EP0483568B1 - Method of producing brown coating layers on copper - Google Patents

Method of producing brown coating layers on copper Download PDF

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Publication number
EP0483568B1
EP0483568B1 EP91117338A EP91117338A EP0483568B1 EP 0483568 B1 EP0483568 B1 EP 0483568B1 EP 91117338 A EP91117338 A EP 91117338A EP 91117338 A EP91117338 A EP 91117338A EP 0483568 B1 EP0483568 B1 EP 0483568B1
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EP
European Patent Office
Prior art keywords
copper
brown
product
semi
production
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP91117338A
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German (de)
French (fr)
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EP0483568A1 (en
Inventor
Helmut Dr. Protzer
Constantin Dipl.-Chem. Puscasu
Stefan Dipl.-Ing. Hoveling
Albert Dr. Scherger
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KM Europa Metal AG
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KM Europa Metal AG
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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D3/00—Roof covering by making use of flat or curved slabs or stiff sheets
    • E04D3/24—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like
    • E04D3/30—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like of metal
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising

Definitions

  • the invention relates to a process for the production of brown cover layers on copper-shaped semi-finished products, in particular on rolled strips and sheets for the roof covering and facade cladding.
  • the surface of bare metal has a firmly adhering and stable top layer made of copper oxide.
  • the initially very thin oxide film stabilizes the surface of the copper material noticeably against the effects of the atmosphere.
  • the slow development of the oxide layer as a result of the reaction of the copper with moisture and atmospheric oxygen ideally gradually produces a uniform brown color (brown patina), the surface of the copper increasingly losing its metallic luster.
  • the brown top layer gets darker over time and then changes to an anthracite brown. This is the final state that usually occurs on vertical building surfaces, such as external wall cladding.
  • the top layer changes color in reaction to the substances contained in the atmosphere, such as sulfur dioxide, carbon dioxide and chlorides, to give basic copper compounds until the copper-typical patina green is reached.
  • the formation of the brown cover layer can, however, under certain atmospheric conditions be considerably delayed in places but also accelerate, so that, as a rule, it is necessary to wait a relatively long time until a uniform discoloration of the copper surface is achieved. Deviations from a uniform color tone can be observed especially in the early stages of weathering. In many cases, uneven dark spots and / or stripes often form on the copper surface. However, as the weathering continues due to atmospheric influences, these color differences disappear.
  • a method for producing uniform layers of copper (I) oxide on the surface of copper wire or ribbon is mentioned, for example, in Chemical Abstracts, Volume 83, No. 2, July 1975, page 258, Summary No. 32184t.
  • the copper oxide layer is formed by an oxidizing heat treatment at a temperature in the temperature range from 300 to 1000 ° C.
  • the invention has for its object to provide a method with which a uniform and firmly adhering brown cover layer (brown patina) can be generated on the surface of copper-shaped semifinished product made of copper, which is not damaged even in the further processing necessary in particular in the construction sector or flakes off.
  • pre-patinated strips or sheets made of copper produced by the process according to the invention have cover layers which both have excellent adhesive strength and remain preform-resistant when bent or folded, i.e. H. show no detachment. Even the fingerprints that are often unavoidable when installing roof covers and facade cladding remain largely unremarkable on the pre-patinated surface.
  • a cold-rolled and possibly degreased band made of SF copper in accordance with DIN 1787 with a thickness of 0.6 mm and a width of 1000 mm was roughened uniformly by means of a grinding device.
  • the copper strip was then fed to a gas heated continuous furnace for heat treatment.
  • a controlled gas atmosphere with approximately 25% by volume oxygen was set in the furnace. After a short cooling distance, the pre-oxidized copper strip was then immersed at a working temperature of about 80 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Roof Covering Using Slabs Or Stiff Sheets (AREA)
  • Paints Or Removers (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemically Coating (AREA)
  • Adornments (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tyre Moulding (AREA)

