• 专利附录
  • 专利说明
  • 权利要求
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  • 优先权
    • 专利摘要:
    The invention relates to a new electrolyte bath with a content of Cu and Sn, as well as those of zinc, there is a maximum of 5g / l, preferably at most 3g / l, for the deposition of a white coating on metallic substrates, in particular jewelry blanks and electronic Components whose content of zinc is at most 10% by weight, the coated objects and articles obtainable using this bath, the method of manufacturing said objects and articles, and the use of the new electrolyte bath.
    公开号:AT514818A1
    申请号:T50594/2013
    申请日:2013-09-18
    公开日:2015-04-15
    发明作者:
    申请人:W Garhöfer Ges M B H Ing；
    IPC主号:
    专利说明:

    Deposition of Cu, Sn, Zn coatings on metallic substrates
    The present invention is directed to an electrolytic bath composition for depositing white, high gloss, abrasion and corrosion resistant ternary bronze alloys of specific composition, free from toxic heavy metals, further to objects and articles coated with these alloys, and to a process for making the same coated objects and articles.
    Methods for the deposition of bronzes or other copper-tin alloys from cyanide baths are known. Such conventional cyanide baths are typically used for both engineering and decorative applications where nickel is undesirable because of its allergy-inducing character, or as a replacement for the much more expensive silver or palladium.
    Areas of application are in particular the production of fashion jewelery, furthermore the clothing industry, in particular for buttons, zipper closures, bra fasteners, belt buckles, leather applications and the production of furniture, door and window fittings.
    In addition to industries working with decorative applications, replacement of nickel is also gaining importance in some technical fields, such as in 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-zinc alloys, which consists essentially of water, copper cyanide, at least one tin (IV) compound, at least one zinc compound, an alkali metal cyanide, an alkali metal hydroxide, and consisting of at least one complexing agent, wetting agents and brighteners.
    For quite extensive prior art in the field, the following is to be made: US 1970549 A describes the deposition of a CuSn alloy to be used as underlayer under chromium. The aim of the invention was the production of a
    Coating that was easy to polish, especially for radiator cowlings for cars. As anodes, a CuSn alloy is used. No. 2079842 A describes the deposition of brilliant white tarnish-resistant CuSnZn layers. The base coat is Ni, nickel silver, brass, Cu, Au, Ag, Fe, steel, brazing alloy and soft solder. No. 2397522 A describes binary Sn alloys> 30% Sn with Cu, Ni, Co, Cd, Zn, Sb and the like. Whether electrolysis uses alloying anodes or anodes of the individual alloying metals, the tin often dissolves in 2-valued form and not in 4-valent form, resulting in roughness and bad coatings. US 2435967 A describes a deposition of coatings with high corrosion resistance with high gloss without pittings. The anodes are alloys similar to the composition that is to be deposited. In particular, as a brightener, a specific betaine is used.
    The composition of the anode alloy: 50 to 75% Cu, 15 to 30% Sn and 5 to 20% Zn. The Sn content of the anodes should be 2 to 3% higher than that in the deposition layer.
    The composition of the bath was: CuCN, Zn (CN) g, sodium stannate, Na 2 CO 3, NaOH, and Zn (SO 4) 2. The current density was ~ 1.6-2.2A / dm 2, the bath temperature: 60 to 71 ° C. The alloy composition of the deposit was 55 to 60% Cu, 25 to 28% Sn and 14 to 18% Zn, and the layer thicknesses were 2.5 μm to 12.7 μm or 25.4 μm to 50.8 μm.
    The corrosion resistance is better than those of Ni, Sn, Cr, Ag when they are cup-plated over.
    The basic substrate was steel or iron, which could be coated directly. Conveniently was Cu or brass as base, and on top of it CuSnZn. No. 2,436,316 A describes the deposition of CuSn or CuSnZn alloys from baths with the addition of special quaternary ammonium compounds, using either alloy anodes or insoluble anodes made of steel or carbon.
    The deposited alloy contained 50 to 75% Cu, 15 to 30% Sn and 5 to 20% Zn. CA 446846 A describes virtually identical, also electrodeposited alloys of CuSn or CuSnZn. CA 450865 A describes the deposition of a very similar alloy to chromium which is high gloss without polishing. Best results have been achieved there with soluble alloy anodes. The Sn content is slightly higher because some precipitates.
