EP0943701B1 - Process and reactive solution for producing a patina - Google Patents

Process and reactive solution for producing a patina Download PDF

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Publication number
EP0943701B1
EP0943701B1 EP99102955A EP99102955A EP0943701B1 EP 0943701 B1 EP0943701 B1 EP 0943701B1 EP 99102955 A EP99102955 A EP 99102955A EP 99102955 A EP99102955 A EP 99102955A EP 0943701 B1 EP0943701 B1 EP 0943701B1
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EP
European Patent Office
Prior art keywords
copper
patina
salts
carbonate
reaction solution
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EP99102955A
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German (de)
French (fr)
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EP0943701A1 (en
Inventor
Sonja Dr. Priggemeyer
Stefan Dr. Priggemeyer
Stefan Hoveling
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KME Special Products GmbH and Co KG
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KM Europa Metal AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon

Definitions

  • the invention relates to a method and a reaction solution for producing a patina on surfaces of objects made of copper or a copper alloy.
  • patina In the air, a thin green protective layer of basic copper compounds forms on copper surfaces. This is called patina.
  • the formation of natural patina sometimes takes several decades, depending on the environment. Artificial patination, for example by application of soluble copper salts or ammonium salts, serves to imitate this natural patina, which often forms over long periods of time.
  • basic copper compounds are applied as color pigments with organic or inorganic film formers to a copper surface.
  • the US-A-3,497,401 discloses a method and reaction solution for producing a patina on the surface of a copper article.
  • the reaction solution consists of an aqueous solution containing potassium chlorate and copper sulfate.
  • a reaction solution is used to produce a patina on copper objects, which in aqueous solution contains hydrochloric acid, copper carbonate, ammonium chloride, copper acetate, arsenic trioxide and copper nitrate.
  • reaction solutions do not always provide the desired results in terms of layer quality and coloration. Also, their handling and storage is sometimes expensive. They are therefore only of limited suitability for industrial use for factory production of a patina or when used on the construction site. Also, when using some of these reaction solutions on preoxidized or partially patinated copper surfaces, for example for repair of damaged patina, there is a risk of uneven layer formation and staining.
  • the WO 97/35046 describes a process in which an artificial patina is to be produced with the aid of a reaction solution of copper sulfate, sodium thiosulfate and lead (II) acetate.
  • This reaction solution has by their lead component the great disadvantage that it is classified in terms of their health and environmental hazards as critical and it does not meet the requirement of the invention for environmentally friendly use.
  • the invention is therefore based on the object to provide a method for producing a mechanically stable patina on preferably pre-weathered copper surfaces, wherein the patina produced has a reduced copper solubility and as in a natural patina, an interaction with the atmosphere is possible. Furthermore, the invention aims at an improved reaction solution for producing a patina on copper surfaces, which is also easy to handle and storage.
  • a reaction solution consisting of an aqueous solution of copper salts in the form of copper (I) carbonate, copper (II) carbonate, copper (I) chloride, copper (II) sulfate, copper nitrate or mixtures thereof is applied to the surface of a copper article after its purification in a concentration between 0.5% and 50% and salts of inorganic acids in the form of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium chloride, potassium chloride, ammonium chloride, sodium sulphate, sodium bisulphate, potassium sulphate, potassium bisulphate or mixtures thereof in a concentration between 0, 5% and 50% applied.
  • the thus treated copper object is then exposed to weathering the drying exposed.
  • the patina produced according to the method is mechanically stable and has only a low copper solubility. The time for producing the patina is comparatively low.
  • the generated patina is provided after drying with a transparent protective layer of paint.
  • this is a two-component water-based paint is used, which contains rubber.
  • the paint is colorless.
  • the paint Before application, the paint is applied with hardener.
  • the ratio of hardener to paint is usually 1: 4.
  • the starting time is a maximum of 20 minutes.
  • the finished mixed paint is then preferably applied to the patina with a sprayer.
  • the paint After the drying phase, the paint is cured and can be weathered. Depending on the prevailing ambient conditions (temperature, humidity, etc.), the dry phase can take 15 to 24 hours.
  • a copper article according to the invention is characterized according to claim 2 by its transparent lacquer layer on the patinated surface.
  • An inventive copper article or its patina surface is improved in resistance to external environmental influences and damage.
  • the patinated copper objects can be machined without the patina flaking off.
  • reaction solution consists of an aqueous solution of copper salts and salts of inorganic acids and contains a wetting agent and / or a thickener in a proportion of up to 5%.
  • the reaction solution according to the invention uses the combination of two different principles for patina formation.
  • the reaction solution contains reactive components in the form of salts of inorganic acids, which react with the copper oxides of the patinated surfaces to form basic copper compounds.
