EP0492566B1 - Method of producing a green protecting coating on copper-containing materials - Google Patents

Method of producing a green protecting coating on copper-containing materials Download PDF

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Publication number
EP0492566B1
EP0492566B1 EP91122083A EP91122083A EP0492566B1 EP 0492566 B1 EP0492566 B1 EP 0492566B1 EP 91122083 A EP91122083 A EP 91122083A EP 91122083 A EP91122083 A EP 91122083A EP 0492566 B1 EP0492566 B1 EP 0492566B1
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EP
European Patent Office
Prior art keywords
green
copper
covering layer
copper strip
production
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91122083A
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German (de)
French (fr)
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EP0492566A1 (en
Inventor
Stefan Dipl.-Ing. Hoveling
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KM Europa Metal AG
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KM Europa Metal AG
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Publication of EP0492566A1 publication Critical patent/EP0492566A1/en
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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
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/48—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 aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon

Definitions

  • the invention relates to a method for producing a green protective and covering layer on rolled copper strip or sheet metal for the roof covering and facade cladding.
  • the resulting patina effectively protects the copper component from further weather influences, so that the rate of removal of the copper approaches zero when the patina reaches the highest basicity. It is therefore not surprising that practitioners began researching and imitating this protective layer at an early stage. the artificial green patina of art objects, such as statues and vessels, has been known for a long time using the dot technique.
  • DE-A-19 60 960 discloses a chemical process for forming a patina, in which the surface of a copper sheet is first cleaned and then treated with a solution which contains ammonium sulfate, mercury-II chloride and copper sulfate.
  • patina-colored plastic layers are applied to copper strips provided for the roof covering and facade cladding.
  • the disadvantage of this process is that the applied layers flake off very easily and that the self-healing mechanism of the natural patina is then missing.
  • the necessary processing techniques, such as soldering or folding, can only be carried out to a limited extent.
  • the invention is based on the object of specifying a method of the type mentioned at the outset with which a green, firmly adhering top layer which is very similar to the natural patina can be produced on an industrial scale on the surface of copper semi-finished products.
  • the artificially green-patinated strips or sheets of copper produced by the process according to the invention have protective layers with excellent adhesive strength. Even the fingerprints that are often unavoidable when installing roof covers and facade cladding remain largely unremarkable on the green patinated surface.
  • the protective and covering layer applied acts as a catalyst for the gradually developing natural patina, that is to say that the artificial protective layer changes over time into a natural patina under atmospheric influences.
  • the protective and cover layer consists of copper oxide (Cu2O) and an essentially copper-free metal salt.
  • the weight per unit area of the completely reacted protective layer is 180 to 680 mg / dm2 after the aging, the range from 330 to 525 mg / dm2 being preferred.
  • a cold-rolled 1000 mm wide strip of SF copper in accordance with DIN 1787 with a thickness of 0.7 mm is first degreased in a continuous device.
  • the copper strip is first moved through a belt grinding machine to deliberately enlarge the surface, for example by a factor of 2, which, for. B. is provided with one or more sanding belts of grain size 40 to 60 and optionally with an additional brushing device.
  • the installed belt center or belt edge control ensures precise positioning of the copper belt in relation to the sanding belt.
  • the copper strip then passes through a duo-roll stand, the rolls of which are preferably in the direction of the roll axis have roughened or textured surfaces.
  • the copper strip then runs in a line through a spraying and squeezing device in which the chemical reaction solution for green patination is applied evenly to the surface. After the reaction solution has been applied, the copper strip is divided into finished lengths according to customer requirements using a cross cutting shear.
  • the copper tape or sheet coated on one side is separated into racks and the racks are then stored for 6 to 48 hours in an air-conditioned room at a temperature of around 20 ° C and a relative humidity of 70%.
  • an additional electrical voltage can be applied or gaseous reaction media can be introduced.
  • the weight per unit area of the protective and top layer was determined from a few test pieces. It averaged about 430 mg / dm2.
  • the bending and folding operations necessary for use in the construction sector can then be carried out on the artificially patinated copper strip without damage or large-scale detachment of the protective and cover layers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

Under normal atmospheric conditions, a uniform green covering layer, the so-called patina, forms on inclined copper surfaces only after exposure to the weather for many years. There has long been a desire to effect preweathering of the surface of semifinished products consisting of copper in the works on a large industrial scale, closely simulating the natural green patination. The method according to the invention for producing an artificial green protective and covering layer comprises first roughening the surface of degreased strip or sheet in a controlled manner by a mechanical treatment. In a further step of the method, the roughened surface of the strip or sheet is then treated in continuous flow with a suitable chemical reaction solution for green patination. After the chemical treatment, the strip or sheet is stored in its final dimensions for some time in an air-conditioned room.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung einer grünen Schutz- und Deckschicht auf gewalztem Kupferband oder -blech für die Dachabdeckung und Fassadenverkleidung.The invention relates to a method for producing a green protective and covering layer on rolled copper strip or sheet metal for the roof covering and facade cladding.