    The deposition can be clearly improved there by potassium or sodium thiocyanate or Bet. US 2,468,825 A describes a similar, silver-white coating of metallic parts, on the one hand with CuSnZn and with an overcoating of chromium, on the other hand with electrodeposited brass, CuSnZn and an overcoating of chromium. DE 815882 A describes similarly composed precipitates on metal surfaces by electrolysis using 3-component alloy anodes. No. 2,530,967 A describes another similar CuSnZn deposition of a brilliant, silver-white, abrasion-resistant precipitate on metal surfaces by means of electrolysis. US 2600699 A describes the deposition of a ZnCuSn alloy having the composition Zn about 90%, Cu about 8.5% and Sn about 1.5%, using soluble alloy anodes. US 2739933 A describes the deposition of CuSnZn alloys with 50 to 75% Cu, 15 to 35% Sn and 5 to 20% Zn from alkaline cyanide solutions with the luminescent addition 2-thiohydantoin or its derivatives and possibly molybdic acid. US Pat. No. 2,886,500 A describes alloys of Cu with Sn, Zn, Cd, wherein the Sn content of the alloy is 5 to 15% and the brightener u.a. Pb, a pyrophosphate salt and the salt of an aliphatic carboxylic acid. US 2916423 A and GB 836978 A and also GB 836979 A describe copper and copper alloy baths for the deposition of brass and bronze, wherein the addition of saccharat ions allows an improved anodic current efficiency to be achieved. CN 101109085 A describes a method for depositing a strong, ternary alloy layer of CuSnZn on the outer Cu conductor of a semi-rigid coaxial cable, an alloy containing no magnetic material whose influence on the cross modulation is neutral and whose appearance resembles that of stainless steel. JP 2002161393 A describes a method of depositing a CuSnZn alloy as the first layer at least 0.1 μm thick, depositing an AuAg alloy as an intermediate layer at least 0.1 μm thick, and depositing a Pd or palladium alloy layer without nickel thereon. The precious metal layer is extremely thin and therefore cheap.
    In particular, this alloy is also suitable for spectacle frames or parts of eyeglass frames and other parts which can also carry a person sensitive to a metal allergy because the noble metal-coated part does not contain allergy-inducing metals.
    JP 10219467 A discloses a CuPd-based alloy electrolyte with a low to at most 1 g / l Zn content as the base material for coating metals.
    JP 09-078286 A discloses an electrolytic solution for depositing white copper alloys wherein Cu cyanide and a soluble Pd compound are added to an electrolytic solution having a soluble Zn and a soluble Sn compound. US 5614327 A describes a process for protecting a silver or silver coated part especially against corrosion, wherein a CuSn alloy deposited with 53-75% Cu, 35-47% Sn and optionally up to 10% Zn with a layer thickness of at most 0.01pm becomes. DE 4324995 A, EP 0 636 713 A1 and US 5534129 A describe various baths for the production of shiny, leveling copper-tin alloys containing at least one complexing agent, such as alkali metal cyanide, alkali metal hydroxide and alkali metal carbonates, and lead. US 4814049 A and US 4496438 A describe alkaline cyanide baths for the production of CuSnZn alloy coatings, which, however, contain small amounts of nickel.
    From EP 1930478 A1 a bath for the deposition of quaternary copper alloys is known, which in addition to Cu, Sn, Zn contains a metal from the group Ga, In or TI.
