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    • 专利摘要:
    The invention relates to a new bath for the cathodic deposition of new ternary bronze alloys as well as objects or articles coated with the alloys. The electrolyte composition includes indium as well as copper and tin as the only third metallic alloying ingredient. It can be deposited with the new alloy high-gloss white, yellow or red precipitates or coatings high corrosion resistance of the objects, especially jewelry and electronic components that are free of toxic heavy metals. On an optional copper layer, a ternary copper-tin indium alloy is deposited directly. This alloy layer may be final layer, or further coated, e.g. with palladium, gold or other precious metals, such as rhodium, ruthenium or alloys thereof.
    公开号:AT514427A4
    申请号:T50444/2013
    申请日:2013-07-05
    公开日:2015-01-15
    发明作者:
    申请人:W Garhöfer Ges M B H Ing；
    IPC主号:
    专利说明:

    Electrolyte bath and thus available objects or articles
    The present invention is directed to an electrolytic bath composition for depositing new ternary copper or bronze alloys free of toxic heavy metals, and further to objects and articles coated with these novel alloys as well as to a corresponding deposition method and use of the bath ,
    Methods for the deposition of bronzes or other copper-tin alloys from cyanidic baths are known. Such conventional cyanidic baths are typically used for decorative applications where nickel is undesirable because of its allergy-inducing character or as a substitute for the much more expensive silver or palladium.
    Field of application is in particular the production of fashion jewelery, furthermore the clothing industry, in particular for buttons, zipper closures, bra closures, belt buckles, leather applications and the production of furniture fittings.
    In addition to industries that work with decorative applications, replacement of nickel is also gaining importance in some technical areas, such as the coating of electronic components, in engineering and process engineering, and in some connector applications where the magnetic properties of nickel are undesirable.
    The invention relates to a novel electrolyte bath for the electrodeposition of coatings based on copper-tin-indium alloys, consisting essentially of water, copper cyanide, at least one tin (IV) compound, at least one indium compound, an alkali metal cyanide, an alkali metal hydroxide , and at least one complexing agent, of wetting agents and brighteners.
    From EP 1930478 A1 a bath for the deposition of quaternary copper alloys is known, which in addition to copper, tin, zinc contains a metal from the group gallium, indium or thallium.
    On the one hand, an electrolyte with four metal salts in the solution is very difficult to control in production, on the other hand, the use of thallium in particular because of its toxicity is fundamentally to be rejected.
    EP 636 713 A1 describes alkaline cyanide baths for the electrodeposition of bright copper-tin alloys which, in addition to the corresponding metal salts, contain complexing agents, alkene sulfonate, alkyne sulfonate, pyridine compounds or sulfur-containing propane sulfonates as luster additives.
    US Pat. No. 5,534,129 A discloses baths for producing lustrous, leveling copper-tin alloys which, in addition to metal salts, contain one or more complexing agents, alkali metal cyanide, alkali metal hydroxide, alkali metal carbonates, various brighteners and lead.
    However, lead may only be used to a limited extent under European legislation. With increasing duration and age of the baths, the concentration of lead usually increases and then exceeds the permitted limit values.
    US 4814049 A describes alkaline cyanide baths for the production of copper-tin-zinc alloys containing small amounts of nickel.
    However, copper-tin alloys are often used as a substitute for nickel coatings, especially for costume jewelery, but also for products that come into constant or prolonged contact with the skin to avoid contact allergies. Co-alloying nickel, even in small amounts, would make replacement impossible.
    It is the object of the present invention to develop baths from which shiny, ternary copper-tin-indium alloys, without the addition of toxic metals, such as e.g. Lead, thallium or nickel, which are at the same time of improved corrosion resistance over comparable copper-tin or copper-tin-zinc alloys and beyond easy to monitor and maintain. Surprisingly, it has been found that the addition of indium to a copper-tin alloy both the optical appearance, ie. Gloss, brightness and Like. Abrasion resistance, corrosion resistance and resistance to artificial perspiration is able to significantly improve.
    Such alloys are thereby very well suited for the decorative coating, e.g. from fashion jewelery, but also for industrial applications as well as in the electronics industry.
    The invention relates to a new electrolyte bath for the cathodic deposition of ternary alloys and / or layer sequences to form white to red, corrosion-resistant glossy coatings on at least on their surface metallic or electrically conductive or conductive coated objects, which bath as the electrolyte at least one complex dissolved Contains copper and at least one such tin compound, which is characterized in that it is present as an aqueous, alkaline solution and, in addition to the present as complex compounds, preferably in the form of anionic, copper and tin compounds as a third component at least contains an indium compound, and in addition at least one of the components contained in the electrodeposition baths usual manner from the group complexing agents, surface-active substances, wetting agents, complexing agents and brighteners.
