EP0797631A1 - Künstliche patina - Google Patents

Künstliche patina

Info

Publication number
EP0797631A1
EP0797631A1 EP95916502A EP95916502A EP0797631A1 EP 0797631 A1 EP0797631 A1 EP 0797631A1 EP 95916502 A EP95916502 A EP 95916502A EP 95916502 A EP95916502 A EP 95916502A EP 0797631 A1 EP0797631 A1 EP 0797631A1
Authority
EP
European Patent Office
Prior art keywords
copper
formulation
acid
substrate
patina
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.)
Withdrawn
Application number
EP95916502A
Other languages
English (en)
French (fr)
Other versions
EP0797631A4 (de
Inventor
Andrej Atrens
Jason Nairn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Queensland UQ
Copper Refineries Pty Ltd
Original Assignee
University of Queensland UQ
Copper Refineries Pty Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Queensland UQ, Copper Refineries Pty Ltd filed Critical University of Queensland UQ
Publication of EP0797631A1 publication Critical patent/EP0797631A1/de
Publication of EP0797631A4 publication Critical patent/EP0797631A4/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C23C8/40—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 liquids, e.g. salt baths, liquid suspensions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00525—Coating or impregnation materials for metallic surfaces

Definitions

  • This invention relates to an artificial patina for coating copper substrates.
  • a patina When exposed to the atmosphere over time copper substrates develop a stable greenish-blue film known as a patina.
  • the copper which is initially bright orange first forms a uniform thin layer of matt brown cuprite (Cu applying0) which is then, over time, coated by a green-blue patina layer of between 5 to 15 micrometre thickness .
  • the nature of the film varies according to the locality of the substrate.
  • the patina consists mainly of basic copper sulphate (brochantite CuSO..3Cu(OH)neig) and in marine localities, the patina consists mainly of basic copper chloride (atacamite) .
  • At least 4 years, more typically at least 10 years is necessary for the formation of a natural patina coating. In normal city atmospheres a patina will generally form after 8 to 12 years. In urban atmospheres, the time period is 16 to 20 years.
  • U.S. patent No. 3,152,927 discloses a formulation for an artificial patina which can be applied in the manufacturing plant to produce a pre-patinated copper sheet. These sheets can then be installed at the chosen site.
  • the patination process comprises producing a basic copper nitrate sludge (with excess Cu(OH)_) which is then applied to oxidised copper sheets and allowed to dry.
  • the artificial patina coating formed is, however, a basic copper nitrate and is unstable and will undergo competitive reaction to convert the patina to the natural form. This can result in peeling of the applied patina.
  • the Copper and Brass Research Association (“CABRA) ("Artificial Patination” from Copper Roofing CDA Publication No. 57, 1959) developed a spray method for the coating of large copper objects (eg. roofs) .
  • the spray solution comprises ammonium sulphate, copper sulphate, ammonia and water.
  • the solution is sprayed onto the surface and allowed to dry. This is repeated five to six times .
  • the development of colour depends on suitable weather conditions and rain within eight hours can wash away the solution before the reaction has started. Ideal conditions need fog or a relative humidity of at least 80%.
  • the sheets obtained a patina after about 4 days .
  • This patina is chemically identical to a natural patina but has a different microstructural morphology resulting in easy removal of most of the blue coating.
  • the patina is also a bright blue colour and not the natural blue-green.
  • Major difficulties were experienced in semi-commercial scale production due to the changing solution chemistry (eg. chloride content) of the bath resulting in poor control of the process .
  • the pre-patinated sheets performed well when installed on exposure racks or a roof.
  • Kobe Steel Ltd (Japan) (Toso Kogaku (Coatings Technology) volume 24 number 7 pages 271-275, 1989) developed a technology allowing the production of an artificial patina in a continuous fashion.
  • the method involves treating a clean plain copper sheet with a colouring agent based on basic copper chloride (atacamite) .
  • This coloured layer is applied with a roller and an upper layer of water based acrylic emulsion resin is sprayed over the top to ensure adhesion of the colour film. It is believed that this upper layer treatment will disappear with time and that the basic copper chloride coloured layer will react to form the naturally occurring patina.
  • the artificial patina formed has excellent adhesion properties and can withstand severe metalworking (bending, deep drawing) . In addition accelerated corrosion tests and atmospheric exposure tests have indicated that the artificial patina will react to form the naturally occurring compounds.