Unter normalen atmosphärischen Einflüssen bildet Kupfer auf seiner Oberfläche erst nach einem relativ langen Zeitraum und auch nur unter bestimmten Bedingungen eine grün- bis türkisfarbene Schutzschicht, die sogenannte Patina. Die Bildungsgeschwindigkeit dieser natürlichen Patina ist beispielsweise von folgenden Parametern abhängig:

  • Zusammensetzung der Atmosphäre (Feuchtigkeit, Verunreinigungsgehalt)
  • Beanspruchung durch feste Teilchen (Sand, Staub)
  • Umgebungstemperatur
  • Neigung der Oberfläche der Kupferbauteile
  • Lage zur Hauptwetterrichtung
So sind in der Veröffentlichung des Deutschen Kupfer-Institus "Chemische Färbung von Kupfer und Kupferlegierungen" für die verschiedenen atmosphärischen Einflüsse folgende Zeiten für die Ausbildung einer natürlichen Patina angegeben:
  • In Meeresluft nach etwa 6 Jahren
  • In Großstadt- und Industrieatmosphäre nach etwa 5 bis 8 Jahren
  • In normaler Stadtatmosphäre nach etwa 8 bis 12 Jahren.
Under normal atmospheric influences, copper only forms a green to turquoise protective layer, the so-called patina, on its surface after a relatively long period of time and only under certain conditions. The rate of formation of this natural patina depends, for example, on the following parameters:
  • Composition of the atmosphere (moisture, impurity content)
  • Exposure to solid particles (sand, dust)
  • Ambient temperature
  • Inclination of the surface of the copper components
  • Location to the main weather direction
The publication by the German Copper Institute "Chemical Coloring of Copper and Copper Alloys" for the various atmospheric influences specifies the following times for the formation of a natural patina:
  • In the sea air after about 6 years
  • In a big city and industrial atmosphere after about 5 to 8 years
  • In a normal city atmosphere after about 8 to 12 years.

Die entstandene Patina schützt das Kupferbauteil wirkungsvoll vor weiteren Witterungseinflüssen, so daß sich die Abtragungsrate des Kupfers mit Erreichen der höchsten Basizität der Patina dem Wert Null nähert. Es ist daher auch nicht überraschend, daß sich schon frühzeitig Praktiker mit der Erforschung und Nachahmung dieser Schutzschicht befaßt haben. so ist die künstliche Grünpatinierung von Kunstgegenständen, wie beispielsweise Statuen und Gefäßen, mittels der Tüpfeltechnik schon seit langer Zeit bekannt.The resulting patina effectively protects the copper component from further weather influences, so that the rate of removal of the copper approaches zero when the patina reaches the highest basicity. It is therefore not surprising that practitioners began researching and imitating this protective layer at an early stage. the artificial green patina of art objects, such as statues and vessels, has been known for a long time using the dot technique.

Weiterhin gibt es eine Reihe von reaktionsfähigen Patinierungslösungen, die in Spritz- oder Bürsttechnik auch auf größere Flächen, wie z. B. Dachabdeckungen, in mehreren Arbeitsgängen aufgetragen werden. Aus der DE-A-19 60 960 ist ein chemisches Verfahren zur Bildung einer Patina bekannt, bei dem die Oberfläche eines Kupferblechs zunächst gereinigt und anschließend mit einer Lösung, die Ammoniumsulfat, Quecksilber-II-chlorid und Kupfersulfat enthält, behandelt wird.Furthermore, there are a number of reactive patination solutions that can be sprayed or brushed onto larger areas, e.g. B. roofing can be applied in several steps. DE-A-19 60 960 discloses a chemical process for forming a patina, in which the surface of a copper sheet is first cleaned and then treated with a solution which contains ammonium sulfate, mercury-II chloride and copper sulfate.

Der Nachteil der bisher bekannten Verfahren ist darin zu sehen, daß sie entweder nur in aufwendiger Handarbeit oder nur für begrenzte Flächen angewendet werden können und damit für eine großtechnische Fertigung zu unwirtschaftlich sind.The disadvantage of the previously known methods can be seen in the fact that they can be used either only with elaborate manual work or only for limited areas and are therefore too uneconomical for large-scale production.

