion protection. These oxide layers protect the aluminum surfaces from the effects of weather and other corrosive media. Furthermore, the anodic oxide layers are also applied in order to obtain a harder surface and thus to achieve increased wear resistance of the aluminum. Due to the intrinsic color of the oxide layers and their partially easy egg coloring, particularly decorative effects can be achieved.
  • a number of methods are known for applying anodic oxide layers to aluminum.
  • the oxide layers are produced with direct current in solutions of sulfuric acid (direct current-sulfuric acid method).
  • These layers can be subsequently colored by dipping in solutions of a suitable dye or by alternating current treatment in an electrolyte containing metal salts.
  • solutions of organic acids such as, in particular, sulfophthalic acid or sulfanilic acid, or else these in a mixture with sulfuric acid, are frequently used for the application of the oxide layers. The latter methods are known as color anodization methods.
  • these anodically applied oxide layers do not meet all requirements with regard to corrosion protection, since they have a porous structure. For this reason, it is necessary to densify the oxide layers. This densification is often carried out with hot or boiling water and referred to as «sealing. This closes the pores and thus significantly increases the protection against corrosion.
  • the so-called sealing coating is also formed on the entire surface.
  • This consists of hydrated aluminum oxide and is not touch-proof, so that the decorative effect of the layer is adversely affected. It also reduces the adhesive strength when gluing such aluminum parts and, due to the increased effective surface area, promotes later contamination and corrosion. For these reasons, it was previously necessary to remove the covering by hand, mechanically or chemically.
  • the object of the present invention is to further improve the previous methods of operation and to make them even safer in order to arrive at an improved method for compacting anodic oxide layers on aluminum or aluminum alloys.
  • phosphinocarboxylic acids used in the process according to the invention can be prepared by known processes.
  • reaction products of hypophosphorous acid are used, such as those used in the reaction with acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, maleic acid, glutaronic acid, citraconic acid, itaconic acid, 2-butene-2-carboxylic acid, dimethyl maleic acid, 2-methylene glutaric acid, butene polycarboxylic acids and ethylene tetracarboxylic acids, ethylene tetracarboxylic acids, ethylene tetracarboxylic acids and ethylene tetracarboxylic acids, ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids Cinnamic acid are created.
  • reaction products with hypophosphorous acid derived from higher unsaturated carboxylic acids can also be used.
  • their use in terms of optimal bath management becomes increasingly complex.
  • their water-soluble salts in which all or part of the acidic protons have been replaced, for example, by alkali metal, ammonium, alkaline earth metal, alkylammonium or alkanolammonium ions, can also be used for carrying out the process.
  • the salts are used in an amount which corresponds to 0.0005 to 0.5 g / l of the free acids.
  • a preferred embodiment of the process is that the compression is carried out in solutions which contain the reaction products formed in the addition of 2-8 molecules of acrylic acid to the two PH functions of the hypophosphorous acid or their water-soluble salts in an amount of 0.0005 to 0.5 g / l included.
  • a further embodiment of the process consists in that the compaction is carried out in solutions which contain the reaction products obtained in the reaction of maleic acid with hypophosphorous acid or their water-soluble salts.
  • the solutions of the acids or salts according to the invention are adjusted to a pH of 4 to 8, preferably 5 to 6. This setting can be made with ammonia or acetic acid.
  • the compression with the solutions according to the invention is carried out at temperatures between 90 ° C. and the boiling point. In general, a temperature of 95 to 100 ° C is maintained.
  • the compression time is within the usual range and is about 1.5 to 3.5 min / gm layer thickness of the anodic oxide layer.
  • Additives known per se, such as nickel or cobalt acetate, can also be added to the compression solutions for this purpose in small amounts between 0.0001 and 0.5 g / l.
  • the new process makes it possible to prevent the formation of sealing coatings without impairing the anodic oxide layer or reducing the quality of the compression.
  • the special properties of the active ingredients used greatly reduce the risk of unintentional harmful overdosing. Rinsing after compaction or spraying to remove any residue from the surface are not required.
  • the appearance of the surface is not influenced by the method according to the invention; the effects that were achieved by pretreatment and anodization are retained.
  • the designation of the aluminum alloys was made in accordance with DIN 1725.
  • the quality of the oxide layers was determined by the apparent conductance or y-value according to DIN 50949 and by the loss factor d according to ISO / TC 79 / SC2 (ALL-1) Doc. 65 E.
  • the quality of the compression was also checked using the chromophosphoric acid test (ISO 3210).
  • Al 99.5 An alkaline degreased and pickled aluminum sheet (Al 99.5) was compressed after the anodic oxidation using the direct current sulfuric acid method (layer thickness 20 ⁇ m) in a solution containing 0.01 g / l of a reaction product of 2 mol maleic acid in deionized water Contained 1 mol of hypophosphorous acid and had been adjusted to pH 5.8 with ammonia.
  • the reaction product of 2 moles of maleic acid with 1 mole of hypophosphorous acid was prepared by adding 45 g of sodium hypophosphite monohydrate to 100 g of maleic acid dissolved in 250 ml of water. The reaction mixture was heated to 60 ° C. and 8 g of ammonium persulfate dissolved in water were added dropwise in small portions over 4 hours. The reaction mixture was kept at 60 ° C. for a further 2 hours. The solution thus obtained was used for the experiments without isolating the reaction product, the active substance content resulting from the raw materials used.
  • the anodized aluminum was densified for 60 min. performed at 98 ° C. After that, the sheets showed no sealing coating. The layer thickness remained unchanged at 20 ⁇ m. The dielectric loss factor was 0.42 and the admittance had dropped from over 400 to 12.5 ⁇ S. A weight loss of 12.9 mg / dm 2 was found in the chromophosphoric acid test.
  • Alkaline degreased and pickled profiles made from the alloy AIMgSi 0.5 were anodized according to the direct current sulfuric acid-oxalic acid method (layer thickness 19 ⁇ m) and colored electrolytically bronze in a tin-containing coloring electrolyte. The profiles were then compacted for a time corresponding to 3 min / ⁇ m layer thickness at 98 ° C. in a solution adjusted to pH 6.0, which solution had been obtained in deionized water 0.001 g / l of a reaction product of hypophosphorous acid with 8 mol of acrylic acid.
  • the reaction product of acrylic acid with hypophosphorous acid was prepared as follows:
  • Profiles made from the alloy AIMgSi 0.5 degreased and pickled by the usual method were anodized using the direct current sulfuric acid method (layer thickness 18-21 ⁇ m). These were at a pH of 5.8 (adjusted with ammonia or acetic acid) in solutions containing the reaction products of hypophosphorous acid with itaconic acid, Citra consic acid or 1-butene-2,3,4-tricarboxylic acid - prepared by the process mentioned in Example 1 - contained in the stated amounts at 97-100 ° C for 60 min. condensed.
  • the table shows the deposit-preventing effect and the influence of the substances on the layer quality, expressed according to the results of the admittance measurement of the dielectric loss factor and the weight loss in the chromium-phosphoric acid test.
  • the sealing coating is prevented and the layer quality is not impaired.
  • Comparative experiments with cyclohexane hexacarboxylic acid and phosphonobutane-2,3,4-tricarboxylic acid were included in the table, which show that, although the sealing coating is prevented in the case of the comparison substances, severe layer damage occurs even at the higher concentrations. (See table on page 6 f.)

