EP1299577A2 - Procede de fabrication de surfaces dorees de pieces en aluminium ou en alliages d'aluminium a l'aide de formulations contenant des sels d'argent - Google Patents

Procede de fabrication de surfaces dorees de pieces en aluminium ou en alliages d'aluminium a l'aide de formulations contenant des sels d'argent

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Publication number
EP1299577A2
EP1299577A2 EP01967140A EP01967140A EP1299577A2 EP 1299577 A2 EP1299577 A2 EP 1299577A2 EP 01967140 A EP01967140 A EP 01967140A EP 01967140 A EP01967140 A EP 01967140A EP 1299577 A2 EP1299577 A2 EP 1299577A2
Authority
EP
European Patent Office
Prior art keywords
aluminum
acid
gold
silver
electrolyte
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.)
Withdrawn
Application number
EP01967140A
Other languages
German (de)
English (en)
Inventor
Werner Hesse
Bernd Laubusch
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1299577A2 publication Critical patent/EP1299577A2/fr
Withdrawn legal-status Critical Current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
    • C25D11/20—Electrolytic after-treatment
    • C25D11/22—Electrolytic after-treatment for colouring layers

Definitions

  • the invention relates to a method for obtaining gold-colored aluminum oxide layers, the use of silver salt-containing electrolytes for gold-colored coloring of aluminum oxide layers, an electrolyte solution for gold-colored coloring of the oxidized surface of aluminum or aluminum alloys and the use of the gold-colored colored workpieces based on the invention of aluminum or aluminum alloys.
  • Workpieces made of aluminum or aluminum alloys are generally provided with a protective aluminum oxide layer for protection against corrosion and wear or for decorative reasons. Since aluminum oxide is colorless and the oxide layer is porous, a colorless aluminum oxide layer with a high absorption capacity is usually obtained. To get decorative surfaces, e.g. for facade walls or visible components, these aluminum oxide layers are often colored.
  • Colored aluminum oxide layers are generally produced in two steps. First, the surface of the aluminum or aluminum alloy is oxidized. This oxide layer is then colored by absorbing organic or inorganic dyes into the capillary-shaped pores of the oxide layer.
  • the surface oxidation of the aluminum surface or the surface of aluminum alloys can be carried out chemically by dipping the workpieces in solutions of weakly attacking agents or by chromating and phosphating.
  • anodic oxidation by electrochemical means is more advantageous since thicker oxide coatings are obtained than by chemical treatment.
  • the most frequently used processes use sulfuric acid (S), oxalic acid (X) or chromic acid solutions as electrolytes. Only direct current is used in the chromic acid process, while the sulfuric acid and oxalic acid processes are operated both with direct current (GS or GX process) and with alternating current (WS or WX process). It is also possible to use a mixture of sulfuric acid and oxalic acid (GSX process). This is of some relevance because the mixture can be used at higher bath temperatures (22 - 24 ° C) than pure sulfuric acid (18 - 22 ° C).
  • the layer thickness of the oxide layer is approximately 10 to 30 ⁇ m in these processes. In some applications, particularly thin (a few ⁇ m in strip anodization) or particularly thick (up to approx. 80 ⁇ in hard anodization) oxide layers are generated.
  • anodized aluminum or aluminum alloy is colored in the aqueous phase with suitable organic or inorganic compounds without the effect of electricity.
  • Organic dyes anodized dyes, for example dyes from the Alizarin series or indigo dyes
  • Inorganic dyes can be deposited in the pores during chemical coloring by precipitation reactions or by hydrolysis of heavy metal salts.
  • the processes involved are difficult to control and there are often problems with reproducibility, that is, with maintaining the same color shades. For this reason, the electrolytic processes for coloring aluminum oxide layers have become more and more common. A number of electrolytic processes for producing colored aluminum oxide layers are known from the prior art.
  • No. 4,128,460 relates to a process for coloring aluminum or aluminum alloys by electrolysis, comprising anodizing the aluminum or aluminum alloys by customary methods and subsequent electrolysis in a bath, which comprises an aliphatic sulfonic acid and a metal salt, in particular a tin, Copper, lead or silver salt containing sulfonic acid.
