EP0186897B1 - Mittel und Verfahren zur Erzeugung farbloser Verdichtungsschichten auf anodisierten Aluminiumoberflächen - Google Patents

Mittel und Verfahren zur Erzeugung farbloser Verdichtungsschichten auf anodisierten Aluminiumoberflächen Download PDF

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Publication number
EP0186897B1
EP0186897B1 EP85116510A EP85116510A EP0186897B1 EP 0186897 B1 EP0186897 B1 EP 0186897B1 EP 85116510 A EP85116510 A EP 85116510A EP 85116510 A EP85116510 A EP 85116510A EP 0186897 B1 EP0186897 B1 EP 0186897B1
Authority
EP
European Patent Office
Prior art keywords
solution
dyes
nickel
solutions
aluminum
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
EP85116510A
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German (de)
English (en)
French (fr)
Other versions
EP0186897A1 (de
Inventor
Dieter Dr. Brodalla
Winfried Kirchhoff
Hans-Jürgen Dr. Göhausen
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT85116510T priority Critical patent/ATE41448T1/de
Publication of EP0186897A1 publication Critical patent/EP0186897A1/de
Application granted granted Critical
Publication of EP0186897B1 publication Critical patent/EP0186897B1/de
Expired 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
    • 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
    • C25D11/243—Chemical after-treatment using organic dyestuffs