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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Sealing Material Composition (AREA)
  • Casings For Electric Apparatus (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Cookers (AREA)
  • Catalysts (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Gasket Seals (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Insulated Conductors (AREA)
  • Physical Vapour Deposition (AREA)

Claims (7)

1. Procédé de compactage de couches d'oxydes anodiquement engendrées sur l'aluminium ou sur les alliages d'aluminium par traitement avec des solutions aqueuses ayant une valeur de pH de 4 à 8 à des températures entre 90 °C et la température d'ébullition, caractérisé en ce qu'on exécute le compactage avec des solutions qui contiennent 0,0005 à 0,5 g/litre d'acides phosphinocarboxyliques qui ont été formés, dans la réaction de l'acide hypophosphoreux avec des acides carboxyliques insaturés mono- ou polyfonctionnels de formule générale I
Figure imgb0017
dans laquelle
R1 représente de l'hydrogène ou un des radicaux
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
de même que
R2, R3 et R4 signifient de l'hydrogène ou un des radicaux -CH3, -C2H5, -COOH, ―CH2―COOH. ―CH2―CH2―COOH, en l'occurrence au moins un des radicaux R1 à R4 représentant ou contenant un groupe COOH, dans le rapport molaire de 1 : 1 à 1 : 8,

ou de leurs sels solubles dans l'eau.
2. Procédé selon la revendication 1, caractérisé en ce qu'on exécute le compactage avec des solutions qui contiennent des acides phosphinocarboxyliques, qui sont formés dans la réaction de 1 mole d'acide hypophosphoreux avec 2 à 8 moles d'acide acrylique, ou leurs sels solubles dans l'eau.
3. Procédé selon la revendication 1, caractérisé en ce qu'on exécute le compactage avec des solutions qui contiennent des acides phosphinocarboxyliques, qui sont formés dans la réaction de 1 mole d'acide hypophosphoreux avec 1 à 2 moles d'acide maléique, ou leurs sels solubles dans l'eau.
4. Procédé selon la revendication 1, caractérisé en ce qu'on exécute le compactage avec des solutions qui contiennent des acides phosphinocarboxyliques, qui sont formés dans la réaction de 1 mole d'acide hypophosphoreux avec 1 à 2 moles d'acide itaconique, ou leurs sels solubles dans l'eau.
5. Procédé selon la revendication 1, caractérisé en ce qu'on exécute le compactage avec des solutions qui contiennent des acides phosphinocarboxyliques, qui sont formés dans la réaction de 1 mole d'acide hypophosphoreux avec 1 à 2 moles d'acide citraconique. ou leurs sels solubles dans l'eau.
6. Procédé selon la revendication 1, caractérisé en ce qu'on exécute le compactage avec des solutions qui contiennent des acides phosphinocarboxyliques, qui sont formés dans la réaction de 1 mole d'acide hypophosphoreux avec 1 à 2 moles d'acide 1-butène-2,3,4-tricarboxylique, ou leurs sels solubles dans l'eau.
7. Procédé selon les revendications 1 à 6, caractérisé en ce que la valeur du pH est de 5 à 6.
EP83108560A 1982-09-09 1983-08-31 Procédé de colmatage de couches d'oxyde obtenues par voie anodique sur de l'aluminium ou des alliages d'aluminium Expired EP0103234B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83108560T ATE28218T1 (de) 1982-09-09 1983-08-31 Verfahren zum verdichten von anodisch erzeugten oxidschichten auf aluminium oder aluminiumlegierungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823233411 DE3233411A1 (de) 1982-09-09 1982-09-09 Verfahren zum verdichten von anodisch erzeugten oxidschichten auf aluminium oder aluminiumlegierungen
DE3233411 1982-09-09