Abstract

For the controlled large-scale production of a uniform and firmly adhering brown covering layer (brown patina) on surfaces of semifinished copper products, especially on rolled strip or sheet for the building sector, the process according to the invention provides for first roughening the surface of the semifinished copper product by mechanical treatment and then subjecting the semifinished copper product to a heat treatment for a period of 0.1 to 30 minutes at a temperature within the range from 150 to 650 DEG C. <??>This method makes it possible to provide semifinished copper products preweathered in the works, without having to wait for the brown surface discolouration which depends on the long-term action of atmospheric influences. <??>For a further improvement in the adhesive strength of the brown patina, the semifinished copper product can advantageously also be subjected to a chemical further oxidation after the heat treatment.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von braunen Deckschichten auf aus Kupfer bestehendem bandförmigem Halbzeug, insbesondere auf gewalzten Bändern und Blechen für die Dachabdeckung und Fassadenbekleidung.The invention relates to a process for the production of brown cover layers on copper-shaped semi-finished products, in particular on rolled strips and sheets for the roof covering and facade cladding.

Unter normalen atmosphärischen Bedingungen bildet sich auf der Oberfläche von metallblankem Kupfer eine festhaftende und beständige Deckschicht aus Kupferoxid. Der zunächst sehr dünne Oxidfilm stabilisiert die Oberfläche des Kupfermaterials bereits merklich gegenüber den Einwirkungen der Atmosphäre. Die langsame Weiterbildung der Oxidschicht infolge der Reaktion des Kupfers mit Feuchtigkeit und Luftsauerstoff läßt im Idealfall allmählich eine gleichmäßige Braunfärbung (Braunpatina) entstehen, wobei die Oberfläche des Kupfers zunehmend den metallischen Glanz verliert. Die braune Deckschicht wird im Laufe der Zeit immer dunkler und geht dann in ein Anthrazit-Braun über. Dies ist der an senkrechten Gebäudeflächen, wie einer Außenwandbekleidung, üblicherweise eintretende Endzustand. Bei geneigten Dachflächen ändert sich die Deckschicht unter Reaktion mit den in der Atmosphäre enthaltenen Stoffen, wie Schwefeldioxid, Kohlendioxid und Chloriden zu basischen Kupferverbindungen farblich weiter, bis das kupfertypische Patinagrün erreicht ist.Under normal atmospheric conditions, the surface of bare metal has a firmly adhering and stable top layer made of copper oxide. The initially very thin oxide film stabilizes the surface of the copper material noticeably against the effects of the atmosphere. The slow development of the oxide layer as a result of the reaction of the copper with moisture and atmospheric oxygen ideally gradually produces a uniform brown color (brown patina), the surface of the copper increasingly losing its metallic luster. The brown top layer gets darker over time and then changes to an anthracite brown. This is the final state that usually occurs on vertical building surfaces, such as external wall cladding. In the case of sloping roof surfaces, the top layer changes color in reaction to the substances contained in the atmosphere, such as sulfur dioxide, carbon dioxide and chlorides, to give basic copper compounds until the copper-typical patina green is reached.

Die Ausbildung der braunen Deckschicht kann sich jedoch unter gewissen atmosphärischen Bedingungen stellenweise erheblich verzögern aber auch beschleunigen, so daß in der Regel relativ lange gewartet werden muß, bis eine gleichmäßige Verfärbung der Kupferoberfläche erreicht ist. Abweichungen von einer einheitlichen Farbtönung sind insbesondere im Anfangsstadium der Bewitterung zu beobachten. Auf der Kupferoberfläche bilden sich vielfach zunächst ungleichmäßig dunkle Flecken und/oder Streifen aus. Im weiteren Verlauf der Bewitterung durch atmosphärische Einflüsse verschwinden diese Farbunterschiede jedoch zusehens.The formation of the brown cover layer can, however, under certain atmospheric conditions be considerably delayed in places but also accelerate, so that, as a rule, it is necessary to wait a relatively long time until a uniform discoloration of the copper surface is achieved. Deviations from a uniform color tone can be observed especially in the early stages of weathering. In many cases, uneven dark spots and / or stripes often form on the copper surface. However, as the weathering continues due to atmospheric influences, these color differences disappear.