  • the speed of this reaction step depends on the weathering conditions.
  • the solution already contains the forming in these reactions copper compounds in the form of copper salts as a kind of color pigments. For this reason, a very good color impression is already achieved immediately after the application. The imitation of the otherwise often only in long periods forming natural patina happens in a short time.
  • the subsequent chemical reaction intensifies the color impression and solidifies the entire patina layer.
  • the best success with the reaction solution according to the invention arises when used on a preoxidized or already partially patinated copper surface. For this reason, the copper articles should receive a corresponding surface pretreatment.
  • the copper surface may be pre-oxidized or pre-patinated at the factory.
  • the copper surface may also have a natural patina caused by natural weathering.
  • An untreated copper surface should be exposed to natural weathering for about two months or more.
  • the treatment can be carried out with the reaction solution according to the invention.
  • a patina layer By applying the reaction solution on a pre-oxidized or already partially patinated copper surface, a patina layer can be produced directly on site or else at the factory. Also, copper surfaces that are not completely patinated green or damaged patina layers obtained when applying the reaction solution according to the invention a uniform patina layer. Depending on the composition of the reaction solution, the color of the patina to be produced can be varied and otherwise adapted to the respective environment.
  • the processing and handling of the reaction solution according to the invention is simple.
  • the order on the copper surfaces can be done for example by means of a brush, roller or a spray device.
  • a storage of the reaction solution is possible over a longer period of several months at room temperature, without aging damage.
  • copper (I) carbonate, copper (II) carbonate, copper (I) chloride, copper (II) chloride, copper (II) sulfate, copper acetate, copper nitrate or mixtures thereof are well suited.
  • the advantageous concentration range is between 5 and 500 g / l.
  • the reactive component used is preferably sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium chloride, potassium chloride, ammonium chloride, sodium sulfate, sodium hydrogensulfate, potassium sulfate, sodium hydrogensulfate, potassium sulfate, potassium hydrogensulfate or mixtures thereof.
  • concentration range of these salts of inorganic acids is preferably between 5 and 500 g / l.
  • the reaction solution according to the invention can be changed in its consistency by the addition of wetting agents or thickeners and be tailored to the particular conditions of use.
  • wetting agents for example surfactants, and / or come Thickeners of known type for use. They are added to the reaction solution to a level of 5%.
  • the reaction solution according to the invention produces a high quality patina from basic copper compounds and is particularly well suited for preoxidized or already partially patinated copper surfaces.
  • the treatment can be done on site or at the factory.
  • the reaction solution is also good for that
  • the reaction solution can be prepared and processed at room temperature. It has been found to be expedient that a patinated surface after treatment with the reaction solution should be protected from rain for at least 48 hours.
  • the patina layer produced in this way can then be coated with a transparent protective layer to avoid damage and to reduce the copper solubility.
  • a transparent protective layer to avoid damage and to reduce the copper solubility.
  • water-vapor-permeable paints are used, which produce an open-pored protective layer and thus allow the natural interaction of the patina surface with the atmosphere.
  • An aqueous solution containing 200 g / l of copper sulfate is first mixed with 200 g / l of sodium carbonate and stirred for one hour at room temperature. Thereafter, 200 g / l of sodium chloride are added and stirred for another hour at room temperature. Subsequently, the solution can be applied directly to the surface to be patinated.
  • a wetting agent for example a surfactant, in a concentration of 50 g / l is added.
  • the solution is thickened with a commercially available thickener in a concentration of 50 g / l.
  • the reaction solution thus prepared can be stored without restriction at room temperature.
  • the copper surface to be patinated has a dark brown copper oxide layer, which in places is already covered with copper salts (patina).
  • the surface is freed from grease and loosely attached dirt before patinating.
  • the removal of loosely adhered dirt particles can be done using water and manual or mechanical means.
  • the surfaces which should not be patinated are masked off. Thereafter, the already prepared ready reaction solution is shaken or stirred and applied.
  • a sprayer has proven particularly suitable for this purpose. Depending on the performance of the sprayer used nozzles between 0.2 mm and 0.6 mm diameter are used. For uniform coating of the surface, spray angles of 60 ° to 90 ° considered advantageous. Care should be taken during treatment to avoid dripping on the surface.
  • the drying process should be as slow and even as possible. This improves the quality of the patina.
  • the protective layer of lacquer can then be applied.
  • a sprayer preferably with nozzles between 0.2 mm and 0.3 mm in diameter, and a spray angle of 90 ° is recommended.
  • a single application of the protective layer is sufficient.
  • the protective layer which can be between 20 minutes and 24 hours depending on weather conditions, the copper object should be protected from precipitation.