Publications (3)

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EP0103234A2 EP0103234A2 (fr) 1984-03-21
EP0103234A3 EP0103234A3 (en) 1985-09-25
EP0103234B1 true EP0103234B1 (fr) 1987-07-08

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US (1) US4445983A (fr)
EP (1) EP0103234B1 (fr)
JP (1) JPS5970797A (fr)
AT (1) ATE28218T1 (fr)
AU (1) AU565677B2 (fr)
BR (1) BR8304885A (fr)
CA (1) CA1212072A (fr)
DE (2) DE3233411A1 (fr)
DK (1) DK158748C (fr)
ES (1) ES8405450A1 (fr)
GR (1) GR79624B (fr)
NO (1) NO159945C (fr)
PT (1) PT77295B (fr)
ZA (1) ZA836673B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3900169A1 (de) * 1989-01-05 1990-07-12 Henkel Kgaa Verfahren zum impraegnieren anodisch erzeugter oberflaechen von aluminium
DE3917188A1 (de) * 1989-05-26 1990-11-29 Happich Gmbh Gebr Verfahren zur erzeugung farbiger oberflaechen auf teilen aus aluminium oder aluminium-legierungen
EP0454323B1 (fr) * 1990-04-25 1995-11-02 Nalco Chemical Company Oligomères de phosphinate, leurs compositions, leur préparation et leur utilisation
DE19621818A1 (de) * 1996-05-31 1997-12-04 Henkel Kgaa Kurzzeit-Heißverdichtung anodisierter Metalloberflächen mit tensidhaltigen Lösungen
DE10161478A1 (de) * 2001-12-14 2003-06-26 Henkel Kgaa Verfahren zum Verdichten von anodisierten Metalloberflächen im mittleren Temperaturbereich
JP4936791B2 (ja) * 2006-05-22 2012-05-23 株式会社東芝 曝気レス水処理装置
US8609254B2 (en) 2010-05-19 2013-12-17 Sanford Process Corporation Microcrystalline anodic coatings and related methods therefor
US8512872B2 (en) 2010-05-19 2013-08-20 Dupalectpa-CHN, LLC Sealed anodic coatings
CN109518253B (zh) * 2017-09-18 2021-05-21 中铝材料应用研究院有限公司 一种基于铝合金表面的高胶接和耐腐蚀的阳极氧化方法
CN109518252B (zh) * 2017-09-18 2021-05-21 中铝材料应用研究院有限公司 一种基于铝合金的高胶接和耐腐蚀的阳极氧化方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3400023A (en) * 1964-05-11 1968-09-03 Kelite Corp Composition for preservation of metals, process and article
US3634146A (en) * 1969-09-04 1972-01-11 American Cyanamid Co Chemical treatment of metal
US3813303A (en) * 1971-04-14 1974-05-28 Alusuisse Method of treating an aluminum surface
US3770513A (en) * 1972-06-08 1973-11-06 American Cyanamid Co Chemical treatment of metal
US4293441A (en) * 1979-03-12 1981-10-06 Minnesota Mining And Manufacturing Company Corrosion inhibiting heat transfer liquid

Also Published As

Publication number Publication date
NO159945C (no) 1989-02-22
JPS5970797A (ja) 1984-04-21
AU565677B2 (en) 1987-09-24
GR79624B (fr) 1984-10-31
PT77295A (de) 1983-10-01
DK371883A (da) 1984-03-10
CA1212072A (fr) 1986-09-30
ES525508A0 (es) 1984-06-01
ZA836673B (en) 1984-04-25
JPH0312159B2 (fr) 1991-02-19
ES8405450A1 (es) 1984-06-01
DE3233411A1 (de) 1984-03-15
DK371883D0 (da) 1983-08-15
DE3372382D1 (en) 1987-08-13
NO832927L (no) 1984-03-12
AU1892383A (en) 1984-03-15
US4445983A (en) 1984-05-01
DK158748C (da) 1990-12-10
NO159945B (no) 1988-11-14
DK158748B (da) 1990-07-09
EP0103234A3 (en) 1985-09-25
BR8304885A (pt) 1984-04-24
PT77295B (de) 1986-02-04
EP0103234A2 (fr) 1984-03-21
ATE28218T1 (de) 1987-07-15

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