    It is therefore in particular a cyanidic-alkaline bath for the electrodeposition of new ternary copper-tin-indium alloys.
    In the context of the present invention, it has proved to be advantageous if copper and indium are originally present as cyanides, sulfates or sulfamates, in particular in the form of alkaline and / or cyanidically-soluble compounds, preferably copper as copper cyanide and tin as stannate or hydroxystannate.
    Using the new electrolyte baths, it is possible, depending on the ratio of the concentrations of the three alloying base metals to one another, to deposit coatings with different metallic primary colors from white to red.
    Accordingly, for the deposition of a white coating, an electrolyte bath is provided, which is characterized in that it has a content of free alkali metal cyanide of 15 to 70 g / l, preferably from 20 to 60 g / l, and particularly preferably from 25 to 45 g / l, and alkali hydroxide of from 5 to 40 g / l, preferably from 10 to 30 g / l, and the content of copper in the range of from 5 to 25 g / l, preferably from 8 to 15 g / l, the content at tin at 15 to 50 g / l, preferably at 20 to 30 g / l, and the content of indium in the range of 0.5 to 5 g / l, preferably from 1 to 3 g / l varies. For the deposition of a yellow coating, it has proved to be favorable if the electrolyte bath has a content of free alkali metal cyanide of 10 to 60 g / l, preferably from 10 to 40 g / l, and particularly preferably from 15 to 30 g / l, and of alkali hydroxide from 10 to 40 g / l, preferably from 15 to 30 g / l, the content of copper in the range of 5 to 25 g / l, preferably from 10 to 20 g / l, the content of tin at 3 to 15 g / l, preferably at 5 to 12 g / l, and the content of indium from 0.5 to 5 g / l, preferably from 1 to 3 g / l, varies.
    Finally, for the deposition of a red coating, the electrolyte bath is characterized by having a content of free alkali metal cyanide of 15 to 70 g / l, preferably 20 to 60 g / l, and more preferably 25 to 45 g / l, and Alkali hydroxide of 10 to 40 g / l, preferably from 15 to 30 g / l, the content of copper in the range of 15 to 40 g / l, preferably from 20 to 30 g / l, the content of tin at 3 to 15 g / l, preferably at 5 to 12 g / l, and the content of indium in the range of 0.5 to 5 g / l, preferably from 1 to 3 g / l, varies.
    As regards other components of the new electrolyte bath, it has proved to be advantageous if it contains as complexing agent at least one selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), phosphonates, pyrophosphates, gluconates, citrates, salts tartaric acid, furthermore phosphonic acids, in particular aminotrismethylenephosphonic acid (ATMP), ethylenediamine-tetramethylenephosphonic acid (EDTMP),
    Diethylenetriaminepentamethylenephosphonic acid (DTPMP) and 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or their alkali metal salts, and preferably further containing surfactants, for example alkyl ether sulfonates, alkyl ether phosphates, betaines or sulfobetaines, and / or pyridine derivatives, epichlorohydrin polymers and aminic polymers as brightener additives ,
    Another essential subject of the invention are objects or articles, in particular jewelery or decorative articles, and further electro-technical or electronic components and components of a physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or alloys thereof or provided with a coating of a ternary alloy of copper, tin and indium deposited from an electrolyte bath deposited as mentioned above.
    In detail, these objects with a white coating are characterized in that, preferably on an on the surface of the object or article metal substrate layer, in particular of copper, an alloy having 45 to 62 wt%, preferably 48 to 60 wt. -%, copper, 32 to 48 wt .-%, preferably 35 to 45 wt .-%, tin and 3 to 15 wt .-%, preferably 6 to 10 wt .-%, indium is arranged.
    The abovementioned objects with a yellow coating are characterized in that, preferably on an underlying metallic surface layer on the surface of the object or article, in particular of copper, an alloy with 76 to 82 wt.%, Preferably 77 to 80 wt. % Copper, 12 to 20 wt .-%, preferably 14 to 18 wt .-%, tin and 2 to 10 wt .-%, preferably 3 to 7 wt .-%, indium.
    Finally, it is provided according to the invention for the above-mentioned objects with a red coating that preferably on an on the surface of the object or article metal substrate layer, in particular of copper, an alloy with 85 to 92 wt .-%, preferably 86 bis 90 wt .-%, copper, 6 to 10 wt .-% tin and 2 to 5 wt .-% indium is arranged.
    As far as the total thickness of the new ternary Cu, Sn, In bronze coating normally to be achieved in the context of the invention is concerned, the same is - depending on the field of use -0.5 to 15 μm, in particular approximately 1 to 3 μm.