    At this point, reference should be made to the relevant non-patent literature:
    In "Galvanic Coatings of Copper and Copper Alloys" by R. Pinner, Eugen-Leuze-Verlag, 1965, various CuSnZn alloys are mentioned: 1. According to Diggin, M.B. and Jernsted g. J., an alloy of 55% Cu, 30% Sn and 15% Zn, white, from a cyanide stannate solution 2. Alballoy process, the electrolyte is not disclosed, anodes: spheres of copper and tin-zinc alloys in steel cages. 3. White alloy with Cu, Sn, Zn with reference to US 2079842 and US 2198365, US 2198365 describing the gold-colored deposits. A. Brenner "Electrodeposition of Alloys", Volume 1, Academic Press Inc., 1963: Information on the electrolytic deposition of CuSnZn with reference to: BP1777, JP 88454, JP 91139, US 2079842, US 2198365, US 2435967, US 2436316, US2468825, CA 450865, US 2530967, US 2600699, US 2739933, US 2886500 GF Jacky, " Electroplating & Copper-Tin-Zinc Alloy ", Plating 58 (1971), 883-887G. F. Jacky investigated the deposition of CuSnZn alloys from alkaline cyanide baths. The alloy composition was: 55-60% Cu, balance Sn and Zn, as known from various US and CA patents described above. &Quot; http: //www.pfonline.com/articles/white-bronze-copper-tin-zinc-tri-metal-expandinq-applications-and-new-developments-in-a-chanaing-landscape" on May 20, 2013, De Potoand AI Gruenwald and Weber and Leyendecker, describes alloy compositions of tri-metal alloys with Cu 55%, Sn 30% and Zn 15% as substitutes for nickel and also as undercoat of a coating with Pd, PdNi, Ag or Au ,
    Many of the coatings mentioned there are alternatives to electrodeposited nickel.
    The use of alloy anodes, which has become known from large parts of the patent literature, is currently no longer recommended, since the production of these anodes is complex and expensive, since the use of insoluble anodes is also known.
    A major problem in the deposition of CuSn alloys from alkaline cyanide baths is the tendency of the Sn to precipitate during electrolysis. This, on the one hand, makes it difficult to deposit a constant alloy composition, on the other hand, high gloss deposition from turbid baths is nearly impossible.
    According to the present invention, this problem is solved by adding at least one very specific complexing agent to the electrolyte.
    Pb may only be used to a very limited extent under European legislation. As the bath ages and ages, the concentration of Pb increases and then exceeds the permitted limits.
    CuSn alloys are often used as a substitute for nickel coatings, especially in fashion jewelry, but also in products that come in constant or prolonged contact with the skin to avoid contact allergies. A co-alloy of nickel, even in small amounts, would make the replacement of Ni impossible.
    Furthermore, an electrolyte with four metal salts in the solution is very difficult to control in production, and in particular the use of thallium is fundamentally to be rejected because of its toxicity.
    It is an object of the present invention to develop baths from which shiny, ternary copper-tin-zinc alloys without any addition of toxic metals, such. Lead, thallium or nickel, which at the same time, due to the very special alloy composition, are of substantially improved corrosion resistance than comparable known copper-tin-zinc alloys and, more importantly, are easy and easy to monitor and maintain , Surprisingly, it has been found that when the zinc content of the deposited alloy is between 2 and 10%, preferably between 4 and 8%, and the tin content is increased above 30% by weight, both the optical appearance,. Gloss, whiteness and Like., As well as the abrasion resistance, corrosion resistance and resistance to artificial perspiration is significantly improved.
    Such alloys are therefore particularly well suited for any metallic white decorative coating, e.g. from fashion jewelery, but also for industrial applications, especially in the electronics industry.
    The invention relates to a novel electrolyte bath for the cathodic deposition of foreign alloys and / or layer sequences to form white, corrosion-resistant and (high) 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 of such tin and one zinc compound, and characterized in that it is present as an aqueous, alkaline solution for the deposition of a CuSnZn alloy containing not more than 10% by weight of Zn and in addition to being complexed. Compounds, preferably in the form of anionic complexes, present copper and tin compounds containing a, preferably cyanidic, zinc compound present in the solution with a maximum content of 5g / l, preferably of at most 3g / l, zinc, and as essential further component at least a complex picture from the group of phosphonic acids and / or alkali phosphonates, and additionally containing at least one of the group surfactants, wetting agents, chelating agents and brightening agents commonly found in electrodeposition baths.
    In particular, it is a cyanide-alkaline bath for electrodepositing new ternary copper-tin-zinc alloys with a novel composition that allows for unexpectedly highly stable and adherent, as well as high strength and high-gloss "bronze" coatings on conductive substrates.