  • a bath which comprises an aliphatic sulfonic acid and a metal salt, in particular a tin, Copper, lead or silver salt containing sulfonic acid.
  • the stability of the electrolysis bath is increased by an increased oxidation stability of the metal salts used and a uniform coloring of the surface of the aluminum or the aluminum alloys.
  • the hues obtained are given in Table 1 for various bath compositions, electrolysis voltages and electrolysis times.
  • EP-A 0 351 680 relates to the electrolytic coloring of anodically produced surfaces of aluminum and / or aluminum alloys in aqueous electrolytes containing silver salts by means of alternating current using p-toluenesulfonic acid. This gives the aluminum a gold color. Silver sulfate is preferably used as the silver salt. The use of p-toluenesulfonic acid is crucial to get a warm but reddish gold tone. If no p-toluenesulfonic acid is added, greenish tints are obtained.
  • the object of the present invention is therefore to provide a method for producing gold-colored aluminum oxide surfaces.
  • the process is said to lead to uniform and reproducible gold colorations, the color tone being as close as possible to that of natural gold.
  • the fastest possible coloring should be made possible without the addition of (environmentally harmful) additives such as p-toluenesulfonic acid.
  • a method for obtaining gold-colored aluminum oxide layers comprising the following steps: a) pretreatment of aluminum or aluminum alloys; b) anodic oxidation of aluminum or aluminum alloys (anodization); c) coloring the oxidized surface of the aluminum or aluminum alloys by an electrolytic process in an electrolyte containing an alkanesulfonic acid and an alkanesulfonate of the silver; d) aftertreatment of the gold-colored workpiece obtained after steps a), b) and c); e) if appropriate, recovery of the alkanesulfonic acid and / or its salts used, step e) being able to follow each step in which an alkanesulfonic acid can be used, in particular steps b) and / or c), or parallel to these steps can be carried out.
  • gold-colored aluminum oxide layers are obtained which are distinguished by a uniform coloring and an excellent surface quality, particularly with regard to light fastness and weather resistance. These preserved gold-colored workpieces are ideal for decorative purposes, for example for the production of window profiles and facade components.
  • Alkanesulfonic acids for the purposes of the present invention are understood to mean aliphatic sulfonic acids. On their aliphatic residue, these may optionally have functional groups or heteroatoms, e.g. Hydroxy groups. Alkanesulfonic acids of the general formulas are preferred
  • R is a hydrocarbon radical which can be branched or unbranched, having 1 to 12 carbon atoms, preferably having 1 to 6 carbon atoms, particularly preferably an unbranched hydrocarbon radical having 1 to 3 carbon atoms, very particularly preferably having 1 carbon atom, that is to say methanesulfonic acid.
  • R ' is a hydrocarbon radical which can be branched or unbranched, having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms, particularly preferably an unbranched hydrocarbon radical having 2 to 4 carbon atoms, it being possible for the hydroxyl group and the sulfonic acid group to be bonded to any carbon atoms, with the restriction that they are not bound to the same carbon atom.
  • methanesulfonic acid is very particularly preferably used as alkanesulfonic acid.
  • aluminum and aluminum alloys can be colored gold.
  • Particularly suitable aluminum alloys are alloys of aluminum with silicon and / or magnesium. Silicon and / or magnesium may be present in the alloy in a proportion of 2% by weight (Si) or 5% by weight (Mg).
  • the pretreatment of aluminum or aluminum alloys is a crucial step, since it determines the optical quality of the end product. Since the oxide layer produced during anodizing is transparent and this transparency is also retained during the coloring process in step c), any surface defect of the metallic workpiece remains visible up to the finished part.
  • the pretreatment is carried out using customary methods such as mechanical and / or electropolishing, dewaxing with neutral surfactants or organic solvents, glosses or pickling. Then it is generally rinsed with water.
  • solutions containing alkanesulfonic acid are also used in step a).
  • alkanesulfonic acids have already been mentioned above.
  • Methanesulfonic acid is particularly preferably used.
  • the anodization in step b) can be carried out by any method known from the prior art.
  • the anodization is preferably carried out in sulfuric acid as the electrolyte base.