Abstract

A patina is produced on a copper article using a reactive aqueous solution of copper salts and inorganic acid salts. A patina is produced on the surface of a copper or copper alloy article by cleaning the surface, applying an aqueous solution of copper salts and salts of inorganic acids and then drying while protecting against the weather. An Independent claim is also included for a reactive solution used in the above process and comprising an aqueous solution of copper salts and inorganic acid salts, preferably together with a wetting agent and a thickener.

Description

Die Erfindung betrifft ein Verfahren und eine Reaktionslösung zur Erzeugung einer Patina auf Oberflächen von Gegenständen aus Kupfer oder einer Kupferlegierung.The invention relates to a method and a reaction solution for producing a patina on surfaces of objects made of copper or a copper alloy.

An der Luft bildet sich auf Kupferoberflächen eine dünne grüne Schutzschicht aus basischen Kupferverbindungen. Diese wird Patina genannt. Die Ausbildung natürlicher Patina dauert je nach Umwelteinflüssen manchmal mehrere Jahrzehnte. Das künstliche Patinieren, beispielsweise durch Auftragen löslicher Kupfersalze oder von Ammoniumsalzen, dient zur Nachahmung dieser sich oft erst in langen Zeiträumen bildenden natürlichen Patina. Bei imitierter Patina werden basische Kupferverbindungen als Farbpigmente mit organischen oder anorganischen Filmbildnern auf eine Kupferoberfläche aufgetragen.In the air, a thin green protective layer of basic copper compounds forms on copper surfaces. This is called patina. The formation of natural patina sometimes takes several decades, depending on the environment. Artificial patination, for example by application of soluble copper salts or ammonium salts, serves to imitate this natural patina, which often forms over long periods of time. In imitated patina, basic copper compounds are applied as color pigments with organic or inorganic film formers to a copper surface.

Die US-A-3,497,401 offenbart ein Verfahren und eine Reaktionslösung zur Erzeugung einer Patina auf der Oberfläche eines Gegenstands aus Kupfer. Die Reaktionslösung besteht aus einer wässerigen Lösung, die Kaliumchlorat und Kupfersulfat enthält.The US-A-3,497,401 discloses a method and reaction solution for producing a patina on the surface of a copper article. The reaction solution consists of an aqueous solution containing potassium chlorate and copper sulfate.

Bei dem aus der US-A-5,160,381 bekannten Verfahren kommt eine Reaktionslösung zur Erzeugung einer Patina auf Kupfergegenständen zur Anwendung, welche in wässriger Lösung Salzsäure, Kupferkarbonat, Ammoniumchlorid, Kupferacetat, Arsentrioxid sowie Kupfernitrat enthält.In the from the US-A-5,160,381 In known processes, a reaction solution is used to produce a patina on copper objects, which in aqueous solution contains hydrochloric acid, copper carbonate, ammonium chloride, copper acetate, arsenic trioxide and copper nitrate.

Weitere Vorschläge zur Erzeugung einer künstlichen Patina auf Kupfergegenständen gehen aus den JP 09 067681 A , JP 55 110780 A und JP 62 192586 A hervor. Hierbei kommen unterschiedliche Reaktionslösungen zur Anwendung, die Kupfersalze und andere Salze organischer Säuren enthalten.Other proposals for producing an artificial patina on copper objects go from the JP 09 067681 A . JP 55 110780 A and JP 62 192586 A out. In this case, different reaction solutions are used which contain copper salts and other salts of organic acids.

Einige der bekannten Reaktionslösungen bringen jedoch nicht immer den gewünschten Erfolg hinsichtlich Schichtqualität und Färbung. Auch ist teilweise ihre Handhabung und Lagerung aufwendig. Sie sind daher für den industriellen Einsatz zur werksseitigen Erzeugung einer Patina oder beim Einsatz auf der Baustelle nur bedingt geeignet. Auch besteht bei der Verwendung einiger dieser Reaktionslösungen auf voroxidierten oder schon teilweise patinierten Kupferoberflächen, beispielsweise zu Reparaturzwecken von beschädigter Patina, die Gefahr einer ungleichmäßigen Schichtausbildung und Färbung.However, some of the known reaction solutions do not always provide the desired results in terms of layer quality and coloration. Also, their handling and storage is sometimes expensive. They are therefore only of limited suitability for industrial use for factory production of a patina or when used on the construction site. Also, when using some of these reaction solutions on preoxidized or partially patinated copper surfaces, for example for repair of damaged patina, there is a risk of uneven layer formation and staining.

Die WO 97/35046 beschreibt ein Verfahren, bei dem mit Hilfe einer Reaktionslösung aus Kupfersulfat, Natriumthiosulfat und Blei(II)acetat eine künstliche Patina erzeugt werden soll.
Diese Reaktionslösung hat durch ihren Bleibestandteil den großen Nachteil, dass sie hinsichtlich ihrer Gesundheits- und Umweltgefährdung als kritisch einzustufen ist und sie nicht dem erfindungsgemäßen Erfordernis der umweltschonenden Verwendung entspricht.The WO 97/35046 describes a process in which an artificial patina is to be produced with the aid of a reaction solution of copper sulfate, sodium thiosulfate and lead (II) acetate.
This reaction solution has by their lead component the great disadvantage that it is classified in terms of their health and environmental hazards as critical and it does not meet the requirement of the invention for environmentally friendly use.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Erzeugung einer mechanisch stabilen Patina auf vorzugsweise vorbewitterten Kupferoberflächen zu schaffen, wobei die erzeugte Patina eine reduzierte Kupferlöslichkeit aufweist und wie bei einer natürlichen Patina eine Wechselwirkung mit der Atmosphäre möglich ist. Ferner zielt die Erfindung auf eine verbesserte Reaktionslösung zur Erzeugung einer Patina auf Kupferoberflächen ab, welche zudem einfach in ihrer Handhabung und ihrer Lagerung ist.The invention is therefore based on the object to provide a method for producing a mechanically stable patina on preferably pre-weathered copper surfaces, wherein the patina produced has a reduced copper solubility and as in a natural patina, an interaction with the atmosphere is possible. Furthermore, the invention aims at an improved reaction solution for producing a patina on copper surfaces, which is also easy to handle and storage.

Die Lösung des verfahrensmäßigen Teils der Aufgabe besteht in den Maßnahmen des Anspruchs 1.The solution of the procedural part of the task consists in the measures of claim 1.