Ein Verfahren zur Herstellung gleichmäßiger Schichten aus Kupfer-(I)-Oxid auf der Oberfläche von Kupferdraht oder -band ist beispielsweise in Chemical Abstracts, Band 83, Nr. 2, Juli 1975, Seite 258, Zusammenfassung Nr. 32184t erwähnt. Bei diesem bekannten Verfahren wird die Kupferoxidschicht durch eine oxidierende Wärmebehandlung bei einer im Temperaturbereich von 300 bis 1000 °C liegenden Temperatur gebildet.A method for producing uniform layers of copper (I) oxide on the surface of copper wire or ribbon is mentioned, for example, in Chemical Abstracts, Volume 83, No. 2, July 1975, page 258, Summary No. 32184t. In this known method, the copper oxide layer is formed by an oxidizing heat treatment at a temperature in the temperature range from 300 to 1000 ° C.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren anzugeben, mit dem auf der Oberfläche von aus Kupfer bestehendem bandförmigem Halbzeug in großtechnischem Maßstab eine gleichmäßige und festhaftende braune Deckschicht (Braunpatina) erzeugt werden kann, die auch bei der insbesondere im Baubereich notwendigen Weiterverarbeitung nicht beschädigt wird oder abplatzt.The invention has for its object to provide a method with which a uniform and firmly adhering brown cover layer (brown patina) can be generated on the surface of copper-shaped semifinished product made of copper, which is not damaged even in the further processing necessary in particular in the construction sector or flakes off.

Diese Aufgabe wird erfindungsgemäß durch die Kombination folgender Verfahrensschritte gelöst:

  • Die Oberfläche des Kupferhalbzeugs wird zunächst durch eine mechanische Behandlung aufgerauht
  • Das Kupferhalbzeug wird anschließend bei einer im Temperaturbereich von 150 bis 650 °C liegenden Temperatur für die Dauer von 0,1 bis 30 Minuten in einer kontrollierten oxidierenden Atmosphäre wärmebehandelt.
  • Das Kupferhalbzeug wird im Anschluß an die Wärmebehandlung mit einer wässrigen Lösung eines Metallsalzes aus der Kaliumchlorat, Kaliumpermanganat und Natriumhypochlorit umfassenden Gruppe allein oder im Gemisch mit Kupfersulfat behandelt.
According to the invention, this object is achieved by combining the following process steps:
  • The surface of the semi-finished copper product is first roughened by mechanical treatment
  • The semi-finished copper product is then heat-treated at a temperature in the range from 150 to 650 ° C. for a period of 0.1 to 30 minutes in a controlled oxidizing atmosphere.
  • Following the heat treatment, the semi-finished copper product is treated with an aqueous solution of a metal salt from the group comprising potassium chlorate, potassium permanganate and sodium hypochlorite, alone or as a mixture with copper sulfate.

Vorteilhafte Weiterbildungen der Erfindung ergeben sich aus den Unteransprüchen.Advantageous developments of the invention result from the subclaims.