  • Natural patinas have a blue-green cast and a streaky, mottled appearance.
  • the coating is softer than a natural patina and can be abraded or peeled off due to the continuous acrylic layer.
  • an artificial patination formulation comprising:
  • a method of coating a copper substrate with an artificial patina comprises applying to the substrate a formulation according to the first aspect.
  • a method of coating a copper substrate with an artificial patina comprises contacting the copper substrate with a persulphate solution, and then allowing the contacted surface to oxidize in a high humidity atmosphere.
  • the copper substrate can be any copper or copper alloy.
  • the substrate will typically be in fabricated or sheet form which may or may not have been pickled and/or acid-cleaned.
  • copper sheeting roofing panels manufactured from copper electrosheet are suitable.
  • Copper "electrosheet” is copper cathode prepared by the electrolytic refining of copper anodes .
  • the substrate is oxidized.
  • an aged electrosheet eg. a four week old electrosheet exhibiting a 3 to 6 micrometer oxide film
  • a four week old electrosheet exhibiting a 3 to 6 micrometer oxide film
  • the substrate may be pretreated with an oxidizing procedure.
  • the formulation can be applied to the copper substrate after installation or can be applied before installation as part of an in-line manufacturing process of the substrate.
  • the formulation can be applied by any suitable application process, typically paintbrush, spray process or by rolling.
  • the hydroxide compound is an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, an alkaline earth metal hydroxide such as barium hydroxide, a transition metal hydroxide or an ammonium hydroxide.
  • the hydroxide is sodium hydroxide.
  • the iron sulphate is added in an amount to provide a patina containing up to 10 wt% iron.
  • the reaction product is formed by dissolving copper sulphate pentahydrate (eg. 500 g) with iron sulphate heptahydrate (eg. 25 g) in water (eg. 4L) , and then adding sodium hydroxide (eg. IM, 40 g/L, 3.132L) preferably quickly so as to form a fine precipitate.
  • the final reaction product has a composition:
  • a suitable binder includes inorganic silicates preferably water-borne, inorganic silicates such as
  • ZincanodeTM 215 available from ICI-Dulux.
  • ZincanodeTM 215 is a high ratio, high build water-borne self curing inorganic silicate.
  • lOOg to l,000g of the reaction product is used per 1 litre of binder, more preferably 350g to 450g per litre.
  • the formulation may further comprise a carboxylic acid.
  • Suitable carboxylic acids include oxalic acid, capric acid, citric acid, tartic acid, D.L. malic acid, sebacic acid, benzoic acid, succinic acid and stearic acid.
  • the carboxylic acid is present in an amount from 0 to 1000 ppm based on the total weight of the formulation.
  • a patina can also be formed by contacting the copper substrate with a strong oxidant such as a persulphate solution.
  • a strong oxidant such as a persulphate solution.
  • the solution of persulphate is a solution of sodium or ammonium persulphate (typically containing between 10 and 200 g/L in the pH range 3 to 8) .
  • the copper substrate can be contacted by spraying the solution onto the substrate.
  • the contacted surface is then allowed to oxidise in high humidity, typically 95% relative humidity by placing the substrate into a humidity cabinet or conducting the process in a natural high humidity environment.
  • An artificial patina on the substrate results.
  • the substrate can then be washed to remove any residual sodium sulphate.
  • EXAMPLE 1 Dissolve 500g CuSO 4 .5H 2 0 and 25g FeSO .7H_0 in 4 litres of water. Add 3.1 litres of IM NaOH (40g/litre) solution. Wash and dry precipitate to produce a "dry" powder. Add 350g of powder to 1 litre of water borne inorganic silicate (Zincanode 215), mix and apply to copper surface.
  • EXAMPLE 2 Dissolve 500g CuS0..5H 2 0 and 5g FeS0..7H 2 0 in 4 litres of water. Add 2.9 litres of IM NaOH (40g/litre) solution. Wash and dry precipitate to produce a "dry" powder. Add 650g of powder to 1 litre of water borne inorganic silicate (Zincanode 215), mix and apply to copper surface.
  • EXAMPLE 3 Dissolve 500g CuSO..H 2 0 and 15g FeS0..7H 2 0 in 4 litres of water. Add 3.0 litres of IM KOH solution. Wash and dry precipitate to produce a "dry" powder. Add 450g of powder and lOOmg oxalic acid to 1 litre of water borne inorganic silicate (Zincanode 215) , mix and apply to copper surface.
  • the processes and formulations of the present invention are suitable for forming a patina on any copper substrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
EP95916502A 1994-04-26 1995-04-21 Künstliche patina Withdrawn EP0797631A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPM5294A AUPM529494A0 (en) 1994-04-26 1994-04-26 Artificial patina
AUPM0529/49 1994-04-26
PCT/AU1995/000236 WO1995029207A1 (en) 1994-04-26 1995-04-21 Artificial patina