    In the context of the present invention, it has proved to be advantageous if copper and zinc were originally prepared as cyanides, sulfates or sulfamates, in particular in formalkalic and / or cyanidically-soluble compounds, preferably copper as copper cyanide, zinc as zinc cyanide and tin as stannate or hydroxystannate the electrolyte bath.
    Accordingly, for the deposition of a 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 metal 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 of tin at 15 to 50 g / l, preferably at 20 to 30 g / l, and the content of zinc in the range of 0.5 to 5 g / l, preferably from 1 to 3 g / l varies.
    The complexing agents from the group of phosphonic acids, in particular aminotrismethylene phosphonic acid (ATMP), ethylenediamine tetramethylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic acid (DTPMP) and 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or their alkali metal salts, which are essential for the extraordinary properties of the new alloy coatings, are disclosed in US Pat Quantities of 5-50 g / l added to the electrolyte.
    With regard to other components of the new electrolyte bath than the essential phosphonic acids and their salts, it has proven advantageous if, as additional complexing agents, at least one of the group consisting of ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), pyrophosphates, gluconates, Citrates, salts of tartaric acid, and preferably further surfactants, for example alkyl ether sulfonates, alkyl ether phosphates, betaines or sulfobetaines, and / or pyridine derivatives, epichlorohydrin polymers and aminic polymers as brightener additives.
    The various electrolyte baths according to the invention or used according to the invention are described in detail in claims 2 to 6.
    Another very essential object of the invention are objects or articles, in particular jewelery or decorative articles, and further electro-technical or electronic components and components of a preferably physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or of alloys thereof or of a plastic with a conductive finish, comprising a coating of a copper, tin and zinc tertiary alloy deposited in an abovementioned electrolyte bath in which the zinc is present at a comparatively particularly low content of at most 10% by weight and thus the sum of the contents Cu and Sn in the coating is correspondingly higher than previously known.
    Specifically, these coated articles are characterized by having an alloy of 45 to 58% by weight, preferably 48 to 56% by weight, preferably on a metallic background layer, especially of copper, on the surface of the article. Copper, 32 to 48 wt .-%, preferably 35 to 45Gew .-%, tin and 2 to 10 wt .-%, preferably 4 to 8 wt .-%, zinc is arranged, to which particular reference is made to claim 8.
    As far as the total thickness of the internal copper-tin-zinc coating normally to be achieved in the context of the invention is concerned, it is 0.5 to 15 μm, in particular approximately 1 to 3 μm, depending on the field of use.
    It can - see in particular claims 7 to 14 - further be provided that on the Cu, Sn, Zn-bronze coating on the outside of a firmly adhering to the other firmly adhering final layer of palladium, gold and / or another precious metal, such as in particular rhodium , Platinum, ruthenium or an alloy of the same, by which the already high usability and the optical appearance of the objects is increased even more. For further improvements of the novel coatings of the new articles, it may further be provided that on the Cu, Sn, Zn-bronze coating there is adhered to the same adherent, electrodeposited, thin intermediate layer of palladium or of a palladium alloy and adhered thereto or otherwise such an intermediate layer of adhesive gold is arranged alone and (only) on this - on the Cu, Sn, Zn-bronze coating deposited - interlayer anelectrically deposited, adherent final layer of palladium, gold and / or another noble metal, in particular rhodium, platinum , Ruthenium or an alloy of the same. Usually, it is ensured 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 ultimate possibility is 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) to (30 to 10), in particular of about 80 to 20, have formed alloy.
    It is the object of the present invention to adjust the concentration of the metal salts, complexing agents and the additional ingredients in the mold and to vary them within the weight ratios according to the invention so that the electrolyte solution is clear and remains so that no metal salts precipitate, and that the same are intended according to the invention , shiny, 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 articles 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 0.50A / dm2 are particularly preferred. In rack coating processes, it is preferred to choose between densities of 0.2 and 10 A / dm 2, more 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 use. Iron or steel must not be used as such anodes will partially dissolve and contaminate the electrolyte.
    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 conductive at least on their surface materials is either directly or on a previously applied copper underlayer, deposited from cyanide or non-cyanide alkaline and / or acid copper baths, the new ternary copper-tin-zinc alloy deposited.