Schließlich ist noch ein Verfahren bekannt, bei dem patinafarbene Kunststoffschichten auf für die Dachabdeckung und Fassadenverkleidung vorgesehenen Kupferbändern aufgebracht werden. Nachteilig an diesem Verfahren ist, daß die aufgebrachten Schichten sehr leicht abplatzen und daß dann der Selbstheilungsmechanismus der natürlichen Patina fehlt. Hinzu kommt, daß die notwendigen Verarbeitungstechniken, wie Löten oder Abkanten, nur eingeschränkt durchführbar sind.Finally, a method is also known in which patina-colored plastic layers are applied to copper strips provided for the roof covering and facade cladding. The disadvantage of this process is that the applied layers flake off very easily and that the self-healing mechanism of the natural patina is then missing. In addition, the necessary processing techniques, such as soldering or folding, can only be carried out to a limited extent.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs erwähnten Art anzugeben, mit dem auf der Oberfläche von aus Kupfer bestehendem Halbzeug in großtechnischem Maßstab eine grüne, festhaftende, der natürlichen Patina sehr ähnliche Deckschicht erzeugt werden kann.The invention is based on the object of specifying a method of the type mentioned at the outset with which a green, firmly adhering top layer which is very similar to the natural patina can be produced on an industrial scale on the surface of copper semi-finished products.

Diese Aufgabe wird erfindungsgemäß durch die Kombination der im Anspruch 1 genannten Verfahrensmaßnahmen gelöst. Vorteilhafte Weiterbildungen der Erfindung ergeben sich aus den Unteransprüchen.This object is achieved according to the invention by the combination of the process measures mentioned in claim 1. Advantageous developments of the invention result from the subclaims.

Die wesentlichen Vorteile des erfindungsgemäßen Verfahrens bestehen insbesondere darin, daß durch die kontinuierliche Fertigung

  • eine äußerst gleichmäßige Vorbehandlung sämtlicher Bänder und Bleche erreicht wird; diese ist eine wichtige Voraussetzung für eine künstliche Grünpatinierung mit einheitlicher Farbgebung,
  • variable Fertiglängen ohne Schneidabfall möglich sind,
  • keine Farbänderungen an den Band- oder Blechenden auftreten können,
  • keine Ausfälle des Schleifbands durch hochstehende Band- oder Blechenden entstehen,
  • eine gezielte Ansteuerung, beispielsweise des Schleifbands, durch die Bandmitten- oder Bandkantenregelung möglich ist.
The main advantages of the method according to the invention are in particular that the continuous production
  • extremely uniform pretreatment of all strips and sheets is achieved; this is an important prerequisite for artificial green patination with a uniform color,
  • variable finished lengths are possible without cutting waste,
  • no color changes can occur at the strip or sheet ends,
  • no grinding belt failures due to upstanding belt or sheet ends,
  • targeted control, for example of the grinding belt, is possible by means of the belt center or belt edge control.

Es hat sich ferner gezeigt, daß die nach dem erfindungsgemäßen Verfahren hergestellten künstlich grünpatinierten Bänder oder Bleche aus Kupfer Schutzschichten mit hervorragender Haftfestigkeit aufweisen. Sogar die bei der Montage von Dachabdeckungen und Fassadenverkleidungen häufig unvermeidlichen Fingerspuren bleiben auf der grünpatinierten Oberfläche weitgehend unauffällig.It has also been found that the artificially green-patinated strips or sheets of copper produced by the process according to the invention have protective layers with excellent adhesive strength. Even the fingerprints that are often unavoidable when installing roof covers and facade cladding remain largely unremarkable on the green patinated surface.

In weiteren Untersuchungen wurde festgestellt, daß die aufgebrachte Schutz- und Deckschicht als Katalysator für die sich allmählich ausbildende natürliche Patina wirkt, daß heißt, die künstliche Schutzschicht wandelt sich unter atmosphärischen Einflüssen im Laufe der Zeit in eine natürliche Patina um. Vorzugsweise besteht die Schutz- und Deckschicht aus Kupferoxid (Cu₂O) und einem im wesentlichen kupferfreien Metallsalz. Das Flächengewicht der vollständig reagierten Schutzschicht beträgt nach der Auslagerung 180 bis 680 mg/dm², wobei der Bereich von 330 bis 525 mg/dm² bevorzugt ist.In further investigations it was found that the protective and covering layer applied acts as a catalyst for the gradually developing natural patina, that is to say that the artificial protective layer changes over time into a natural patina under atmospheric influences. Preferably, the protective and cover layer consists of copper oxide (Cu₂O) and an essentially copper-free metal salt. The weight per unit area of the completely reacted protective layer is 180 to 680 mg / dm² after the aging, the range from 330 to 525 mg / dm² being preferred.