Publications (2)

Publication Number Publication Date
EP0797631A1 true EP0797631A1 (de) 1997-10-01
EP0797631A4 EP0797631A4 (de) 1998-05-06

Family

ID=3779871

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95916502A Withdrawn EP0797631A4 (de) 1994-04-26 1995-04-21 Künstliche patina

Country Status (5)

Country Link
EP (1) EP0797631A4 (de)
JP (1) JPH10503224A (de)
AU (1) AUPM529494A0 (de)
CA (1) CA2188661A1 (de)
WO (1) WO1995029207A1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20020307A1 (it) * 2002-02-15 2003-08-18 Beretta Armi Spa Procedimento per conferire un effetto cromatico a tartaruga a substrati metallici
FI20020669A7 (fi) * 2002-04-09 2003-10-10 Outokumpu Oy Menetelmä keinotekoisen patinan valmistamiseksi ja patinapasta
KR100467939B1 (ko) * 2002-05-13 2005-01-24 김부현 건축자재 산화 동판 제조용 산화제 조성물
KR20030088550A (ko) * 2002-05-13 2003-11-20 김부현 건축 자재용 산화 동판의 제조방법
DE10243139A1 (de) * 2002-09-17 2004-03-25 Omg Galvanotechnik Gmbh Dunkle Schichten
DE102006053192A1 (de) 2006-11-09 2008-05-15 Kme Germany Ag Verfahren zum Schutz von patinierten Oberflächen von Kupferprodukten sowie patiniertes Kupferprodukt
KR101678135B1 (ko) * 2015-09-15 2016-11-21 포항공과대학교 산학협력단 녹청 형성 방법
CN109988477A (zh) * 2019-04-23 2019-07-09 广东金涂宝新材料股份有限公司 一种水性仿铁锈涂料及其施工方法
CN111549336A (zh) * 2020-04-02 2020-08-18 福建捷思金属科技发展有限公司 一种铜绿预氧化热着色方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5935937B2 (ja) * 1974-07-16 1984-08-31 関西ペイント株式会社 水性塗料組成物
JPS52131236A (en) * 1976-04-26 1977-11-04 Sekisui Chem Co Ltd Solar energy absorber
AU532049B2 (en) * 1980-02-01 1983-09-15 Cook Paint & Varnish Co. Zinc rich paints having silicate and titanate ester copoly- mer binder

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9529207A1 *

Also Published As

Publication number Publication date
EP0797631A4 (de) 1998-05-06
CA2188661A1 (en) 1995-11-02
AUPM529494A0 (en) 1994-05-19
JPH10503224A (ja) 1998-03-24
WO1995029207A1 (en) 1995-11-02

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