  • the anodization is carried out in an electrolyte which contains 3 to 30% by weight of an alkanesulfonic acid.
  • the anodization is particularly preferably carried out in an electrolyte based on an alkanesulfonic acid or a mixture of an alkanesulfonic acid and another acid selected from sulfuric acid, phosphoric acid and oxalic acid.
  • the electrolyte very particularly preferably contains 20 to 100 parts by weight of an alkanesulfonic acid and 80 to 0 parts by weight of the other acid, the sum of alkanesulfonic acid and the other acid being 100 parts by weight and a concentration of 3 to 30 parts by weight .-% of the electrolyte.
  • anodization takes place more quickly than when using pure sulfuric acid.
  • anodizing is the rate-determining step. Depending on the coloring of the surface, this is 5 to 50 times slower than the subsequent coloring.
  • the electrolyte In addition to the corresponding acid, preferably sulfuric acid or an alkanesulfonic acid or a mixture of different acids selected from alkanesulfonic acid, sulfuric acid, phosphoric acid or oxalic acid, the electrolyte generally contains water and, if necessary, further additives such as aluminum sulfate.
  • the electrolysis time for achieving an optimum aluminum oxide layer thickness of generally 10 to 30 ⁇ m, preferably 15 to 30 ⁇ m, for a subsequent dyeing step is generally 10 to 60 minutes 30 to 50 minutes, whereby the exact time depends, among other things, on the current density.
  • the anodization of aluminum or aluminum alloys in step b) can be carried out either with the electrodeposition process or with continuous anodization, for example of strips, tubes or wires, by means of an electrolytic drawing process, for example for the production of tinplate.
  • the anodization can be operated both with direct current and with alternating current; the anodization is preferably operated with direct current.
  • the anodization is preferably carried out at temperatures from 17 to 24 ° C. If excessive temperatures are used, an irregular deposition of the oxide layer occurs, which is undesirable. If an electrolyte based on an alkanesulfonic acid is used, it is possible to carry out the anodization at temperatures up to 30 ° C. By carrying out at higher temperatures, energy costs for cooling the electrolyte can be saved. Cooling of the electrolyte during anodization is generally necessary because the anodization is exothermic.
  • the anodization is carried out at a current density of 0.5 to 5 A / dm 2 , preferably 0.5 to 3 A / dm, particularly preferably 1.0 to 2.5 A / dm.
  • the voltage is generally 1 to 30 V, preferably 2 to 20 V.
  • Suitable devices for carrying out the anodization are generally all known devices which are suitable for electro-immersion or for the continuous anodic oxidation of aluminum or aluminum alloys, e.g. by means of an electrolytic drawing process.
  • the aluminum oxide layer obtained is gold colored according to the invention.
  • This gold coloring is achieved in an electrolyte containing an alkanesulfonate of silver and an alkanesulfonic acid.
  • Such gold-colored aluminum workpieces are of particular interest for the production of decorative objects, since the demand for gold-colored objects made of aluminum is great.
  • These gold-colored aluminum oxide surfaces are preferably obtained by dyeing in step c) at a concentration of the silver salt, calculated as Ag + , of 2 to 50 g / 1, preferably 3 to 20 g / 1 and a product of current density and voltage from 9
  • AV / dm preferably from 1 to 5 AV / dm over a period of generally 0.05 to 4 minutes, preferably 0.3 to 3 minutes, particularly preferably from 0.5 to 2 minutes
  • an exact coordination of the three parameters concentration of the silver salt, product of current density and voltage and electrolysis time is crucial. The deviation of only one parameter already leads to undesirable coloring.
  • a relatively high concentration of the silver salt, calculated as Ag + , of 2 to 50 g / l is used. A green cast of the gold-colored layers is only avoided at high silver salt concentrations. Such high silver salt concentrations can only be achieved with a readily soluble salt, an alkanesulfonic acid salt according to the present invention.
  • Silver sulfate is therefore not suitable because its solubility limit in water is approx. 0.9 g / 1.
  • the better solubility of the alkanesulfonates further facilitates automatic metering of the silver salt in liquid form, ie in solution.
  • faster deposition on the aluminum oxide surface can be achieved by higher silver salt concentrations.