Danach wird auf die Oberfläche eines Kupfergegenstands nach deren Reinigung eine Reaktionslösung bestehend aus einer wässerigen Lösung von Kupfersalzen in Form von Kupfer(I)carbonat, Kupfer(II)carbonat, Kupfer(I)chlorid, Kupfer(II)sulfat, Kupfernitrat oder Mischungen hiervon in einer Konzentration zwischen 0,5 % und 50 % und Salzen anorganischer Säuren in Form von Natriumcarbonat, Kaliumcarbonat, Ammoniumcarbonat, Natriumhydrogencarbonat, Kaliumhydrogencarbonat, Natriumchlorid, Kaliumchlorid, Ammoniumchlorid, Natriumsulfat, Natriumhydrogensulfat, Kaliumsulfat, Kaliumhydrogensulfat oder Mischungen hiervon in einer Konzentration zwischen 0,5 % und 50 % aufgetragen. Der so behandelte Kupfergegenstand wird dann vor Witterungseinflüssen geschützt der Trocknung ausgesetzt.Thereafter, a reaction solution consisting of an aqueous solution of copper salts in the form of copper (I) carbonate, copper (II) carbonate, copper (I) chloride, copper (II) sulfate, copper nitrate or mixtures thereof is applied to the surface of a copper article after its purification in a concentration between 0.5% and 50% and salts of inorganic acids in the form of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium chloride, potassium chloride, ammonium chloride, sodium sulphate, sodium bisulphate, potassium sulphate, potassium bisulphate or mixtures thereof in a concentration between 0, 5% and 50% applied. The thus treated copper object is then exposed to weathering the drying exposed.

Die Trocknung erfolgt üblicherweise an der Luft, bis die Patina vollkommen durchgehärtet ist. Die verfahrensgemäß hergestellte Patina ist mechanisch stabil und weist nur eine geringe Kupferlöslichkeit auf. Die Zeit für die Herstellung der Patina ist vergleichsweise gering.Drying is usually done in air until the patina is fully cured. The patina produced according to the method is mechanically stable and has only a low copper solubility. The time for producing the patina is comparatively low.

Die erzeugte Patina wird nach der Trocknung mit einer transparenten Schutzschicht aus Lack versehen.The generated patina is provided after drying with a transparent protective layer of paint.

Vorzugsweise kommt hierzu ein Zweikomponentenlack auf Wasserbasis zum Einsatz, welcher Kautschuk enthält. Der Lack ist farblos.Preferably, this is a two-component water-based paint is used, which contains rubber. The paint is colorless.

Vor dem Auftrag wird der Lack mit Härter angesetzt. Das Verhältnis von Härter zu Lack beträgt üblicherweise 1:4. Die Ansetzzeit beträgt maximal 20 Minuten. Der fertig angemischte Lack wird dann vorzugsweise mit einem Spritzgerät auf die Patina aufgetragen.Before application, the paint is applied with hardener. The ratio of hardener to paint is usually 1: 4. The starting time is a maximum of 20 minutes. The finished mixed paint is then preferably applied to the patina with a sprayer.

Nach der Trockenphase ist der Lack ausgehärtet und kann bewittert werden. Je nach den vorherrschenden Umgebungsbedingungen (Temperatur, Luftfeuchte etc.) kann die Trockenphase 15 bis 24 Stunden dauern.After the drying phase, the paint is cured and can be weathered. Depending on the prevailing ambient conditions (temperature, humidity, etc.), the dry phase can take 15 to 24 hours.

Die erfindungsgemäß aufgebrachte Lackschicht hat insbesondere folgende Eigenschaften und Vorteile:

  • Die Lackschicht ist transparent und matt. Sie verändert nicht die optischen Eigenschaften der darunter liegenden Patina.
  • Die Lackschicht kann mit Reinigungslösungen behandelt werden. Dementsprechend können beispielsweise Verunreinigungen wie aufgesprühte Graffities mit speziellen Reinigungslösungen rückstandsfrei entfernt werden, ohne daß die Patina beschädigt wird.
  • Die Lackschicht ist wasserdampfdiffusionsdurchlässig. Hierdurch kann die darunter liegende Patina weiter mit der Atmosphäre in Wechselwirkung treten.
  • Die Lackschicht bewirkt eine Verfestigung der darunter liegenden Patinaoberfläche. Patinierte Kupfergegenstände können folglich mechanisch bearbeitet werden, beispielsweise durch Biegen oder Falzen, ohne daß die Patinierung abplatzt.
The lacquer layer applied according to the invention has in particular the following properties and advantages:
  • The lacquer layer is transparent and matt. It does not alter the optical properties of the underlying patina.
  • The lacquer layer can be treated with cleaning solutions. Accordingly, for example, impurities such as sprayed graffiti with special cleaning solutions can be removed without residue without the patina is damaged.
  • The lacquer layer is permeable to water vapor diffusion. This allows the underlying patina to continue interacting with the atmosphere.
  • The lacquer layer causes a solidification of the underlying patina surface. Patinated copper articles can thus be mechanically processed, for example by bending or folding, without the patination flaking off.