    It may further be provided that on the outside of the Cu, Sn, In-bronze coating there is a further, electrodeposited final layer of palladium, gold and / or another noble metal, in particular rhodium, platinum, ruthenium or an alloy from the same, is arranged. For further improvements of the novel coatings of the new articles, it may be envisaged that on the white, yellow or red Cu, Sn, In-bronze coating thereon a palladium or palladium alloy thin adherent, electrodeposited thin intermediate layer thereon or above deposited adhesive gold or such an intermediate layer of adhesive gold is arranged alone and on this - deposited on the Cu, Sn, ln-bronze coating - intermediate layer an electrodeposited, adherent final layer of palladium, gold and / or other precious metal, in particular rhodium, platinum, ruthenium or an alloy thereof. Usually, care is taken that the intermediate layer of palladium or a palladium alloy has a thickness of 0.1 to 1 μm, and that of adhesive gold has a thickness of 0.05 to 0.3 μm.
    Finally, the possibility ultimately exists that the new objects or articles should have a final layer of one with rhodium and ruthenium, preferably in the weight% ratio of (70 to 90) :( 30 to 10), in particular of about 80:20 , formed alloy.
    It is the object of the present invention to adjust and vary the concentration of the metal salts, complexing agents and additional ingredients in the mold such that the electrolyte solution is clear, ie that no metal salts precipitate, and that glossy, adherent, abrasion and corrosion resistant layers or Coatings are deposited.
    In the course of the process for the electrolytic application of the new ternary bronze alloys to the respective base materials, the objects, objects or particles to be coated are immersed in the respective electrolyte bath according to the invention and switched there as a cathode.
    The working temperature of the electrolyte baths according to the invention is between 40 and 70 ° C. The current density can be set to between 0.01 and 10 amps / dm2, depending on the type of coating equipment.
    Thus, in drum coating processes, current densities between 0.05 and 0.50 A / dm 2 are particularly preferred. In rack coating processes, preference is given to choosing current densities between 0.2 and 10 A / dm 2, particularly preferably 0.2 to 5 A / dm 2.
    When using the electrolyte baths according to the invention, various insoluble anodes can be used.
    As such insoluble anodes, those made of a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon" DLC) or combinations of these materials are preferably used. Mixed oxide anodes of iridium-ruthenium mixed oxide, iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide are particularly preferably used.
    The production of the objects or articles coated according to the invention is usually carried out as follows:
    On a respective base material, for example made of brass, zinc, iron, steel or their alloys or other materials made conductive at least on its surface is either directly or on a previously applied copper undercoat, deposited from cyanide or non-cyanide alkaline and / or from acidic copper baths, the new ternary copper-tin-indium alloy deposited.
    This copper-tin-indium alloy can be either final or final layer, or further coated according to methods known per se. Other coatings may, as already mentioned above, be palladium-containing, gold-containing or other noble metal-containing layers such as those of rhodium, platinum, ruthenium or their alloys.
    From the prior art is - in addition to the documents already mentioned - further known that palladium is used as a nickel substitute, as a diffusion barrier and as corrosion protection. In these products, the base material is first copper-plated, then coated with palladium and finally receives the desired finish by coating with gold, rhodium or other precious metals or their alloys.
    In order to provide sufficient corrosion protection, a thickness of the palladium layer of about 0.5-5 pm is recommended. Usually, a layer thickness of about 1 pm is considered sufficient.
    According to the present invention it has been found that the application of e.g. 2 to 5 pm thick ternary copper-tin-indium alloy alone, e.g. on a copper
    Primary coating, almost equally good corrosion results, as obtained in palladium-coated base materials leads.
    If, instead of 1 pm of pure palladium, only 0.5 pm of pure palladium and 2 pm of the new bronze are deposited on the Cu base coat, then the savings in the intermediate layers alone are almost 50%; If only 4 pm of Cu, Sn, In-Bronze without palladium interlayer are deposited, the saving is almost 99%.
    If one wants to produce the products particularly efficiently, one can deposit a rhodium-ruthenium alloy instead of a rhodium final layer. If, for example, an alloy in the ratio by weight of rhodium to ruthenium of 80:20 is deposited as the final layer, in addition to the savings in the intermediate layers mentioned above, 20% of the very expensive rhodium would be saved.
    In detail, reference is made in particular to claims 12 to 15.
    The invention further relates to a, in particular conventional, method for the cathodic deposition of the ternary alloys according to the invention on at least their surface metallic or electrically conductive or conductive coated objects or articles using the electrolyte according to the invention and further objects or articles, available, or obtained manufactured by such a method for the cathodic deposition of ternary alloys, using the electrolyte bath according to the invention. The invention also relates to the use of the electrolyte bath according to the invention for the cathodic deposition of ternary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles.
    The invention will be explained in more detail with reference to the following non-limiting examples.