    This copper-tin-zinc alloy may be either final or final, or further coated by methods known in the art. Further z. B. intermediate or final coatings can, as already mentioned, palladium-containing, gold-containing or other noble metal-containing layers, such as those of rhodium, platinum, ruthenium or their alloys.
    In addition to the documents already mentioned at the beginning, it is known from the prior art that palladium is used as a nickel substitute, as a diffusion barrier and as corrosion protection. In these products, the base material is first-coated, then coated with palladium, and finally obtains the desired finish by coating with gold, rhodium or other noble metals or their alloys.
    To provide adequate corrosion protection, a palladium layer thickness of about 0.5-5 μm 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-zinc alloy alone, e.g. to a copper base coat, results in at least as good corrosion results as are achieved with clad primary coated base materials.
    If, instead of 1 pm of pure palladium, only 0.5 pm of pure palladium and below 2 pm of the new bronze are deposited on the Cu base coating, then the savings in the intermediate layers alone are almost 50%; If only 4 pm Cu, Sn, Zn bronze are deposited without palladium intermediate layer, 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 weight ratio rhodium to ruthenium of 80:20 is deposited as the final layer, then in addition to the savings in the intermediate layers mentioned above, 20% of the very expensive rhodium would still be saved.
    In detail, reference is made in particular to the claims 7 to 14.
    The invention further relates to a per se conventional method for the cathodic deposition of the ternary alloys according to the invention having a Zn content of at most 10% by weight on at least on their surface metallic or electrically conductive or conductive coated objects or articles using the inventive electrolyte bath according to claim 15.
    The invention further relates to the use of the electrolyte bath according to the invention for the cathodic deposition of ternary alloys on at least their surface metallic or electrically conductive or conductive coated articles or articles according to claim 16.
    The invention will be explained in more detail by means of the following non-limiting examples:
    Example 1:
    electrolyte:
    9 g / l Cu from CuCN 22 g / l Sn from alkali stannate 1 g / l Zn from zinc cyanide 40 ml / l 1-hydroxyethane-1,1-diphosphonic acid (as essential complexing agent)
    60 g / l Seignette salt 45 g / l KCN25 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 degreased electrolytically 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.
    The jewelry blank is then rinsed in deionized water, stripped in 5% sulfuric acid solution for 30 seconds, and acidified in a copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of Ing. W. Garhöfer GesmbH), 20 pm of copper are deposited, leveling and high-gloss, at 4 A / dm 2 and 25 ° C. The blank is again rinsed and pre-immersed in a 10% KCN solution.
    Then, from a bronze electro-bath according to the present invention, 2 pm bronze alloy of composition copper: 55%, tin: 39%, zinc: 6%, at 60 ° C, and 1 A / dm2 are deposited 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 containing copper-tin-zinc layers with a zinc content greater than 10% in the alloy produced on the same base material in the SO 2 test is about twice as good.
    Example 2:
    Electrolyte:
    9 g / l Cu from CuCN 22 g / l Sn from alkali tannin 1 g / l Zn from zinc cyanide 40 ml / l 1-hydroxyethane-1,1-diphosphonic acid (as essential complexing agent)
    60 g / l Seignette salt 45 g / l KCN25 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 zinc die casting is electrolytically degreased in a slightly 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 pre-copper bath containing 22 g / l Cu and 34 g / l KCN (" Cuproga ", product of Ing. W. Garhöfer GesmbH), 5 pm copper at 1 A / dm2 and 50 ° Cabgeschieden.
    The pre-plated jewelry blank is then de-capped in 5% sulfuric acid solution for 30 seconds and in an acid copper bath with 50 g / l Cu and 60 g / l sulfuric acid (" IWGCu 550 ", product of Ing. W. Garhöfer GesmbH) becomes 15pm Copper depositing and high gloss deposited at 4 A / dm2 and 25 ° C. The thus coppered part is rinsed and pre-immersed in a 10% KCN solution.
    Then, from a bronze electrolytic bath according to the present invention, 2 pm bronze alloy of the composition copper: 55%, tin: 39%, zinc: 6%, at 60 ° C. and 1 A / dm2 are precipitated from the electrolyte within 10 minutes. Thereafter, deionized water is rinsed, 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 at 1A / dm2 and 25 ° C coated.