Ein erfindungsgemäßer Kupfergegenstand ist gemäß Anspruch 2 durch seine transparente Lackschicht auf der patinierten Oberfläche charakterisiert. Ein erfindungsgemäßer Kupfergegenstand bzw. seine Patinaoberfläche ist in der Resistenz gegen äußere Umwelteinflüsse und Beschädigungen verbessert. Die patinierten Kupfergegenstände können mechanisch bearbeitet werden, ohne daß die Patina abplatzt.A copper article according to the invention is characterized according to claim 2 by its transparent lacquer layer on the patinated surface. An inventive copper article or its patina surface is improved in resistance to external environmental influences and damage. The patinated copper objects can be machined without the patina flaking off.

Die Lösung des auf die Reaktionslösung gerichteten Teils der Aufgabe sieht nach Anspruch 3 vor, daß die Reaktionslösung aus einer wässrigen Lösung von Kupfersalzen sowie Salzen anorganischer Säuren besteht und ein Netzmittel und/oder einen Verdicker jeweils in einem Anteil von bis zu 5 % enthält.The solution of the directed to the reaction solution part of the task according to claim 3 that the reaction solution consists of an aqueous solution of copper salts and salts of inorganic acids and contains a wetting agent and / or a thickener in a proportion of up to 5%.

Die erfindungsgemäße Reaktionslösung nutzt die Kombination zweier unterschiedlicher Prinzipien zur Patinabildung. Zum einen enthält die Reaktionslösung reaktive Komponenten in Form von Salzen anorganischer Säuren, die mit den Kupferoxiden der patinierten Oberflächen zu basischen Kupferverbindungen reagieren. Die Geschwindigkeit dieses Reaktionsschrittes hängt von den Bewitterungsbedingungen ab. Ferner enthält die Lösung bereits die sich bei diesen Reaktionen bildenden Kupferverbindungen in Form von Kupfersalzen als eine Art Farbpigmente. Aus diesem Grund wird unmittelbar nach der Auftragung bereits ein sehr guter Farbeindruck erreicht. Die Nachahmung der ansonsten oft erst in langen Zeiträumen sich bildenden natürlichen Patina geschieht in kurzer Zeit. Durch die anschließende chemische Reaktion erfolgt eine Intensivierung des Farbeindrucks und eine Verfestigung der gesamten Patinaschicht.The reaction solution according to the invention uses the combination of two different principles for patina formation. On the one hand, the reaction solution contains reactive components in the form of salts of inorganic acids, which react with the copper oxides of the patinated surfaces to form basic copper compounds. The speed of this reaction step depends on the weathering conditions. Furthermore, the solution already contains the forming in these reactions copper compounds in the form of copper salts as a kind of color pigments. For this reason, a very good color impression is already achieved immediately after the application. The imitation of the otherwise often only in long periods forming natural patina happens in a short time. The subsequent chemical reaction intensifies the color impression and solidifies the entire patina layer.

Der beste Erfolg mit der erfindungsgemäßen Reaktionslösung stellt sich ein bei der Anwendung auf einer voroxidierten bzw. schon teilweise patinierten Kupferoberfläche. Aus diesem Grund sollten die Kupfergegenstände eine entsprechende Oberflächenvorbehandlung erhalten. Die Kupferoberfläche kann werksseitig voroxidiert oder vorpatiniert sein. Die Kupferoberfläche kann aber auch eine durch natürliche Bewitterung entstandene Patinaschicht aufweisen. Eine nicht vorbehandelte Kupferoberfläche sollte ca. zwei Monate oder länger der natürlichen Bewitterung ausgesetzt sein.The best success with the reaction solution according to the invention arises when used on a preoxidized or already partially patinated copper surface. For this reason, the copper articles should receive a corresponding surface pretreatment. The copper surface may be pre-oxidized or pre-patinated at the factory. The copper surface may also have a natural patina caused by natural weathering. An untreated copper surface should be exposed to natural weathering for about two months or more.

Nach einer derartigen Oberflächenvorbehandlung kann die Behandlung mit der erfindungsgemäßen Reaktionslösung erfolgen.After such a surface pretreatment, the treatment can be carried out with the reaction solution according to the invention.

Durch Anwendung der Reaktionslösung auf einer voroxidierten bzw. schon teilweise patinierten Kupferoberfläche kann direkt vor Ort oder auch werksseitig eine Patinaschicht erzeugt werden. Auch Kupferoberflächen, die nicht vollständig grün patiniert sind oder beschädigte Patinaschichten erhalten bei Anwendung der erfindungsgemäßen Reaktionslösung eine gleichmässige Patinaschicht. Je nach Zusammensetzung der Reaktionslösung kann die Farbgebung der zu erzeugenden Patina variiert und sonst der jeweiligen Umgebung angepaßt werden.By applying the reaction solution on a pre-oxidized or already partially patinated copper surface, a patina layer can be produced directly on site or else at the factory. Also, copper surfaces that are not completely patinated green or damaged patina layers obtained when applying the reaction solution according to the invention a uniform patina layer. Depending on the composition of the reaction solution, the color of the patina to be produced can be varied and otherwise adapted to the respective environment.

Die Verarbeitung und die Handhabung der erfindungsgemäßen Reaktionslösung ist einfach. Der Auftrag auf die Kupferoberflächen kann beispielsweise mittels Pinsel, Rolle oder einer Sprühvorrichtung erfolgen.The processing and handling of the reaction solution according to the invention is simple. The order on the copper surfaces can be done for example by means of a brush, roller or a spray device.