    Example 1 - white coating layer:
    Electrolyte bath: 10 g / l Cu from CuCN 25 g / l Sn from alkali stannate 3 g / l In from In 2 (SO 4) 3
    40 ml / l 1-hydroxyethane-1,1-diphosphonic acid 60 g / l Seignette salt 45 g / l KCN 25 g / l KOH 2 ml / l Brightener: " Brightener CT 16/1 " (Product of the company Ing. W. Garhöfer GesmbH) 4 ml / l brightener: " Brightener CT 16/2 " (Product of the company Ing. W. Garhöfer GesmbH)
    Layer sequence and its production:
    A brass jewelry blank is electrolytically degreased in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm2.
    Subsequently, the jewelry blank is rinsed in deionized water, deboned in 5% sulfuric acid solution for 30 seconds and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W Garhöfer GesmbH), 20 pm of copper are deposited to a leveling and high gloss at 4 A / dm2 and 25 ° C. The blank is rinsed again and pre-immersed in a 10% KCN solution.
    Thereupon, from a bronze electrode bath according to the present invention, 2 pm bronze alloy of the composition copper: 48%, tin: 43%, indium: 9%, at 60 ° C., 1 A / dm 2 is precipitated from the electrolyte bath within 10 minutes.
    Finally, the galvanized jewelry was rinsed in deionized water and dried.
    Optical assessment:
    The obtained in this way, galvanized jewelry part or its surface was white and high gloss.
    Corrosion resistance according to DIN 50018:
    The corrosion resistance of the galvanized decorative part was tested in accordance with DIN 50018, Testing in a condensed water climate with sulfur dioxide-containing atmosphere, June 1997.
    The corrosion resistance of the white coating compared to a coating of a similar working electrolyte producing copper-tin-zinc layers on the same base material in the SO 2 test is about twice as good.
    Corrosion resistance according to AVON TEST APJTM 62.303-1:
    In the artificial sweat test, parts coated from the electrolytic bath containing only the three metals according to the invention could remain for at least six days without any detectable attack, while parts from a comparable electrolytic bath, but without indium, showed signs of attack after only one day.
    Examples 2 - white coating layer:
    Electrolyte: 9 g / l Cu from CuCN 22 g / l Sn from alkali stannate 3 g / l In from In 2 (SO 4) 3
    40 ml / l 1-hydroxyethane-1,1-diphosphonic acid 60 g / l Seignette salt 45 g / l KCN 25 g / l KOH 2 ml / l Brightener: " Brightener CT 16/1 " (Product of the company Ing. W. Garhöfer GesmbH) 4 ml / l brightener: " Brightener CT 16/2 " (Product of the company Ing. W. Garhöfer GesmbH)
    A jewelery blank made of die-cast zinc is electrolytically degreased in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm2.
    Subsequently, the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN (" Cuproga ", product of the company Ing. W. Garhöfer GesmbH) were 5pm copper at 1 A / dm2 and 50 ° C deposited.
    The pre-encrusted jewelry blank is then stripped in 5% sulfuric acid solution for 30 seconds and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH) 15 pm of copper are deposited, leveling and high-gloss, at 4 A / dm 2 and 25 ° C. The thus coppered part is again rinsed and pre-immersed in a 10% KCN solution.
    Thereupon, 2 μm bronze alloy of the composition copper: 55%, tin: 38%, indium: 7%, at 60 ° C. and 1 A / dm 2 are precipitated from the electrolyte within 10 minutes from a bronzeelectroelectrode according to the present invention. It is then rinsed in deionized water, stripped in 5% sulfuric acid solution and in a weakly alkaline, ammonia-containing pure palladium electrolyte with 2 g / l Pd ("Gapal FS", product of the company Ing. W. Garhöfer GesmbH) with 0.5 pm palladium finally coated at 1 A / dm2 and 25 ° C.
    After renewed rinsing and acid immersion, the jewelery thus obtained is mixed with 0.1 pm of adhesive gold from a weakly acidic electrolyte with 2.5 g / l Au (" MC 218 ", product of the Fa.
    Ing. W. Garhöfer GesmbH) at 1.5A / dm2 and 35 ° C. It is then rinsed thoroughly in demineralised water, stripped in 5% sulfuric acid solution and treated with 0.2 pm rhodium from an electrolyte containing 2 g / l Rh and 50 g / l sulfuric acid (" Rhodium C2 ", product of Ing. W Garhöfer GesmbH) at 3V and 35 ° C rhodium.
    Finally, the galvanized part was rinsed in deionized water and dried.
    Optical assessment:
    The obtained in this way, galvanized jewelry part or its surface was white and high gloss.
    Corrosion resistance:
    The electroplated piece of jewelry performed significantly better in the corrosion tests than pieces of jewelery which had been coated by the same method but with a comparable copper-tin-zinc alloy.