Anhand eines Ausführungsbeispiels soll die Erfindung im folgenden noch weiter erläutert werden.The invention will be explained in more detail below using an exemplary embodiment.

Ein kaltgewalztes 1000 mm breites Band aus SF-Kupfer gemäß DIN 1787 mit einer Dicke von 0,7 mm wird zunächst in einer Durchlaufeinrichtung entfettet. Unmittelbar anschließend wird daß Kupferband zur gezielten Vergrößerung der Oberfläche, beispielsweise um den Faktor 2, zunächst durch eine Bandschleifmaschine gefahren, die z. B. mit einem oder mehreren Schleifbändern der Körnung 40 bis 60 sowie gegebenenfalls mit einer zusätzlichen Bürsteinrichtung versehen ist. Die installierte Bandmitten- oder Bandkantenregelung sorgt für eine genaue Positionierung des Kupferbands gegenüber dem Schleifband. Danach durchläuft das Kupferband noch ein Duowalzgerüst, dessen Walzen vorzugsweise in Richtung der Walzenachse aufgerauhte bzw. texturierte Oberflächen aufweisen. In Linie durchläuft das Kupferband anschließend eine Sprüh- und Abquetscheinrichtung, in der die chemische Reaktionslösung zur Grünpatinierung gleichmäßig auf die Oberfläche aufgebracht wird. Nach Aufbringen der Reaktionslösung wird das Kupferband durch eine mitlaufende Querteilschere in Fertiglängen je nach Kundenanforderungen eingeteilt. Das einseitig beschichtete Kupferband oder -blech wird in Gestelle vereinzelt und die Gestelle werden dann 6 bis 48 Stunden in einem klimatisierten Raum bei einer Temperatur von etwa 20 °C und einer relativen Luftfeuchtigkeit von 70 % ausgelagert. Um die Ausbildung der Schutzschicht auf dem Kupfer in dem klimatisierten Raum zu beschleunigen, kann entweder zusätzlich eine elektrische Spannung angelegt oder gasförmige Reaktionsmedien eingeleitet werden. Nach der Auslagerung wurde das Flächengewicht der Schutz- und Deckschicht von einigen Probestücken bestimmt. Es betrug durchschnittlich etwa 430 mg/dm².A cold-rolled 1000 mm wide strip of SF copper in accordance with DIN 1787 with a thickness of 0.7 mm is first degreased in a continuous device. Immediately afterwards, the copper strip is first moved through a belt grinding machine to deliberately enlarge the surface, for example by a factor of 2, which, for. B. is provided with one or more sanding belts of grain size 40 to 60 and optionally with an additional brushing device. The installed belt center or belt edge control ensures precise positioning of the copper belt in relation to the sanding belt. The copper strip then passes through a duo-roll stand, the rolls of which are preferably in the direction of the roll axis have roughened or textured surfaces. The copper strip then runs in a line through a spraying and squeezing device in which the chemical reaction solution for green patination is applied evenly to the surface. After the reaction solution has been applied, the copper strip is divided into finished lengths according to customer requirements using a cross cutting shear. The copper tape or sheet coated on one side is separated into racks and the racks are then stored for 6 to 48 hours in an air-conditioned room at a temperature of around 20 ° C and a relative humidity of 70%. In order to accelerate the formation of the protective layer on the copper in the air-conditioned room, either an additional electrical voltage can be applied or gaseous reaction media can be introduced. After removal from storage, the weight per unit area of the protective and top layer was determined from a few test pieces. It averaged about 430 mg / dm².

An dem künstlich grünpatinierten Kupferband können anschließend die für die Verwendung im Baubereich notwendigen Biege- und Abkantoperationen durchgeführt werden, ohne daß Beschädigungen oder großflächige Ablösungen der Schutz- und Deckschicht auftreten.The bending and folding operations necessary for use in the construction sector can then be carried out on the artificially patinated copper strip without damage or large-scale detachment of the protective and cover layers.