Eine Lagerung der Reaktionslösung ist über einen längeren Zeitraum von mehreren Monaten bei Raumtemperatur möglich, ohne daß Alterungsschäden auftreten.A storage of the reaction solution is possible over a longer period of several months at room temperature, without aging damage.

Für die in der wässrigen Reaktionslösung verwendeten Kupfersalze sind Kupfer(I)carbonat, Kupfer(II)carbonat, Kupfer(I)chlorid, Kupfer(II)chlorid, Kupfer(II)sulfat, Kupferacetat, Kupfernitrat oder Mischungen hiervon gut geeignet. Der vorteilhafte Konzentrationsbereich liegt zwischen 5 und 500 g/l.For the copper salts used in the aqueous reaction solution, copper (I) carbonate, copper (II) carbonate, copper (I) chloride, copper (II) chloride, copper (II) sulfate, copper acetate, copper nitrate or mixtures thereof are well suited. The advantageous concentration range is between 5 and 500 g / l.

Als reaktive Komponente kommt vorzugsweise Natriumcarbonat, Kaliumcarbonat, Ammoniumcarbonat, Natriumhydrogencarbonat, Kaliumhydrogencarbonat, Natriumchlorid, Kaliumchlorid, Ammoniumchlorid, Natriumsulfat, Natriumhydrogensulfat, Kaliumsulfat, Natriumhydrogensulfat, Kaliumsulfat, Kaliumhydrogensulfat oder Mischungen hiervon zum Einsatz. Auch der Konzentrationsbereich dieser Salze anorganischer Säuren liegt vorzugsweise zwischen 5 und 500 g/l.The reactive component used is preferably sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium chloride, potassium chloride, ammonium chloride, sodium sulfate, sodium hydrogensulfate, potassium sulfate, sodium hydrogensulfate, potassium sulfate, potassium hydrogensulfate or mixtures thereof. The concentration range of these salts of inorganic acids is preferably between 5 and 500 g / l.

Die erfindungsgemäße Reaktionslösung kann durch den Zusatz von Netzmitteln oder Verdickern in ihrer Konsistenz verändert und auf die jeweiligen Einsatzbedingungen abgestimmt werden. Hierbei kommen Netzmittel, beispielsweise Tenside, und/oder Verdicker bekannter Art zum Einsatz. Sie werden der Reaktionslösung bis zu einem Anteil von 5 % zugesetzt.The reaction solution according to the invention can be changed in its consistency by the addition of wetting agents or thickeners and be tailored to the particular conditions of use. In this case, wetting agents, for example surfactants, and / or come Thickeners of known type for use. They are added to the reaction solution to a level of 5%.

Die erfindungsgemäße Reaktionslösung erzeugt eine hochqualitative Patina aus basischen Kupferverbindungen und ist besonders gut für voroxidierte oder bereits teilweise patinierte Kupferoberflächen geeignet. Die Behandlung kann vor Ort auf der Baustelle oder werksseitig erfolgen. Die Reaktionslösung ist ferner gut für dasThe reaction solution according to the invention produces a high quality patina from basic copper compounds and is particularly well suited for preoxidized or already partially patinated copper surfaces. The treatment can be done on site or at the factory. The reaction solution is also good for that

Ausbessern einer vorhandenen Patina oder einem farblichen Angleich einer Patina geeignet.Repairing an existing patina or matching a patina suitable.

Die Reaktionslösung kann bei Raumtemperatur aufbereitet und verarbeitet werden. Es hat sich als zweckmäßig erwiesen, daß eine patinierte Fläche nach der Behandlung mit der Reaktionslösung mindestens 48 Stunden vor Regen geschützt werden sollte.The reaction solution can be prepared and processed at room temperature. It has been found to be expedient that a patinated surface after treatment with the reaction solution should be protected from rain for at least 48 hours.

Mit besonderem Vorteil kann die derart erzeugte Patinaschicht anschließend zur Vermeidung von Beschädigungen und zur Reduktion der Kupferlöslichkeit mit einer transparenten Schutzschicht überzogen werden. Hierzu kommen wie bereits erwähnt wasserdampfdiffusionsdurchlässige Lacke zur Anwendung, die eine offenporige Schutzschicht erzeugen und so die natürliche Wechselwirkung der Patinaoberfläche mit der Atmosphäre ermöglichen.With particular advantage, the patina layer produced in this way can then be coated with a transparent protective layer to avoid damage and to reduce the copper solubility. For this purpose, as already mentioned, water-vapor-permeable paints are used, which produce an open-pored protective layer and thus allow the natural interaction of the patina surface with the atmosphere.

Ein Ausführungsbeispiel der Reaktionslösung und deren Herstellung ist nachfolgend beschrieben:An embodiment of the reaction solution and its preparation is described below:

Eine wässrige Lösung mit 200 g/l Kupfersulfat wird zunächst mit 200 g/l Natriumcarbonat versetzt und eine Stunde bei Raumtemperatur gerührt. Danach werden 200 g/l Natriumchlorid zugegeben und nochmals eine Stunde bei Raumtemperatur gerührt. Anschließend kann die Lösung direkt auf die zu patinierende Oberfläche aufgebracht werden.An aqueous solution containing 200 g / l of copper sulfate is first mixed with 200 g / l of sodium carbonate and stirred for one hour at room temperature. Thereafter, 200 g / l of sodium chloride are added and stirred for another hour at room temperature. Subsequently, the solution can be applied directly to the surface to be patinated.