    Example 3 - Yellow Coating Layer
    Electrolyte bath: 17 g / l Cu of CuCN 8 g / l Sn of alkali stannate 3 g / l In In 2 (SO 4) 3
    20 ml / l ethylenediamine-tetramethylenephosphonic acid 40 g / l sodium gluconate 20 g / l NaCN 25 g / l NaOH 2 ml / l Brightener: " Brightener CT 16/1 " (Product of the company Ing. W. Garhöfer GesmbH) 4 ml / l brightener: " Brightener CT 16/2 " (Product of the company Ing. W. Garhöfer GesmbH)
    Working conditions: 45 ° C, 1 A / dm2
    A brass jewelry blank is degreased electrolytically in a slightly alkaline, cyanide-free cleaner, (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C for 30 seconds at 10A / dm2.
    Subsequently, the jewelry blank is rinsed in deionized water, stripped in 5% sulfuric acid solution for 30 seconds and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH), 20 pm of copper are deposited, leveling and high-gloss, at 4 A / dm2 and 25 ° C. The part is again rinsed and pre-immersed in a 10% KCN solution.
    Thereupon, 1 pm bronze alloy of the composition copper: 78%, tin: 16%, indium: 6%, at 45 ° C., 1 A / dm 2 is precipitated from the electrolyte within 5 min from a bronzeelectroelectrode according to the present invention.
    After renewed rinsing and acid immersion with 1pm gold from a weakly acidic electrolyte with 2.5 g / l Au (" MC 218 ", product of the company Ing. W. Garhöfer GesmbH) at 1.5 A / dm2 and 35 ° C as a final layer.
    Finally, the galvanized part was rinsed in deionized water and dried. Optical assessment:
    The obtained in this way, galvanized jewelry or its surface was yellow and high gloss.
    Corrosion resistance:
    The electroplated piece of jewelry performed significantly better in the corrosion tests than pieces of jewelery which had been coated by the same method but with a comparable copper-tin-zinc alloy.
    Example 4 - red coating layer:
    Electrolyte bath: 26 g / l Cu of CuCN 9 g / l Sn of alkali distannate 3 g / l In In 2 (S04) 3
    10 ml / l 1-hydroxyethane-1,1-diphosphonic acid 30 g / l ethylenediaminetetraacetic acid 30 g / l KCN 30 g / l KOH 2 ml / l Brightener: " Brightener CT 16/1 " (Product of the company Ing. W. Garhöfer GesmbH) 4 ml / l brightener: " Brightener CT 16/2 " (Product of the company Ing. W. Garhöfer GesmbH)
    Layer sequence:
    A jewelery blank made of zinc die casting is electrolytically degreased in a weakly alkaline, cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2.
    Subsequently, the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN ("Cuproga", product of the company Ing. W. Garhöfer GesmbH) are 5 pm copper at 1 A. / dm2 and 50 ° C deposited.
    The pre-encrusted jewelry blank is then stripped in 5% sulfuric acid solution for 30 seconds and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH) 15 pm of copper are deposited, leveling and high-gloss, at 4 A / dm 2 and 25 ° C. The part is again rinsed and pre-immersed in a 10% KCN solution.
    Then, from a bronze electrolytes according to the present invention, 2 pm ternary bronze alloy of composition copper: 88%, tin: 8%, indium: 4%, deposited at 45 ° C., 1 A / dm2 from the electrolyte within 10 min.
    The jewelery, after rinsing in demineralized water and pickling in 10% KCN solution with 1pm of 4N gold from a 5 g / l Au cyanide electrolyte (" MC 118 PI ", product of Ing. W. Garhöfer GesmbH) at 0.7 A / dm2 and 65 ° C as final layer.
    Finally, the galvanized part was rinsed in deionized water and dried. Optical assessment:
    The galvanized jewelry obtained in this way or its surface was pink 4N and high gloss.
    Corrosion resistance:
    The galvanized part of the jewelry performed significantly better in the corrosion tests than jewelry parts that were coated by the same process but with a comparable copper-tin-zinc alloy.
    权利要求:
    Claims (18)
    [1]
    1. Electrolyte bath for the cathodic deposition of ternary alloys and / or layer sequences to form white to red, corrosion-resistant glossy coatings on at least on their surface metallic or electrically conductive or conductive coated objects, which bath as electrolyte at least one complex dissolved copper - And at least one such tin compound contains, characterized in that the bath is present as an aqueous, alkaline solution and, in addition to the complex compounds, preferably in the form of anionic complexes, present copper and tin compounds as a third component at least one indium Contains compound, as well as in addition at least one of the usual manner in galvanic deposition baths contained components from the group complexing agents, surface-active substances, wetting agents, complexing agents and brighteners.
    [2]
    2. electrolytic bath according to claim 1, characterized in that copper and indium originally as cyanides, sulfates or sulfamates, in particular in the form of alkaline and / or cyanidisch-soluble compounds, preferably copper as copper cyanide and tin as stannate or hydroxystannate present.
