EP3211113A1 - Produit galvanisé et procédé - Google Patents

Produit galvanisé et procédé Download PDF

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Publication number
EP3211113A1
EP3211113A1 EP16157254.0A EP16157254A EP3211113A1 EP 3211113 A1 EP3211113 A1 EP 3211113A1 EP 16157254 A EP16157254 A EP 16157254A EP 3211113 A1 EP3211113 A1 EP 3211113A1
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EP
European Patent Office
Prior art keywords
galvanized
product
zinc
zinc carbonate
water
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Withdrawn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
EP16157254.0A
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German (de)
English (en)
Inventor
Ville Saarima
Aaretti Kaleva
Pasi VÄISÄNEN
Antti Markkula
Erkki LEVÄNEN
Saara Heinonen
Juha-Pekka NIKKANEN
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.)
Rautaruukki Oyj
Original Assignee
Rautaruukki Oyj
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 Rautaruukki Oyj filed Critical Rautaruukki Oyj
Priority to EP16157254.0A priority Critical patent/EP3211113A1/fr
Priority to PL17707552T priority patent/PL3420114T3/pl
Priority to EP17707552.0A priority patent/EP3420114B1/fr
Priority to PCT/EP2017/054509 priority patent/WO2017144721A1/fr
Priority to ES17707552T priority patent/ES2853205T3/es
Priority to DK17707552.0T priority patent/DK3420114T3/da
Publication of EP3211113A1 publication Critical patent/EP3211113A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
    • C23C22/53—Treatment of zinc or alloys based thereon