Mit Hilfe der Maßnahmen des erfindungsgemäßen Verfahrens gelingt es in überraschend einfacher Weise, eine werksseitige Vorbewitterung (Braunpatinierung) der Oberfläche von aus Kupfer bestehendem bandförmigem Halbzeug zu erzielen, ohne daß auf die von der Langzeiteinwirkung atmosphärischer Einflüsse abhängige dunkelbraune Verfärbung der Kupferoberfläche gewartet werden muß. Dieser Vorteil kommt insbesondere dem ästhetischen Empfinden nach einer gleichmäßigen Einfärbung der Kupferoberfläche entgegen, beispielsweise bei einer aus Kupferprofilelementen zusammengesetzten Dachabdeckung oder Fassadenbekleidung. Ein wesentlicher Vorteil ist auch darin zu sehen, daß dem Klempner bei eventuell notwendig werdenden Reparaturarbeiten entsprechende mit einer Braunpatina versehene Kupferbänder oder -bleche zur Verfügung gestellt werden können. Dieses vorpatinierte Material ermöglicht dann eine übergangslose Einfügung in bereits seit längerer Zeit den atmosphärischen Einflüssen ausgesetzten Fassadenbekleidungen, ohne daß Unterschiede bezüglich der Farbtönung der braunen Deckschichten auf den einzelnen Fassadenelementen sichtbar werden.With the help of the measures of the method according to the invention, it is possible in a surprisingly simple manner to obtain a pre-weathering (brown patination) of the surface of the band-shaped semi-finished product made of copper without having to wait for the dark brown discoloration of the copper surface which is dependent on the long-term effects of atmospheric influences. This advantage comes in particular against the aesthetic feeling after a uniform coloring of the copper surface, for example with a roof covering or facade cladding composed of copper profile elements. A significant advantage is also to be seen in the fact that the plumber can be provided with appropriate copper strips or sheets provided with a brown patina if repairs are necessary. This pre-patinated material then enables one seamless insertion in facade cladding that has been exposed to atmospheric influences for a long time, without differences in the color of the brown cover layers on the individual facade elements becoming visible.

Es hat sich ferner gezeigt, daß die nach dem erfindungsgemäßen Verfahren hergestellten vorpatinierten Bänder oder Bleche aus Kupfer Deckschichten aufweisen, die sowohl eine hervorragende Haftfestigkeit aufweisen als auch beim Biegen oder Abkanten vorformungsfest bleiben, d. h. keine Ablösung zeigen. Sogar die bei der Montage von Dachabdeckungen und Fassadenbekleidungen häufig unvermeidlichen Fingerspuren bleiben auf der vorpatinierten Oberfläche weitgehend unauffällig.It has also been shown that the pre-patinated strips or sheets made of copper produced by the process according to the invention have cover layers which both have excellent adhesive strength and remain preform-resistant when bent or folded, i.e. H. show no detachment. Even the fingerprints that are often unavoidable when installing roof covers and facade cladding remain largely unremarkable on the pre-patinated surface.

Eine noch bessere Haftfestigkeit der Deckschicht und eine insbesondere noch einheitlichere Braunfärbung der vorpatinierten Kupferoberfläche läßt sich dadurch erreichen, daß unmittelbar im Anschluß an die Wärmebehandlung eine chemische Nachoxidierung mit einer wässerigen Lösung mindestens eines Metallsalzes aus der Kaliumchlorat, Kaliumpermanganat und Natriumhypochlorit umfassenden Gruppe allein oder im Gemisch mit Kupfersulfat durchgeführt wird.An even better adhesive strength of the top layer and, in particular, an even more uniform brown coloration of the prepatinated copper surface can be achieved in that, immediately after the heat treatment, chemical post-oxidation with an aqueous solution of at least one metal salt from the group comprising potassium chlorate, potassium permanganate and sodium hypochlorite, alone or in a mixture is carried out with copper sulfate.

Grundsätzlich sind bereits zahlreiche chemische und elektrolytische Verfahren zum Braunfärben von Kupferoberflächen bekannt. Diese führen ohne vorherige thermische Oxidation jedoch häufig, insbesondere im großtechnischen Maßstab, zu einer ungenügenden Farbsättigung der Deckschichten. Ferner läßt es sich sonst nicht vermeiden, daß insbesondere bei einer durch Tauchbehandlung aufgebrachten Behandlungslösung Flecken und Schlieren auf der Oberfläche zurückbleiben.In principle, numerous chemical and electrolytic processes for browning copper surfaces are already known. Without prior thermal oxidation, however, these often lead to insufficient color saturation of the outer layers, especially on an industrial scale. Furthermore, it cannot otherwise be avoided that stains and streaks remain on the surface, particularly in the case of a treatment solution applied by immersion treatment.

Anhand eines Ausführungsbeispiels wird die Erfindung im folgenden noch näher erläutert.The invention is explained in more detail below using an exemplary embodiment.