    [3]
    3. electrolyte bath according to claim 1 or 2, characterized in that it - for the deposition of a white coating - a content of free alkali metal cyanide of 15 to 70 g / l, preferably from 20 to 60 g / l, and particularly preferably from 25 to 45 g / l, and of alkali metal hydroxide of 5 to 40 g / l, preferably of 10 to 30 g / l, and the content of copper in the range of 5 to 25 g / l, preferably 8 to 15 g / l, the content of tin is 15 to 50 g / l, preferably 20 to 30 g / l, and the content of indium varies in the range of 0.5 to 5 g / l, preferably 1 to 3 g / l.
    [4]
    4. electrolyte bath according to claim 1 or 2, characterized in that it - for the deposition of a yellow coating - a content of free alkali metal cyanide of 10 to 60 g / l, preferably from 10 to 40 g / l, and particularly preferably from 15 to The content of copper in the range of 5 to 25 g / l, preferably from 10 to 20 g / l, of. 30 g / l, and of alkali metal hydroxide of 10 to 40 g / l, preferably from 15 to 30 g / l Content of tin at 3 to 15 g / l, preferably at 5 to 12 g / l, and the content of indium from 0.5 to 5 g / l, preferably from 1 to 3 g / l, varies.
    [5]
    5. electrolyte bath according to claim 1 or 2, characterized in that it - for the deposition of a red coating - a content of free alkali metal cyanide of 15 to 70 g / l, preferably from 20 to 60 g / l, and particularly preferably from 25 to 45 g / l, and of alkali metal hydroxide of 10 to 40 g / l, preferably of 15 to 30 g / l, the content of copper in the range of 15 to 40 g / l, preferably from 20 to 30 g / l, the content of tin is 3 to 15 g / l, preferably 5 to 12 g / l, and the content of indium varies in the range of 0.5 to 5 g / l, preferably 1 to 3 g / l.
    [6]
    6. electrolyte bath according to one of claims 1 to 4, characterized in that it contains as complexing agent at least one selected from the group ethylenetriamine tetraacetic acid (EDTA), Diethylenetriaminepentaessigsäure (DTPA), nitrilotriacetic acid (NTA), phosphonates, pyrophosphates, gluconates, citrates, salts of tartaric acid and phosphonic acids, in particular aminotrismethylene phosphonic acid (ATMP), ethylenediamine tetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or their alkali metal salts, and preferably also surfactants, for example alkyl ether sulfonates, alkyl ether phosphates , Betaines or sulfobetaines, and / or pyridine derivatives, epichlorohydrin polymers and aminic polymers as shine additives.
    [7]
    7. Objects or articles, in particular jewelry or decorative items, and further electro-technical or electronic components and components of a physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or alloys thereof or from a conductive equipped plastics having a coating based on copper and tin deposited from an electrolyte bath of one of the claims 1 to 6, characterized in that they are provided with a coating of a ternary alloy of copper, tin and indium.
    [8]
    8. objects or articles according to claim 7, characterized in that they are provided with a deposited from the electrolyte bath according to one of claims 1 to 3 white coating or with such a corrosion-resistant, abrasion-resistant and adherent, glossy coating, wherein, preferably on an on the surface of the object or article located metallic background layer, in particular of copper, an alloy with 45 to 62 wt%, preferably 48 to 60 wt .-%, copper, 32 to 48 wt .-%, preferably 35 to 45 wt .-%, tin and 3 to 15 wt .-%, preferably 6 to 10 wt .-%, indium is arranged.
    [9]
    9. objects or articles according to claim 7, characterized in that they are provided with a deposited from the electrolyte bath according to any one of claims 1, 2 or 4 yellow coating or with such a corrosion-resistant, abrasion-resistant and adherent, shiny coating, wherein preferably on a surface of the object or article located metallic base layer, in particular of copper, an alloy having 76 to 82 wt .-%, preferably 77 to 80 wt .-% copper, 12 to 20 wt .-%, preferably 14 to 18 wt .-%, tin and 2 to 10 wt .-%, preferably 3 to 7 wt .-%, indium is arranged.
    [10]
    10. objects or articles according to claim 7, characterized in that they are provided with a deposited from the electrolyte bath according to any one of claims 1, 2 or 5 red coating or with such a corrosion-resistant, abrasion-resistant and adherent, shiny coating, wherein preferably on a metal substrate layer on the surface of the object or article, in particular of copper, an alloy with 85 to 92 wt .-%, preferably 86 to 90 wt .-%, copper, 6 to 10 wt .-% tin and 2 to 5 wt .-% indium is arranged.
    [11]
    11. objects or articles according to any one of claims 7 to 10, characterized in that the total thickness of the ternary Cu, Sn, ln bronze coating - depending on the application area -0.5 to 15 μηι, in particular about 1 to 3 μηι , is.