Für die Verarbeitung mit einem Sprühgerät wird ein Netzmittel, beispielsweise ein Tensid, in einer Konzentration von 50 g/l zugesetzt.For processing with a spray device, a wetting agent, for example a surfactant, in a concentration of 50 g / l is added.

Zum Erhalt einer streichfähigen Lösung wird die Lösung mit einem handelsüblichen Verdicker in einer Konzentration von 50 g/l verdickt.To obtain a spreadable solution, the solution is thickened with a commercially available thickener in a concentration of 50 g / l.

Die so hergestellte Reaktionslösung ist bei Raumtemperatur unbeschränkt lagerbar.The reaction solution thus prepared can be stored without restriction at room temperature.

Die Vorgehensweise zur Erzeugung einer Patina auf der Oberfläche eines Kupfergegenstands ist nachfolgend beispielhaft erläutert:The procedure for producing a patina on the surface of a copper article is explained below by way of example:

Üblicherweise weist die zu patinierende Kupferoberfläche eine dunkelbraune Kupferoxidschicht auf, die stellenweise bereits mit Kupfersalzen (Patina) bedeckt ist. Die Oberfläche wird vor dem Patinieren von Fett und lose anhaftendem Schmutz befreit. Die Entfernung von lose anhaftenden Schmutzpartikeln kann unter Verwendung von Wasser und manuellen oder mechanischen Hilfsmitteln erfolgen.Usually, the copper surface to be patinated has a dark brown copper oxide layer, which in places is already covered with copper salts (patina). The surface is freed from grease and loosely attached dirt before patinating. The removal of loosely adhered dirt particles can be done using water and manual or mechanical means.

Die auf der Oberfläche verbleibenden Kupferoxide und bereits vorhandene Patina werden nicht entfernt. Vorteilhafterweise erfolgt die Behandlung der Kupfergegenstände bei einer trockenen Witterung, gegebenenfalls muß die zu patinierende Oberfläche durch geeignete Abdeckungen vor Niederschlag geschützt werden.The remaining on the surface copper oxides and existing patina are not removed. Advantageously, the treatment of copper objects in a dry weather, possibly the surface to be patinated must be protected by suitable covers from precipitation.

Nach dem Abtrocknen der gereinigten Oberflächen werden die Flächen abgeklebt, die nicht patiniert werden sollen. Danach wird die bereits fertig angesetzte Reaktionslösung aufgeschüttelt bzw. -gerührt und aufgetragen. Als besonders geeignet hat sich hierzu ein Sprühgerät erwiesen. Je nach Leistung des verwendeten Sprühgeräts kommen Düsen zwischen 0,2 mm und 0,6 mm Durchmesser zum Einsatz. Zur gleichmäßigen Beschichtung der Oberfläche werden Spritzwinkel von 60° bis 90° als vorteilhaft angesehen. Bei der Behandlung ist darauf zu achten, daß eine Tropfenbildung auf der Oberfläche vermieden wird.After the cleaned surfaces have dried, the surfaces which should not be patinated are masked off. Thereafter, the already prepared ready reaction solution is shaken or stirred and applied. A sprayer has proven particularly suitable for this purpose. Depending on the performance of the sprayer used nozzles between 0.2 mm and 0.6 mm diameter are used. For uniform coating of the surface, spray angles of 60 ° to 90 ° considered advantageous. Care should be taken during treatment to avoid dripping on the surface.

Falls erforderlich können mehrere Patiniervorgänge durchgeführt werden. Vor jedem weiteren Patiniervorgang ist darauf zu achten, daß die Oberfläche vollständig abgetrocknet ist.If necessary, several patinating procedures can be performed. Before each further patinating process, care must be taken that the surface is completely dry.

Nach Erreichen des gewünschten Erscheinungsbilds der Kupferoberfläche wird diese der Trocknung ausgesetzt. Der Trocknungsvorgang sollte möglichst langsam und gleichmäßig erfolgen. Hierdurch wird die Qualität der Patina verbessert.After reaching the desired appearance of the copper surface it is exposed to drying. The drying process should be as slow and even as possible. This improves the quality of the patina.

Je nach Witterungsverhältnissen, zweckmäßigerweise jedoch frühestens nach 48 Stunden, kann dann die Schutzschicht aus Lack aufgebracht werden. Auch hierzu empfiehlt sich die Verwendung eines Sprühgeräts, vorzugsweise mit Düsen zwischen 0,2 mm und 0,3 mm Durchmesser, und einem Sprühwinkel von 90°.Depending on the weather conditions, but expediently after 48 hours at the earliest, the protective layer of lacquer can then be applied. Also for this purpose, the use of a sprayer, preferably with nozzles between 0.2 mm and 0.3 mm in diameter, and a spray angle of 90 ° is recommended.