    After renewed rinsing and acid dipping, the jewelery thus obtained is mixed with 0.1 .mu.mol. Of a weakly acidic electrolyte with 2.5 g / l Au ("MC 218", product of Fab. Ing. W. Garhöfer GesmbH) at 1.5 A. / dm2 and 35 ° C provided. It is then rinsed thoroughly with demineralised water, stripped in 5% sulfuric acid solution and 0.2 ppm rhodium from an electrolyte containing 2 g / l Rh and 50 g / l sulfuric acid (" Rhodium C2 ", product of Ing. W. Garhöfer GesmbH ) rhodinated at 3V and 35 ° C.
    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 bright white and high gloss.
    Corrosion resistance according to DIN 50018:
    The electroplated article performed significantly better in the corrosion tests than did the parts using the same method, but with a copper-tin-zinc alloy comparable in content to Cu and Sn, but with a zinc content of more than 10% zinc in the alloy had been coated.
    权利要求:
    Claims (16)
    [1]
    1. Electrolyte bath for the cathodic deposition of ternary alloys and / or layers to form white, corrosion-resistant and (high) 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 contains at least one such tin and one zinc compound, characterized in that it is - for the deposition of a CuSnZn alloy containing not more than 10% by weight Zn - as an aqueous, alkaline-reacting solution and except as complex compounds, preferably in the form of anionic complexes, of the present copper and tin compounds, contains a zinc compound in an amount which is present in the solution with a maximum content of 5 g / l, preferably of not more than 3 g / l, of zinc, and as essential further component at least one complex from the group of phosphonic acids and / or A Lkaliphosphonate and additionally at least one of the components contained in the electrodeposition baths commonly contained in the group surface-active substances, wetting agents, complexing agents and brighteners.
    [2]
    Electrolyte bath according to claim 1, characterized in that it has a content of free alkali metal cyanide of 15 to 70 g / l, preferably of 20 to 60 g / l, and more preferably of 25 to 45 g / l, and of alkali hydroxide of 5 to 40 g / l, preferably from 10 to 30 g / l, and that the content of copper is from 5 to 25 g / l, the content of tin is from 15 to 50 g / l and that of zinc from 1 to 3 g / l.
    [3]
    3. An electrolyte bath according to claim 1 or 2, characterized in that it has a content of free alkali metal cyanide and alkali metal hydroxide, as indicated in claim 2, and that the content of Cu from 8 to 15 g / l, the content of Sn from 20 to 30 g / l and that of Zn is from 1 to 3 g / l.
    [4]
    4. electrolyte bath according to one of claims 1 to 3, characterized in that the alloying metals contained therein originally in the form of cyanides, sulfates, sulfamates, in particular as alkaline and / or cyanidically soluble compounds, preferably Cu as copper cyanide, tin as stannate or hydroxystannate ( Hydroxostannate) and zinc as cyanide.
    [5]
    5. electrolyte bath according to one of claims 1 to 4, characterized in that it contains as essential complexing agent at least one phosphonic acid or at least one alkali metal salt of a phosphonic acid from the group of Aminotrismethylenphosphonsäure (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), Diethylentriaminpentamethylenphosphonsäure (DTPMP) and 1-hydroxyethane 1,1-diphosphonic acid (HEDP) or its alkali metal salts are contained in amounts of 5 to 50 g / l.
    [6]
    6. electrolytic bath according to one of claims 1 to 4, characterized in that it contains as complexing agents in addition to the phosphonic acid and / or Alkaliphosphonatenzat least one from the group of ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), pyrophosphates, gluconates, Citrates, salts of tartaric acid, and preferably further surfactants. Wetting agents, for example alkyl ether sulfonates, alkyl ether phosphates, betaines or sulfobetaines, and / or pyridine derivatives, epichlorohydrin polymers and aminic polymers, as brightener additives.
    [7]
    7. Objects or articles, in particular jewelery or decorative articles, and further electrical or electronic components and components of a, preferably physiologically acceptable, metal, in particular brass, zinc, tin, iron or steel, or alloys thereof or else a conductive plastic comprising a white coating based on copper, tin and zinc deposited from an electrolyte bath of any one of claims 1 to 6, characterized in that it is coated with a coating of a ternary alloy of copper, tin and zinc containing less than 10% by weight % Zn are present.