    [12]
    12. objects or articles according to any one of claims 7 to 11, characterized in that on its white, yellow or red coating on the same adherent further, electrodeposited final layer of palladium, gold and / or other precious metal, such as rhodium , Platinum, ruthenium or an alloy of the same.
    [13]
    13. Objects or articles according to any one of claims 7 to 12, characterized in that on the white, yellow or red Cu, Sn, ln-bronze coating on a firmly adherent, electrodeposited thin intermediate layer of palladium or a palladium alloy and Adhesive gold deposited thereon or above, or an intermediate layer of adhesive gold alone, and on this intermediate layer deposited on the Cu, Sn, In bronze coating, an electrodeposited, adherent final layer of palladium, gold and / or another noble metal in particular rhodium, platinum, ruthenium or an alloy thereof.
    [14]
    14. Objects or articles according to any one of claims 7 to 13, characterized in that the intermediate layer of palladium or a palladium alloy has a thickness of 0.1 to 1 μηι, and those of adhesive gold a thickness of 0.05 to 0.3 μηι having.
    [15]
    15. Objects or articles according to any one of claims 7 to 14, characterized in that they - instead of a 100% rhodium final layer - a final layer of a with rhodium and ruthenium, preferably in the wt .-% ratio of (70 to 90) :( 30 to 10), in particular of about 80:20, have formed alloy.
    [16]
    16. A method for the cathodic deposition of ternary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles using an electrolyte bath according to one of claims 1 to 6.
    [17]
    17. Objects or articles, in particular according to one of claims 7 to 15, obtainable by a method for the cathodic deposition of ternary alloys, using an electrolyte bath according to one of claims 1 to 6.
    18. Use of an electrolyte bath according to one of claims 1 to 6 for the cathodic deposition of ternary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles. new patent claims: 1. Electrolyte bath for the cathodic deposition of ternary alloys and / or layer sequences to form white to red, corrosion-resistant glossy coatings on at least on their surface metallic or electrically conductive or conductive coated objects, which bath as electrolyte at least one complex dissolved Contains copper and at least one such tin compound, characterized in that the bath is formed as an aqueous, alkaline solution of in the form of anionic complexes, copper and tin compounds present and contains at least one indium compound as the third component, and in that it additionally contains at least one of the components of the group complexing agents, surface-active substances, wetting agents, complexing agents and brightener additives which is normally present in alkaline electrodeposition baths. 2. electrolytic bath according to claim 1, characterized in that copper and tin in the electrolyte bath in the form of alkaline and / or cyanidisch-soluble compounds, preferably copper as copper (l) cyanide and tin as stannate or hydroxystannate present. 3. electrolyte bath according to claim 1 or 2, characterized in that it - for the deposition of a white coating - a content of free alkali metal cyanide of 15 to 70 g / l, preferably from 20 to 60 g / l, and particularly preferably from 25 to 45 g / l, and of alkali metal hydroxide of 5 to 40 g / l, preferably of 10 to 30 g / l, and the content of copper in the range of 5 to 25 g / l, preferably 8 to 15 g / l, the content of tin is 15 to 50 g / l, preferably 20 to 30 g / l, and the content of indium varies in the range of 0.5 to 5 g / l, preferably 1 to 3 g / l. 4. electrolyte bath according to claim 1 or 2, characterized in that it - for the deposition of a yellow coating - a content of free alkali metal cyanide of 10 to 60 g / l, preferably from 10 to 40 g / l, and particularly preferably from 15 to The content of copper in the range of 5 to 25 g / l, preferably from 10 to 20 g / l, of. 30 g / l, and of alkali metal hydroxide of 10 to 40 g / l, preferably from 15 to 30 g / l Content of tin at 3 to 15 g / l, preferably at 5 to 12 g / l, and the content of indium from 0.5 to 5 g / l, preferably from 1 to 3 g / l, varies. 5. electrolyte bath according to claim 1 or 2, characterized in that it - for the deposition of a red coating - a content of free alkali metal cyanide of 15 to 70 g / l, preferably from 20 to 60 g / l, and particularly preferably from 25 to 45 g / l, and of alkali metal hydroxide of 10 to 40 g / l, preferably of 15 to 30 g / l, the content of copper in the range of 15 to 40 g / l, preferably from 20 to 30 g / l, the content of tin is 3 to 15 g / l, preferably 5 to 12 g / l, and the content of indium varies in the range of 0.5 to 5 g / l, preferably 1 to 3 g / l. 6. electrolyte bath according to one of claims 1 to 4, characterized in that it contains as complexing agent at least one selected from the group ethylenetriamine tetraacetic acid (EDTA), Diethylenetriaminepentaessigsäure (DTPA), nitrilotriacetic acid (NTA), phosphonates, pyrophosphates, gluconates, citrates, salts of tartaric acid and phosphonic acids, in particular aminotrismethylene phosphonic acid (ATMP), ethylenediamine tetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or their alkali metal salts, and preferably also surfactants, for example alkyl ether sulfonates, alkyl ether phosphates , Betaines or sulfobetaines, and / or pyridine derivatives, epichlorohydrin polymers and aminic polymers as shine additives. 