Definitions

  • the invention relates to a solution and a method for producing colorless, compacted layers on anodized aluminum surfaces in the course of the so-called “cold compression”.
  • the technology In contrast to the so-called “hot compression", in which the pores of anodized aluminum surfaces are closed by treatment with water, water vapor or metal salt solutions above 90 ° C and aluminum surfaces are made corrosion-resistant and resistant to other external influences, the technology generally means the so-called «Cold compression or « cold impregnation or «low-temperature compression processes with which the porosity of anodized aluminum surfaces is reduced at temperatures between 15 and 70 ° C and the surface properties are significantly improved. The main goal is improved corrosion protection compared to an undensified surface.
  • DE-A-3 301 507 also describes a method for cold-compacting workpieces made of aluminum and its alloys, in which solutions containing fluorine or fluoride, for. a. solutions containing nickel fluoride and / or cobalt fluoride can also be used.
  • DE-A-3411 678 discloses a process for the post-compression of aluminum and aluminum alloys after the anodization, in which aqueous solutions of at least one nickel salt are added nonionic surfactants which are capable of lowering the surface tension of the compression bath. Organosilicon compounds are preferably used for this purpose.
  • All of the described processes have in common that aqueous solutions of certain nickel salts are used.
  • the nickel ions are incorporated into the surface layer when they come into contact with the freshly anodized aluminum surfaces, whereby - depending on the anions that are also incorporated - there is a more or less strong greenish discolouration of the aluminum surfaces, particularly when viewed from an angle or at an acute angle becomes visible.
  • the greenish surface discoloration is very annoying because it changes the actual natural tone of the aluminum metal.
  • Monoazo dyes are mainly used in the aluminum industry to consciously color anodized aluminum surfaces.
  • the dyes penetrate into the porous surfaces of anodized aluminum parts under adsorption, after which the colored layers are usually compacted by treatment in hot aqueous solutions.
  • substances are added to the compression solutions that prevent the formation of sealing coatings (see: Aluminum 47, 245 (1971)).
  • nickel salts such as nickel acetate
  • the invention is therefore based on the object of providing a method for cold compression of anodized aluminum surfaces in which, despite the use of nickel salt aqueous solutions, colorless layers can be generated and the greenish discoloration caused by nickel ions in the surface layers can be avoided.
  • Aqueous solutions of nickel fluoride absorb light in the wavelength ranges 350 to 450 nm and 650 to 850 nm.
  • the invention relates to an aqueous solution for producing colorless compression layers on anodized aluminum surfaces at temperatures in the range from 15 to 70 ° C. and pH values in the range from 5 to 7.5, the 1 to 5 g of nickel per liter of solution in the form of a water-soluble nickel salt , and optionally further organic and inorganic auxiliaries customary in the cold compaction of anodized aluminum surfaces, one or more organic dyes which have an absorption maximum in the range from 450 to 600 nm, an extinction coefficient of at least 1 - 10 3 l ⁇ mol- '- cm-' have in a molecularly dispersed solution in the solution and do not undergo any precipitation reactions with nickel ions and any auxiliaries present in the solution.
  • the invention also relates to a process for producing colorless compression layers by treating anodized aluminum surfaces with nickel ions and optionally further aqueous solutions containing organic and / or inorganic auxiliaries customary in cold compression anodized aluminum surfaces at temperatures in the range from 15 to 70 ° C. and pH values in Range from 5 to 7.5, which is characterized in that one or more organic dyes are added to the compression solutions, which have an absorption maximum in the range from 450 to 600 nm, an extinction coefficient of at least 1 103 1 - mol -1 ⁇ cm - 1, have a molecular dispersion in the solution and do not undergo precipitation reactions with nickel ions and / or the other constituents of the solution.
  • azo or azo metal dyes proved to be suitable for fulfilling all of the criteria (a) to (d) mentioned. From the large group of azo or azo metal dyes, however, those are not suitable which either cannot diffuse into the pores of the aluminum oxide hydrate surface due to their molecular size or which result in the precipitation with the nickel ions of the solutions.
  • the use of the azo and azo metal dyes suitable according to the invention means that, for a given nickel concentration of, for example, 1 to 5 g of nickel / I on the one hand and concentrations of dye molecules of, for example, 1 to 10 mg of dye / I on the other hand, within a treatment time of 0.1 to 1 , 5 min per micron layer thickness, the nickel ions and dye molecules are embedded in the aluminum oxide hydrate layer in such a ratio that the result is absorption of the light energy of the entire visible spectrum.
  • Azo dyes which are sold by the company SANDOZ under the names Aluminum Red GLW or Aluminum Violet CLW were preferably used in the context of the present invention.
  • Aluminum red GLW is an azo metal complex with copper and aluminum violet CLW is a purely organic azo dye.
  • the dyes mentioned At high color intensity (extinction coefficient about 1. 10 4 I - moH - cm- 1 ), the dyes mentioned have an absorption maximum at 500 or 555 nm and, due to their molecular size (molecular weight approx. 800 to 1,000), diffuse easily into the pores of the anodized Aluminum surfaces.
  • Using these dyes have proven to be expedient in the compression process at nickel concentrations in the range of approximately 2 g nickel / l dye concentrations of approximately 2.5 mg dye / l, the treatment solution containing all components appearing colorless.
  • Aqueous solutions of nickel salts which are prepared by dissolving in particular NiF 2 - 4 H 2 O or other nickel salts such as nickel sulfate or nickel acetate, and adding appropriate amounts of alkali metal fluorides, are used for the compression.
  • the solutions according to the invention can optionally contain further organic and / or inorganic auxiliaries customary in cold compression anodized aluminum surfaces.
  • Surfactants and / or organic compounds such as alcohols, amines, ketones and / or ethers and / or organosilicon compounds and / or fluorides of different metals and / or salts with complex anions are suitable as such.
  • these solutions are not essential and the anodized aluminum surfaces are colorlessly compacted even in the absence of such customary auxiliaries.
  • anodized surfaces made of aluminum or its alloys primarily with an aqueous solution of the dyes which can be used according to the invention and then to compact them with an aqueous nickel salt solution using the cold method.
  • the reddish coloration of the aluminum oxide surface obtained in the first process step compensates for the subsequent greenish coloration resulting from the sealing process, so that aluminum oxide surfaces are formed with the natural color of the aluminum.
  • a dye rinsing bath must always be operated with a water overflow, which makes it difficult to maintain a certain dye concentration and results in large dye losses.
  • anodizing lines that are commonly used for the fully automatic treatment of surfaces made of aluminum and its alloys have no space for the installation of a separate pre-dye bath.
  • aqueous solutions which contain 1 to 5 g of nickel per liter of solution in the form of a water-soluble nickel salt, 0.5 to 80 mg per liter of solution of one or more organic dyes which meet the above-mentioned criteria (a) to (d) must and, if necessary, contain further organic and / or inorganic auxiliaries customary in the cold compaction of anodized aluminum surfaces.
  • the solutions preferably have a dye content of 1 to 10 mg, particularly preferably 1 to 2.9 mg of dye per liter of solution, this amount of dye being dependent on the one hand on the nickel concentration and on the other hand on the color intensity of the dye used.
  • Treatment solutions are used in which the coloring of the nickel ions is compensated for by the red coloring caused by the dye molecules and which thus appear colorless.
  • Dyes with an extinction coefficient in the range from 5. 103 to 5 ⁇ 10 5 l ⁇ ml -1 ⁇ cm- 'with an absorption maximum in the range from 490 to 560 nm decolorize in a concentration of 1 to 10 mg / l solutions containing 1 to Contain 5 g / l nickel.
  • anodized surfaces made of aluminum or its alloys are treated with such dye solutions. This takes place in that the corresponding aluminum parts are immersed in the solutions containing the components according to the invention for a time of 0.1 to 1.5 min / ⁇ m layer thickness, preferably for a time of 0.4 to 1.2 min / ⁇ m layer thickness . It is then conveniently rinsed with demineralized water.
  • the solutions are re-sharpened in accordance with the consumption of their components, so that continuous process control is possible.
  • the bath components in solid form or in the form of suitable supplementary solutions, both the nickel content and the dye content are set to a constant value and the exact observance of these and the other bath parameters is continuously monitored.
  • aqueous solutions were used which had the composition mentioned in the individual examples.
  • the pH was between 5.5 and 6.5 and was corrected with acetic acid if necessary.
  • the treatment temperature was 28 to 32 ° C, the treatment time was 0.5 min / ⁇ m layer thickness.
  • the nickel content of the solutions was monitored by complexometric titration.
  • the solution was photometrized in cuvettes with a layer thickness of 1 cm in a spectrophotometer.
  • the extinctions (cm- ') at the characteristic absorption wavelength (Ni: 395 and 720 nm; dyes: 500 and 555 nm) are directly dependent on the respective concentration and can therefore be correlated.
  • the pH was 5.8.
  • Nickel ions and dye were thus simultaneously embedded in the pores of the aluminum oxide hydrate layer.
  • Example 2 Under the same conditions as in Example 1, a solution was used for densification which contained only 7.0 g of NiF 2 .4H 2 0 per liter of solution, ie no dye. A comparable drop in the absorption typical of nickel was observed, but surfaces with greenish discoloration resulted.
  • the pH was 5.8.
  • the pH was 5.8.
  • nickel ions By adding the supplementary solution, the content of nickel ions was kept almost constant, while the dye concentration was still subject to wide fluctuations. However, nickel and dyes were incorporated into the pores of the aluminum oxide hydrate surfaces and consequently colorless surfaces with a natural metallic luster were obtained.
  • the nickel ion and dye content could be adjusted to almost constant values.
  • the present supplementary solution proved to be the most suitable for the given experimental setup.
  • the content of nickel ions and dye molecules could be kept almost constant by re-sharpening the solution with the supplementary solutions mentioned. To the extent necessary, both coloring components were built into the pores of the aluminum oxide hydrate surface. This resulted in undyed layers with a natural metallic sheen.
  • a cold impregnation solution containing 2 g / l of nickel and 1.4 g / l of fluoride was prepared in an 18 m 3 bath container. 1.25 mg / l aluminum red GLW and 1.25 mg / l aluminum violet CLW were added so that the solution appeared colorless when visually assessed. Over a first test period of 8 weeks, a total of 11,500 m 2 of anodized aluminum parts with layer thicknesses of the oxide layer between 2 and 25 ⁇ m and different anodization conditions were treated in this bath.
  • the nickel content was determined by complexometric titration. The dye content was checked photometrically. If necessary to maintain the nickel concentration at 2 g / l, a nickel salt solution, which also contained the above-mentioned dyes, was added. This solution contained nickel and dye (50% aluminum red GLW and 50% aluminum violet) in a weight ratio of 1: 0.0015. The total consumption was 12.3 kg Ni and 18 g dye mixture. All parts treated in this way could be colorless in this bath, i. H. without greenish discoloration. The solution also remained colorless when viewed visually.