    [8]
    8. 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 to 6 white coating or with such a corrosion-resistant, highly abrasion and adherent, shiny coating, preferably one aufeiner directly on the surface of the article located and deposited thereon, preferably of copper, an alloy of 45 to 58 wt% copper, 32 to 48 wt% tin, and 2 to 10 wt% zinc.
    [9]
    9. objects or articles according to claim 7, characterized in that they are provided with a abgeabeschiedenen from the electrolyte bath according to one of claims 1 to 6 white coating or with such a corrosion-resistant, highly abrasion and adherent, shiny coating, wherein, preferably one on directly on the surface of the object or metallic underlying layer, preferably made of copper, an alloy with 48 to 56 wt .-% copper, 35 to 45 wt .-% tin and 4 to 8 wt .-% zinc is arranged.
    [10]
    10. objects or articles according to any one of claims 7 to 9, characterized in that the total thickness of the ternary Cu, Sn, Zn bronze coating - depending on the application area -0.5 to 15 μηι, in particular about 1 to 3 μηι, is.
    [11]
    11. Objects or articles according to any one of claims 7 to 10, characterized in that on their white Cu, Sn, Zn-bronze coating on the same festhaftende another, electrodeposited final layer of palladium, gold and / or other precious metal, such as especially rhodium, platinum, ruthenium or an alloy of these precious metals.
    [12]
    12. An article according to any one of claims 7 to 11, characterized in that on the white Cu, Sn, Zn-bronze coating thereon is a firmly adherent, electrodeposited thin intermediate layer of palladium or of a palladium alloy and adhered thereto or otherwise such an intermediate layer of adhesive gold is arranged alone and on this - deposited on the Cu, Sn, Zn-bronze coating - intermediate layer an electrodeposited, adherent final layer of palladium, gold and / or another noble metal, in particular rhodium, platinum, ruthenium or an alloy from these precious metals, is arranged.
    [13]
    13. Objects or articles according to any one of claims 7 to 12, 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 has a thickness of 0.05 to 0.3 μηι.
    [14]
    14. An article according to any one of claims 7 to 13, characterized in that it comprises, instead of a 100% rhodium final layer, a final layer of rhodium and ruthenium, preferably in the weight% ratio of (70 to 90 ) :( 30 to 10), especially about 80:20.
    [15]
    15. A process for the preparation of a white coating or with such a corrosion-resistant, highly abrasion-resistant and adherent, shiny coating are provided, wherein, preferably on a surface of the object or article befindliches metallic background layer, in particular copper, alloys, objects or Articles, in particular jewelery or decorative articles, and other electrical or electronic components and components of a physiologically acceptable metal, in particular of brass, zinc, tin, iron or steel, or of alloys thereof or of a conductive plastic, characterized in that to be coated Objektebzw. An article, optionally after a basecoat with copper, by means of electrolytes in an electrolyte bath according to any one of claims 1 to 6 at temperatures of 40 to 70 ° C and current densities of 0.1 to 10 A / dm2, in the case of a drum coating process at current densities of 0.2 to 10 A / dm2, in particular from 0.2 to 5 A / dm2, are subjected to electrolysis using at least one insoluble cathode.
    [16]
    16. Use of an electrolyte bath according to any one of claims 1 to 6 for the preservation of an object or article coated with a white Cu, Sn, Zn bronze having a zinc content of at most 10% by weight, according to one of claims 7 to 14.
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    同族专利:
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    法律状态:
    2020-08-15| MM01| Lapse because of not paying annual fees|Effective date: 20190918 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50594/2013A|AT514818B1|2013-09-18|2013-09-18|Deposition of Cu, Sn, Zn coatings on metallic substrates|ATA50594/2013A| AT514818B1|2013-09-18|2013-09-18|Deposition of Cu, Sn, Zn coatings on metallic substrates|
    PCT/AT2014/050202| WO2015039152A1|2013-09-18|2014-09-11|Deposition of cu, sn, zn-layers on metallic substrates|
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