Ein kaltgewalztes und gegebenenfalls entfettetes Band aus SF-Kupfer gemäß DIN 1787 mit einer Dicke von 0,6 mm und einer Breite von 1 000 mm wurde mittels einer Schleifvorrichtung gleichmäßig aufgerauht. Zur Oberflächenbehandlung wurden Schleifbänder mit den Körnungen Nr. 180 und Nr. 320 verwendet. Das Kupferband wurde dann zur Wärmebehandlung einem gasbeheizten Durchlaufofen zugeführt. Zur Oberflächenoxidation des im Temperaturbereich von 150 bis 350 °C, vorzugsweise bei etwa 275 °C im Durchlauf wärmebehandelten Kupferbands wurde im Ofen eine kontrollierte Gasatmosphäre mit etwa 25 Vol.% Sauerstoffanteil eingestellt. Nach einer kurzen Abkühlungsstrecke wurde das voroxidierte Kupferband dann bei einer Arbeitstemperatur von etwa 80 °C in ein Bad getaucht, das eine wässerige Lösung aus einem Gemisch von 50 g/l Kaliumchlorat und 100 g/l Kupfersulfat-Pentahydrat enthielt. Die Einwirkungsdauer der Behandlungslösung betrug etwa 2 bis 3 Minuten. Anschließend wurde das Kupferband mit Wasser gespült und mit Heißluft getrocknet. Nach diesen Behandlungsschritten wies das Kupferband eine sehr gleichmäßige Deckschicht mit einer intensiven dunkelbraunen Färbung auf. Die Braunpatina erwies sich als sehr abriebfest. Nach ergänzenden Biege- und Abkantoperationen zeigten sich weder Beschädigungen noch Ablösungen der Deckschicht.A cold-rolled and possibly degreased band made of SF copper in accordance with DIN 1787 with a thickness of 0.6 mm and a width of 1000 mm was roughened uniformly by means of a grinding device. Sanding belts with grit no. 180 and no. 320 were used for surface treatment. The copper strip was then fed to a gas heated continuous furnace for heat treatment. In order to oxidize the surface of the copper strip heat-treated in the temperature range from 150 to 350 ° C., preferably at about 275 ° C., a controlled gas atmosphere with approximately 25% by volume oxygen was set in the furnace. After a short cooling distance, the pre-oxidized copper strip was then immersed at a working temperature of about 80 ° C. in a bath which contained an aqueous solution of a mixture of 50 g / l potassium chlorate and 100 g / l copper sulfate pentahydrate. The duration of exposure to the treatment solution was about 2 to 3 minutes. The copper strip was then rinsed with water and dried with hot air. After these treatment steps, the copper tape had a very uniform top layer with an intense dark brown color. The brown patina turned out to be very resistant to abrasion. After additional bending and folding operations, there was no damage or detachment of the top layer.

Claims (4)

  1. Process for the production of brown covering layers on semi-product in strip form made of copper, in particular on rolled strips and sheets for roof covering and façade cladding, characterised by the combination of the following process steps:
    - the surface of the copper semi-product is first roughened by a mechanical treatment;
    - the copper semi-product is then heat-treated in a controlled oxidising atmosphere at a temperature lying in the temperature range from 150 to 650°C for a period from 0.1 to 30 minutes;
    - following the heat treatment, the copper semi-product is treated with an aqueous solution of a metal salt from the group comprising potassium chlorate, potassium permanganate and sodium hypochlorite on its own or in a mixture with copper sulphate.
  2. Process for the production of brown covering layers according to claim 1, characterised in that the mechanical treatment is effected by sanding or brushing.
  3. Process for the production of brown covering layers according to claim 1, characterised in that an aqueous solution of 20 to 70 g/l potassium chlorate and 50 to 150 g/l copper sulphate pentahydrate is applied to the surface of the copper semi-product.
  4. Process for the production of brown covering layers according to one of claims 1 to 3, characterised in that the copper semi-product is immersed in the aqueous solution at a temperature lying in the temperature range from 20 to 90°C for a period from approximately 1 to 10 minutes.
EP91117338A 1990-10-27 1991-10-11 Method of producing brown coating layers on copper Expired - Lifetime EP0483568B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4034249 1990-10-27
DE4034249A DE4034249A1 (en) 1990-10-27 1990-10-27 METHOD FOR PRODUCING BROWN COVER LAYERS ON COPPER