Claims (6)

  1. Process for the production of a green protective and covering layer on rolled copper strip or sheet for roof covering and façade cladding, characterised by the combination of the following process steps:
    - degreased copper strip is first roughened by means of a textured working roller to enlarge the surface by a factor of 1.1 to 5;
    - the copper strip is then treated with a chemical reaction solution in a continuous process to produce a green patina, the weight per unit area of the coating lying between 180 and 680 mg/dm²;
    - the chemically treated copper strip is then aged in an air-conditioned room.
  2. Process for the production of a green protective and covering layer according to claim 1, characterised in that the layer on the copper strip consists of copper oxide and an essentially copper-free metal salt.
  3. Process for the production of a green protective and covering layer according to claim 1 or 2, characterised in that the weight per unit area of the coating is 330 to 525 mg/dm².
  4. Process for the production of a green protective and covering layer according to one of claims 1 to 3, characterised in that the chemically treated copper strip is aged at a temperature lying in the range between 15 and 35°C and an air humidity between 70 and 100%.
  5. Process for the production of a green protective and covering layer according to one of claims 1 to 4, characterised in that the aging of the chemically treated copper strip is accelerated by applying a voltage or by adding gaseous reaction means.
  6. Process for the production of a green protective and covering layer according to one of claims 1 to 5, characterised in that the copper strip is continuously cut transversely to the required lengths after the mechanical treatment step or after the application of the chemical reaction solution.
EP91122083A 1990-12-24 1991-12-21 Method of producing a green protecting coating on copper-containing materials Expired - Lifetime EP0492566B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4041854 1990-12-24
DE4041854A DE4041854A1 (en) 1990-12-24 1990-12-24 METHOD FOR PRODUCING A GREEN PATINA ON A SEMI-PRODUCT CONSTRUCTED FROM COPPER
JP03528892A JP3550570B2 (en) 1990-12-24 1992-02-21 Method for producing green protective coatings based on copper semi-finished products
US07/894,104 US5376190A (en) 1990-12-24 1992-06-05 Method for producing a green protective coating on copper

Publications (2)

Publication Number Publication Date
EP0492566A1 EP0492566A1 (en) 1992-07-01
EP0492566B1 true EP0492566B1 (en) 1995-09-20

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EP91122083A Expired - Lifetime EP0492566B1 (en) 1990-12-24 1991-12-21 Method of producing a green protecting coating on copper-containing materials

Country Status (8)

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US (1) US5376190A (en)
EP (1) EP0492566B1 (en)
JP (1) JP3550570B2 (en)
AT (1) ATE128193T1 (en)
DE (2) DE4041854A1 (en)
DK (1) DK0492566T3 (en)
ES (1) ES2077149T3 (en)
GR (1) GR3018030T3 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
FI97975C (en) * 1995-05-11 1997-03-25 Outokumpu Copper Oy A method of treating a coating material of a metallic material
JPH11152581A (en) * 1997-11-17 1999-06-08 Sanbo Copper Alloy Co Ltd Artificial patina copper material and ots production
DE19809904A1 (en) * 1998-03-07 1999-09-09 Km Europa Metal Ag Process and reaction solution to create a patina
ES2156425T3 (en) * 1998-10-01 2001-06-16 Lamitref Ind N V INITIATING CATODES CONSTITUTED OF COPPER TAPE FOR THE ELECTROLYSIS OF COPPER AND PROCESS FOR ITS MANUFACTURE.
DE10354527B4 (en) * 2003-11-17 2008-08-28 Kme Germany Ag Process for patination of copper
KR100890607B1 (en) * 2007-07-02 2009-03-27 김부현 A oxidized verdigris copper manufacture method

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Publication number Priority date Publication date Assignee Title
US1951304A (en) * 1932-01-20 1934-03-13 Copper And Brass Res Ass Method of coloring copper and copper alloys
US3497401A (en) * 1967-09-20 1970-02-24 Intern Copper Research Ass Inc Patination of copper
US3669766A (en) * 1969-11-28 1972-06-13 Mitsunosuke Fukawa Formation of coating on copper containing materials
JPS5613483A (en) * 1979-07-14 1981-02-09 Matsushita Electric Works Ltd Artificial verdigris generating method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMISCHE FÄRBUNGEN VON KUPFER UND KUPFERLEGIERUNGEN, Deutsches Kupfer-Institut, 1974, Berlin (DE); Seiten 35-41 *
WPI/DERWENT, Derwent Publications Ltd., London (GB); Nr. 90-295491(39) *

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GR3018030T3 (en) 1996-02-29
DK0492566T3 (en) 1996-01-02
JP3550570B2 (en) 2004-08-04
ATE128193T1 (en) 1995-10-15
ES2077149T3 (en) 1995-11-16
US5376190A (en) 1994-12-27
EP0492566A1 (en) 1992-07-01
DE59106540D1 (en) 1995-10-26
JPH05271953A (en) 1993-10-19
DE4041854A1 (en) 1992-06-25

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