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  • 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)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Sealing Material Composition (AREA)
EP85116510A 1985-01-03 1985-12-23 Mittel und Verfahren zur Erzeugung farbloser Verdichtungsschichten auf anodisierten Aluminiumoberflächen Expired EP0186897B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85116510T ATE41448T1 (de) 1985-01-03 1985-12-23 Mittel und verfahren zur erzeugung farbloser verdichtungsschichten auf anodisierten aluminiumoberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3500079 1985-01-03
DE19853500079 DE3500079A1 (de) 1985-01-03 1985-01-03 Mittel und verfahren zur erzeugung farbloser verdichtungsschichten auf anodisierten aluminiumoberflaechen

Publications (2)

Publication Number Publication Date
EP0186897A1 EP0186897A1 (de) 1986-07-09
EP0186897B1 true EP0186897B1 (de) 1989-03-15

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EP85116510A Expired EP0186897B1 (de) 1985-01-03 1985-12-23 Mittel und Verfahren zur Erzeugung farbloser Verdichtungsschichten auf anodisierten Aluminiumoberflächen

Country Status (8)

Country Link
US (1) US4756771A (ja)
EP (1) EP0186897B1 (ja)
JP (1) JPS61159597A (ja)
AT (1) ATE41448T1 (ja)
AU (1) AU573065B2 (ja)
CA (1) CA1268604A (ja)
DE (2) DE3500079A1 (ja)
ZA (1) ZA8618B (ja)

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Publication number Publication date
US4756771A (en) 1988-07-12
ATE41448T1 (de) 1989-04-15
AU5179386A (en) 1986-07-10
AU573065B2 (en) 1988-05-26
CA1268604A (en) 1990-05-08
JPS61159597A (ja) 1986-07-19
JPS6363639B2 (ja) 1988-12-08
DE3500079A1 (de) 1986-07-10
ZA8618B (en) 1986-08-27
EP0186897A1 (de) 1986-07-09
DE3568800D1 (en) 1989-04-20

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