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EP0483568A1 EP0483568A1 (en) 1992-05-06
EP0483568B1 true EP0483568B1 (en) 1995-09-20

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EP91117338A Expired - Lifetime EP0483568B1 (en) 1990-10-27 1991-10-11 Method of producing brown coating layers on copper

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US (1) US5282890A (en)
EP (1) EP0483568B1 (en)
JP (1) JP3111094B2 (en)
AT (1) ATE128192T1 (en)
AU (1) AU633764B2 (en)
CA (1) CA2054166C (en)
DE (2) DE4034249A1 (en)
DK (1) DK0483568T3 (en)
ES (1) ES2077133T3 (en)
FI (1) FI96777C (en)
GR (1) GR3018053T3 (en)
NO (1) NO303787B1 (en)
PT (1) PT99330B (en)
RU (1) RU2023750C1 (en)
ZA (1) ZA917973B (en)

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ES2069501B1 (en) * 1993-10-11 1996-02-16 Collado Manuel Torrejon COPPER AGING PROCEDURE.
DE4404699A1 (en) * 1994-02-15 1995-08-17 Kabelmetal Ag Process for the production of tinned strips or sheets made of copper or a copper alloy
DE19542410A1 (en) * 1994-11-14 1996-05-15 Furukawa Electric Co Ltd Building material quickly forming natural patina
DE19523646A1 (en) * 1995-06-29 1997-01-02 Km Europa Metal Ag Copper tape or sheet with a brown top layer and process for its manufacture
US6086743A (en) * 1997-08-06 2000-07-11 Gould Electronics, Inc. Adhesion enhancement for metal foil
DE19809904A1 (en) * 1998-03-07 1999-09-09 Km Europa Metal Ag Process and reaction solution to create a patina
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
US8057587B2 (en) 2008-05-12 2011-11-15 Michael Beeck Composition for coloring solder

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JPS589831B2 (en) * 1976-03-29 1983-02-23 古河電気工業株式会社 Copper blackening treatment method
DE3108160C2 (en) * 1981-02-06 1984-12-06 M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 8000 München Process for the production of oxide layers on chrome and / or nickel alloy steels
JPS60159174A (en) * 1984-01-27 1985-08-20 Daikan:Kk Manufacture of copper plate for roof having artificial patina
JPS634053A (en) * 1986-06-24 1988-01-09 Susumu Ishikawa Method for forming patina film on surface of copper product or the like
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Title
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ES2077133T3 (en) 1995-11-16
DE59106523D1 (en) 1995-10-26
FI914862A0 (en) 1991-10-15
NO914196D0 (en) 1991-10-25
EP0483568A1 (en) 1992-05-06
JP3111094B2 (en) 2000-11-20
CA2054166A1 (en) 1992-04-28
PT99330B (en) 1999-02-26
FI96777C (en) 1996-08-26
DE4034249A1 (en) 1992-04-30
CA2054166C (en) 1999-08-17
RU2023750C1 (en) 1994-11-30
PT99330A (en) 1992-09-30
ATE128192T1 (en) 1995-10-15
AU8677691A (en) 1992-04-30
JPH05339701A (en) 1993-12-21
GR3018053T3 (en) 1996-02-29
NO914196L (en) 1992-04-28
NO303787B1 (en) 1998-08-31
AU633764B2 (en) 1993-02-04
FI96777B (en) 1996-05-15
US5282890A (en) 1994-02-01
ZA917973B (en) 1992-06-24
DK0483568T3 (en) 1996-01-02
FI914862A (en) 1992-04-28

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