  • the aluminum oxide layers obtained after step b) of the process according to the invention are colored in a metal salt-containing electrolyte by means of direct or alternating current, preferably by means of alternating current. Metal is deposited from the metal salt solution at the pore base of the oxide layer.
  • the gold color obtained with the process according to the invention is very lightfast. An even and reproducible color tone is achieved.
  • An acid selected from an alkanesulfonic acid or a mixture of an alkanesulfonic acid and sulfuric acid is preferably used in the electrolyte in step c).
  • the silver salt-containing electrolyte contains 20 to 100 parts by weight of an alkanesulfonic acid and
  • Sulfuric acid is 100 parts by weight and a concentration of 0.1 to 20% by weight, preferably makes up 1 to 15% by weight of the electrolyte.
  • the electrolyte very particularly preferably contains 100 parts by weight of an alkanesulfonic acid.
  • the electrolytes according to the present invention are aqueous electrolytes.
  • Alkanesulfonic acids suitable for the process according to step c) have already been disclosed above. Methanesulfonic acid is particularly preferred.
  • electrolytes based on alkanesulfonic acids have a higher electrical conductivity, cause quicker coloring, show a reduced oxidation effect, which prevents the precipitation of metal salts from the electrolyte containing the metal salts. It is not necessary to add additives such as the environmentally harmful phenolic or toluenesulfonic acid or similar additives to increase the bath stability and improve the scatter or to avoid a green tint of the gold color.
  • alkanesulfonic acids when used in the electrolyte, a faster coloring is achieved than when using pure sulfuric acid. In addition, reproducible gold colorations are obtained, so that a constant product quality is ensured. In addition, the scatter-improving effect of alkanesulfonic acids is to be emphasized, which leads to a uniform deposition of the metal salts used and thus to a very good surface quality.
  • suitable metal salts are generally selected from tin, copper, cobalt, nickel, bismuth, chromium, palladium and lead or mixtures of two or more of these metal salts.
  • the silver salts-containing electrolytes can preferably contain copper and / or tin salts in addition to silver salts, as a result of which the gold color tone can be varied in subtle shades.
  • the copper and / or tin salts optionally present in the electrolyte are alkanesulfonates and / or sulfates. Alkanesulfonates are particularly preferred.
  • Alkanesulfonates for the purposes of the present invention are understood to mean aliphatic sulfonates. Their aliphatic residue can optionally be functional Groups or heteroatoms, for example hydroxyl groups, may be substituted. Alkanesulfonates of the general formulas are preferred
  • R is a hydrocarbon radical which can be branched or unbranched, having 1 to 12 carbon atoms, preferably having 1 to 6 carbon atoms, particularly preferably an unbranched hydrocarbon radical having 1 to 3 carbon atoms, very particularly preferably having 1 carbon atom, that is to say methanesulfonate.
  • R is a hydrocarbon radical which can be branched or unbranched, having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms, particularly preferably an unbranched hydrocarbon radical having 2 to 4 carbon atoms, it being possible for the hydroxyl group and the sulfonate group to be bonded to any carbon atom the restriction that they are not bound to the same carbon atom.
  • Silver methanesulfonate is very particularly preferably used as the silver salt in the process according to the invention.
  • the electrolyte In addition to the corresponding acid, an alkanesulfonic acid or a mixture of sulfuric acid and an alkanesulfonic acid and the alkanesulfonate of silver used and optionally further metal salts, the electrolyte generally contains water and, if necessary, further additives such as aromatic sulfonic acids to improve the scatter. If an alkanesulfonic acid, in particular methanesulfonic acid, is used as the acid, additives for improving the scatter can generally be dispensed with.
  • the electrodes which are usually suitable in a process for the electrolytic coloring of aluminum oxide layers are electrodes, such as stainless steel or graphite. Suitable electrodes. It is also possible to use silver electrodes or electrodes made from one of the other metals that may be used, which dissolve during the electrolysis and thus deliver the corresponding metal salt during the electrolysis.