7. Objects or articles, in particular jewelry or decorative items, and further electro-technical or electronic components and components of a physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or alloys thereof or from a conductive equipped plastics having a coating based on copper and tin deposited from an electrolyte bath of one of the claims 1 to 6, characterized in that they are provided with a coating of a ternary alloy of copper, tin and indium. 8. objects or articles according to claim 7, characterized in that they are provided with a deposited from the electrolyte bath according to one of claims 1 to 3 white coating or with such a corrosion-resistant, abrasion-resistant and adherent, glossy coating, wherein, preferably on an on the surface of the object or article located metallic background layer, in particular of copper, an alloy with 45 to 62 wt%, preferably 48 to 60 wt .-%, copper, 32 to 48 wt .-%, preferably 35 to 45 wt .-%, tin and 3 to 15 wt .-%, preferably 6 to 10 wt .-%, indium is arranged. 9. objects or articles according to claim 7, characterized in that they are provided with a deposited from the electrolyte bath according to any one of claims 1, 2 or 4 yellow coating or with such a corrosion-resistant, abrasion-resistant and adherent, shiny coating, wherein preferably on a surface of the object or article located metallic base layer, in particular of copper, an alloy having 76 to 82 wt .-%, preferably 77 to 80 wt .-% copper, 12 to 20 wt .-%, preferably 14 to 18 wt .-%, tin and 2 to 10 wt .-%, preferably 3 to 7 wt .-%, indium is arranged. 10. objects or articles according to claim 7, characterized in that they are provided with a deposited from the electrolyte bath according to any one of claims 1, 2 or 5 red coating or with such a corrosion-resistant, abrasion-resistant and adherent, shiny coating, wherein preferably on a metal substrate layer on the surface of the object or article, in particular of copper, an alloy with 85 to 92 wt .-%, preferably 86 to 90 wt .-%, copper, 6 to 10 wt .-% tin and 2 to 5 wt .-% indium is arranged. 11. objects or articles according to any one of claims 7 to 10, characterized in that the total thickness of the ternary Cu, Sn, ln bronze coating - depending on the application area -0.5 to 15 μηι, in particular about 1 to 3 μηι , is. 12. objects or articles according to any one of claims 7 to 11, characterized in that on their white, yellow or red coating on the same adherent further, electrodeposited final layer of palladium, gold and / or other precious metal, such as rhodium , Platinum, ruthenium or an alloy of the same. 13. Objects or articles according to any one of claims 7 to 12, characterized in that on the white, yellow or red Cu, Sn, ln-bronze coating on a firmly adherent, electrodeposited thin intermediate layer of palladium or a palladium alloy and Adhesive gold deposited thereon or above, or an intermediate layer of adhesive gold alone, and on this intermediate layer deposited on the Cu, Sn, In bronze coating, an electrodeposited, adherent final layer of palladium, gold and / or another noble metal in particular rhodium, platinum, ruthenium or an alloy thereof. 14. Objects or articles according to any one of claims 7 to 13, characterized in that the intermediate layer of palladium or a palladium alloy has a thickness of 0.1 to 1 μηι, and those of adhesive gold a thickness of 0.05 to 0.3 μηι having. 15. Objects or articles according to any one of claims 7 to 14, characterized in that they - instead of a 100% rhodium final layer - a final layer of a with rhodium and ruthenium, preferably in the wt .-% ratio of (70 to 90) :( 30 to 10), in particular of about 80:20, have formed alloy. 16. A method for the cathodic deposition of ternary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles using an electrolyte bath according to one of claims 1 to 6. 17. Objects or articles, in particular according to one of the claims 7 to 15, obtainable by a method for cathodic deposition of ternary alloys, using an electrolyte bath according to one of claims 1 to 6.
    [18]
    18. Use of an electrolyte bath according to one of claims 1 to 6 for the cathodic deposition of ternary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles according to one of claims 7 to 17.
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    同族专利:
    公开号 | 公开日
    WO2015000010A1|2015-01-08|
    AT514427B1|2015-01-15|
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    法律状态:
    2021-03-15| MM01| Lapse because of not paying annual fees|Effective date: 20200705 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50444/2013A|AT514427B1|2013-07-05|2013-07-05|Electrolyte bath and thus available objects or articles|ATA50444/2013A| AT514427B1|2013-07-05|2013-07-05|Electrolyte bath and thus available objects or articles|
    PCT/AT2014/050151| WO2015000010A1|2013-07-05|2014-07-03|Electrolyte bath and objects or articles coated with the aid of the bath|
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