Ein einmaliger Auftrag der Schutzschicht ist ausreichend. Während der Trocknung der Schutzschicht, die je nach Witterungsverhältnissen zwischen 20 Minuten und 24 Stunden betragen kann, sollte der Kupfergegenstand vor Niederschlag geschützt werden.A single application of the protective layer is sufficient. During the drying of the protective layer, which can be between 20 minutes and 24 hours depending on weather conditions, the copper object should be protected from precipitation.

Praktische Versuche entsprechend DIN 50 017/KFW bzw. entsprechend DIN 50 917, Teil 1, bei denen mit der erfindungsgemäßen Reaktionslösung behandelte Muster sechs Monate lang bewittert bzw. der natürlichen Witterung ausgesetzt wurden, haben gezeigt, daß keine nennenswerten Veränderungen an der Patina festzustellen ist. Die mit der Reaktionslösung erzeugte Patina weist mithin eine sehr gute Bewitterungsbeständigkeit auf.Practical tests according to DIN 50 017 / KFW or according to DIN 50 917, Part 1, in which treated with the reaction solution according to the invention for six months weathered or exposed to natural weather, have shown that no appreciable changes in the patina is observed , The patina produced with the reaction solution thus has a very good weathering resistance.

Claims (3)

  1. Method for producing a patina on the surface of an object made of copper or a copper alloy, wherein the surface is firstly cleaned and then a reaction solution, consisting of an aqueous solution of copper salts in the form of copper (I) carbonate, copper (II) carbonate, copper (I) chloride, copper (II) sulphate, copper nitrate or mixtures thereof in a concentration between 0.5% and 50% and salts of inorganic acids in the form of sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium chloride, potassium chloride, ammonium chloride, sodium sulphate, sodium hydrogen sulphate, potassium sulphate, potassium hydrogen sulphate or mixtures thereof in a concentration between 0.5% and 50%, is applied to the surface and then allowed to dry while being protected from atmospheric influences, after which a transparent varnish layer is applied to the patina.
  2. Object made of copper or of copper alloy, which has, at least on one surface, a patina layer, produced by the method according to claim 1, characterised in that the patina layer is provided with a transparent varnish layer.
  3. Reaction solution for producing a patina on surfaces of objects made of copper or of copper alloy consisting of an aqueous solution of copper salts and salts of inorganic acids according to claim 1, to which is added a wetting agent up to a proportion of 5% and/or a thickener up to a proportion of 5%.
EP99102955A 1998-03-07 1999-02-13 Process and reactive solution for producing a patina Expired - Lifetime EP0943701B1 (en)

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DE19809904A DE19809904A1 (en) 1998-03-07 1998-03-07 Process and reaction solution to create a patina
DE19809904 1998-03-07

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FI20020669A (en) * 2002-04-09 2003-10-10 Outokumpu Oy Procedure for preparing artificial patina and a patina paste
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KR20020089223A (en) * 2002-08-29 2002-11-29 서상환 The process of a copper patina
US7018677B2 (en) * 2003-07-17 2006-03-28 Crown-Pn L.L.C. Simulated patina for copper
US7060325B2 (en) * 2003-07-17 2006-06-13 Percy Greenberg Simulated patina for copper
DE10354527B4 (en) * 2003-11-17 2008-08-28 Kme Germany Ag Process for patination of copper
DE102004036082A1 (en) * 2004-07-24 2006-02-09 Km Europa Metal Ag Method for producing an inorganic covering layer on the surface of a product and panel or band-shaped product
US20090045169A1 (en) * 2004-08-31 2009-02-19 Timothy Ray Poe Mirror etching composition
FI120048B (en) * 2004-09-29 2009-06-15 Luvata Espoo Oy A method of making a multilayer patina and a multilayer patina
DE102005059421B4 (en) * 2005-12-07 2007-12-20 Susan Krieger Process for producing patina on textile surfaces of fabrics consisting of artificial or natural fibers
DE102006053192A1 (en) * 2006-11-09 2008-05-15 Kme Germany Ag Process for protecting patinated surfaces of copper products and patinated copper product
KR100890607B1 (en) * 2007-07-02 2009-03-27 김부현 A oxidized verdigris copper manufacture method
DE102009012461A1 (en) 2009-03-12 2010-09-16 Kme Germany Ag & Co. Kg Metallic carrier body such as metal sheet or strip useful as pollutant-reducing component in building construction and civil engineering, comprises patina layer applied on the carrier body, where the patina layer contains metal compounds
US10119038B2 (en) 2015-05-08 2018-11-06 PatinaNow, LLC Patina solution, method for producing patina on object, and patina kit
CN114323842B (en) * 2021-12-14 2022-08-26 北京科技大学 Rusty metal cultural relic simulation sample and manufacturing method thereof

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DE4041854A1 (en) * 1990-12-24 1992-06-25 Kabelmetal Ag METHOD FOR PRODUCING A GREEN PATINA ON A SEMI-PRODUCT CONSTRUCTED FROM COPPER
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DE59914396D1 (en) 2007-08-16
ATE366329T1 (en) 2007-07-15
DE19809904A1 (en) 1999-09-09
PT943701E (en) 2007-08-01
ES2286866T3 (en) 2007-12-01
EP0943701A1 (en) 1999-09-22
SG75920A1 (en) 2000-10-24
DK0943701T3 (en) 2007-11-05
US6176905B1 (en) 2001-01-23

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