  • the workpieces are generally rinsed with water, in particular with running water. This rinsing step follows both step b) and step c).
  • the pores of the oxide layer produced are generally sealed off after step c) in order to obtain good corrosion protection.
  • This re-sealing can be achieved by immersing the workpieces in boiling, distilled water for about 30 to 60 minutes.
  • the oxide layer swells, which closes the pores.
  • the water can also contain additives.
  • the workpieces are post-treated in steam at 4 to 6 bar instead of in boiling water.
  • the sealing is preferably carried out by means of water or steam.
  • e) Recovery of the alkanesulfonic acid and / or its salts used In order to save costs and for ecological reasons, the alkanesulfonic acid and / or its salts used can be recovered. This recovery can follow every step in which an alkanesulfonic acid can be used or can be carried out in parallel with these steps. A recovery is possible, for example, together with the rinsing step (dl)) following step b) and step c). Such recovery can take place, for example, by means of electrolytic membrane cells, by cascade rinsing, or by simple concentration, for example of the rinsing solutions.
  • Another object of the present invention is the use of an electrolyte containing an alkanesulfonate of silver for the gold-colored coloring of aluminum oxide layers based on aluminum or aluminum alloys in an electrolytic process.
  • Another object is an electrolyte solution for the gold-colored coloring of the oxidized surface of aluminum or aluminum alloys by an electrolytic process, containing an alkanesulfonate of silver, optionally together with copper and / or tin salts, and an acid selected from an alkanesulfonic acid or a mixture of an alkanesulfonic acid and sulfuric acid.
  • silver alkane sulfonates preferably silver methane sulfonate, if appropriate together with other metal salts, preferably tin and copper salts, are suitable for gold coloring aluminum oxide layers.
  • alkane sulfonates of silver and the use of electrolytes containing an alkane sulfonate of silver for gold coloring aluminum oxide surfaces uniform and reproducible gold-colored aluminum oxide surfaces can be produced in a short time.
  • the present invention further relates to the use of the gold-colored workpieces produced by the process according to the invention based on aluminum or aluminum alloys for decorative purposes.
  • Gold-colored workpieces based on aluminum or aluminum alloys can be used wherever aluminum workpieces are used on the outside. Examples of a use of the invention Gold-colored aluminum workpieces are used in construction, in particular for the production of window profiles or facade components, as well as for handles of all kinds, fittings and fittings, for the production of household items, in car or aircraft construction, in particular for body and interior parts, and in packaging ,
  • MSA methanesulfonic acid
  • Table 2 below shows the colors obtained as a function of time:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Procédé permettant de produire des couches d'oxyde d'aluminium de couleur dorée selon lequel la coloration de la surface oxydée de la pièce en aluminium ou en alliages d'aluminium est obtenue à l'aide d'un procédé électrolytique dans un électrolyte contenant un acide alcanesulfonique et un sulfonate d'alcane de l'argent. La présente invention concerne également l'utilisation à des fins décoratives de pièces en aluminium ou en alliages d'aluminium à coloration dorée obtenue selon ledit procédé. La présente invention concerne en outre une solution électrolytique pour la coloration dorée de la surface oxydée de pièces en aluminium ou en alliages d'aluminium à l'aide d'un procédé électrolytique, et l'utilisation d'un électrolyte contenant un sulfonate d'alcane de l'argent pour la coloration dorée de couches d'oxyde d'aluminium situées sur des pièces en aluminium ou en alliages d'aluminium lors d'un procédé électrolytique.
EP01967140A 2000-07-10 2001-07-10 Procede de fabrication de surfaces dorees de pieces en aluminium ou en alliages d'aluminium a l'aide de formulations contenant des sels d'argent Withdrawn EP1299577A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10033434 2000-07-10
DE10033434A DE10033434A1 (de) 2000-07-10 2000-07-10 Verfahren zur Herstellung von goldfarbenen Oberflächen von Aluminium oder Aluminium-Legierungen mittels silbersalzhaltigen Formulierungen
PCT/EP2001/007936 WO2002004717A2 (fr) 2000-07-10 2001-07-10 Procede de fabrication de surfaces dorees de pieces en aluminium ou en alliages d'aluminium a l'aide de formulations contenant des sels d'argent

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EP1299577A2 true EP1299577A2 (fr) 2003-04-09

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EP01967140A Withdrawn EP1299577A2 (fr) 2000-07-10 2001-07-10 Procede de fabrication de surfaces dorees de pieces en aluminium ou en alliages d'aluminium a l'aide de formulations contenant des sels d'argent

Country Status (9)

Country Link
US (1) US7097756B2 (fr)
EP (1) EP1299577A2 (fr)
JP (1) JP2004502878A (fr)
CN (1) CN1220797C (fr)
AU (1) AU2001287593A1 (fr)
CA (1) CA2412647A1 (fr)
DE (1) DE10033434A1 (fr)
TW (1) TWI238858B (fr)
WO (1) WO2002004717A2 (fr)

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US7090762B2 (en) * 2003-08-05 2006-08-15 Kemet Electronics Corp. Method of passing electric current through highly resistive anodic oxide films
TWI354716B (en) * 2007-04-13 2011-12-21 Green Hydrotec Inc Palladium-containing plating solution and its uses
DE102007027628B3 (de) * 2007-06-12 2008-10-30 Siemens Ag Verfahren zum Einbringen von Nanopartikeln in eine anodisch oxidierte Aluminiumoberfläche
CN102312264B (zh) * 2011-08-22 2013-10-09 吴江市精工铝字制造厂 铝及铝合金的装饰性氧化法
DE102013000433B4 (de) * 2013-01-14 2019-03-21 Awg Fittings Gmbh Feuerlöscharmatur
CN104152969B (zh) * 2014-08-04 2016-07-27 石狮市星火铝制品有限公司 一种铝合金交流电解沉积银铜的着色方法
CN104651905B (zh) * 2015-01-28 2017-11-07 永保纳米科技(深圳)有限公司 一种阳极铝匀染缓染助剂及其操作液，和阳极铝匀染缓染处理工艺
CN105239133A (zh) * 2015-10-08 2016-01-13 昆明理工大学 一种钛及钛合金表面阳极氧化着色方法
JP7113357B2 (ja) * 2019-03-26 2022-08-05 パナソニックＩｐマネジメント株式会社 複合部材、並びにそれを用いた建築部材及び装飾部材

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CN1441858A (zh) 2003-09-10
JP2004502878A (ja) 2004-01-29
TWI238858B (en) 2005-09-01
US20030098240A1 (en) 2003-05-29
DE10033434A1 (de) 2002-01-24
US7097756B2 (en) 2006-08-29
WO2002004717A2 (fr) 2002-01-17
CN1220797C (zh) 2005-09-28
WO2002004717A3 (fr) 2002-05-10
AU2001287593A1 (en) 2002-01-21
CA2412647A1 (fr) 2002-12-23

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