Definitions

  • the present invention concerns a galvanized product having a surface comprising zinc carbonate and a method for manufacturing such a galvanized product.
  • Patina is a thin layer that naturally forms on the surface of copper, bronze and ferrous metals i.e. steels and irons, on environmental exposure to atmospheric elements such as air and precipitation, in the form of rain, snow, dew, ice, humidity, condensation, etc.
  • Patinas which may comprise various chemical compounds such as oxides, carbonates, sulfides or sulfates, can provide a protective covering to materials that would otherwise be damaged by corrosion or weathering.
  • Galvanization is the process of applying a protective zinc coating to a ferrous metal, i.e. iron or steel, to prevent rusting.
  • the most common galvanization method is hot-dip galvanization, in which ferrous metal parts are submerged in a bath of molten zinc. Galvanizing protects the ferrous metal surface in two ways: it forms a coating of corrosion-resistant zinc which prevents corrosive substances from reaching the more delicate part of the metal, and the zinc serves as a sacrificial anode so that even if the coating is scratched, the exposed metal will still be protected by the remaining zinc.
  • a patina layer (i.e. a zinc carbonate layer) forms naturally on a galvanized ferrous metal that is exposed to atmospheric elements during its use in the following stages: the zinc in the galvanized ferrous metal surface reacts with oxygen in the air to form zinc oxide, ZnO, water or moisture from atmospheric precipitation reacts with the zinc oxide to form zinc hydroxide, Zn(OH) 2 , and oxygen and carbon dioxide in the air reacts with the zinc hydroxide to form zinc carbonate, 2ZnCO 3 ⁇ Zn(OH) 2 .
  • patina layer on a galvanized ferrous metal can take up to several years depending on environmental conditions.
  • This natural formation of a patina layer is disadvantageous since it is necessary to wait until a patina layer has formed before a galvanized ferrous metal can be painted in order to ensure that the paint will properly adhere to the surface of the ferrous metal steel.
  • galvanized ferrous metal is passivated to protect the relatively sensitive zinc layer from corrosion. Paint applied to a surface of a passivated galvanized ferrous metal may lose its adhesion over time since such a freshly applied passivation layer is not an optimum surface for painting.
  • a naturally formed patina layer may not be uniform as regards its thickness and/or structure, and it may contain impurities, i.e.
  • a naturally formed patina does provide a good substrate for painting.
  • the continuous colour coating of galvanized ferrous metal usually requires several chemical pre-treatments, which may at least partly be rendered unnecessary by allowing a patina layer to form and applying paint directly on the patina layer.
  • US patent no. US 3,767,478 discloses the formation of a smooth, even, corrosion resistant patina on a zinc surface by abrading or otherwise mechanically graining the surface, and thereafter forming an even zinc phosphate Zn 3 (PO 4 ) 2 coating thereon, preferably in the presence of a nickel ion.
  • This solution involves the formation of a protective layer having a different chemical composition and structure than a naturally formed patina layer.
  • An object of the invention is to provide an improved galvanized product.
  • a galvanized product having a galvanized surface comprising a zinc carbonate layer that comprises at least one type of metallic ion of a metal that is more noble than zinc and that excludes avoidable impurities in a delivery condition of the galvanized product, i.e. the zinc carbonate layer is not a naturally formed zinc carbonate layer but it has been artificially formed in under controlled conditions before it is delivered to an end user and put into use.
  • controlled conditions means that impurities such as dust, dirt, oil, grease, sea salt, and/or any impurities from air pollution caused by industry or traffic for example, will not be incorporated into the zinc carbonate layer during its formation, as would be the case if the zinc carbonate layer was naturally formed on environmental exposure during its use.
  • the galvanized product according to the present invention therefore comprises a zinc carbonate layer that is more uniform and of a higher quality, i.e. more pure and ideal, than a naturally formed zinc carbonate layer.
  • This artificially formed zinc carbonate layer is advantageously formed much more quickly than a naturally formed zinc carbonate layer.
  • the artificially formed zinc carbonate layer will protect the galvanized product from corrosion during the transportation, the storage and the use of the galvanized product and it serves as a good substrate for post-patination operations such as painting. Post-patination operations may be carried out, without pre-treatment or cleaning in many cases, as soon as the zinc carbonate has been artificially formed or as soon as the galvanized product is delivered to an end user, or as soon as the galvanized product has been mounted ready for use. Such an artificially formed zinc carbonate layer may also at least partly eliminate the need for chemical pre-treatments in post-patination operations such as continuous colour coating.
  • the artificially formed zinc carbonate layer will have the same chemical composition as a naturally formed patina layer (but will exclude avoidable impurities, such as dust, dirt, oil, grease, sea salt, and/or any impurities from air pollution caused by industry or traffic for example) and the same structure as a naturally formed patina layer (but will exclude structural irregularities). It is non-toxic, non-combustible and thereby environmentally friendly.
  • layer as used in this document is intended to mean any amount of material of any uniform or non-uniform thickness that is uniformly or non-uniformly spread over an area of a substrate, i.e. over at least a part of a galvanized surface.
  • a zinc carbonate layer may namely be artificially formed on a galvanized surface of a galvanized product in any desired manner or pattern depending on the end use of the galvanized product, or even for aesthetic reasons.
  • the galvanized product according to the present invention may be of any shape, weight, or size. It may be in the form any flat, tubular or shaped product, such as strip, sheet, plate, wire or profile, it may be a hot-rolled or cold-rolled product.
  • the galvanized product may be used for any suitable application, such as applications in the automotive, construction, marine, engineering or metal-producing industries.
  • the galvanized product may for example constitute at least one part of a vehicle, a civil engineering construction, such as a bridge, part of a building, such as a roof, a façade, a silo, a trailer, a monument, etc.
  • the galvanized product is a galvanized ferrous metal product, i.e. zinc-coated iron or steel.
  • the galvanized product is a hot-dip galvanized product, an electrogalvanized product or a product with a thermal spray zinc coating.
  • the at least one type of metallic ion of a metal that is more noble than zinc is preferably an ion of at least one of the following: copper, iron, silver, palladium, platinum, gold, titanium, molybdenum, tungsten, tin, lead, steel, brass, tantalum, nickel, indium, aluminium, cadmium or beryllium.
  • the present invention also concerns a method for manufacturing a galvanized product comprising an artificially formed zinc carbonate layer (artificial patination) according to any of the embodiments of the invention.
  • the method comprises the step of treating a galvanized surface of a galvanized product with carbon dioxide (in any form, i.e. in solid, liquid, gaseous or supercritical form, or in any combination of these forms), water and at least one type of metallic ion of a metal that is more noble than zinc under controlled conditions, for example in a controlled environment, such as under controlled temperature, pressure and time, in order to provide an artificially formed zinc carbonate layer on the galvanized surface of the galvanized product.
  • This method is performed before the galvanized product leaves the factory, i.e. before it is delivered to an end user, or before it undergoes a subsequent manufacturing or finishing step, such as painting.
  • the method is performed in a continuous line manufacturing process in which the galvanized product is produced without interruption, whereby a material is substantially continuously in motion while it undergoes galvanizing and/or artificial patination and/or one or more chemical reactions, mechanical treatments and/or heat treatments.
  • at least part of the method according to the present invention may be carried out using batch production in which one or more galvanized products are created stage by stage over a series of workstations.
  • the step of treating the galvanized surface of a galvanized product involves subjecting the galvanized surface to a temperature of at least 293 K, or a temperature of 293-343 K, 300-340 K or 310-330 K, and/or to a pressure of 6-30 MPa, or 6-20 MPa or 10-20 MPa for a predetermined exposure time.
  • the predetermined exposure time is up to 60 minutes, or 5-50 minutes or 5-30 minutes or 10-30 minutes or until a zinc carbonate layer having the desired properties has formed on at least part of the galvanized surface.
  • an exposure time of a fraction of one second or up to 10 seconds may be sufficient.
  • the method comprises the step of decreasing the pressure at a rate, such as 6-30 MPa per minute, after the predetermined exposure time has elapsed. This may be done by decreasing the pressure in a pressure chamber in batch production, or by merely moving a galvanized product out of an artificial patination section of a continuous line manufacturing process at a predetermined rate.
  • the galvanized product is a galvanized ferrous metal product.
  • the product is a hot-dip galvanized product, an electrogalvanized product or a product with a thermal spray zinc coating.
  • the at least one type of metallic ion of a metal that is more noble than zinc is preferably an ion of at least one of the following: copper, iron, silver, palladium, platinum, gold, titanium, molybdenum, tungsten, tin, lead, steel, brass, tantalum, nickel, indium, aluminium, cadmium or beryllium.
  • the precursor is preferably non-soluble in water, although it can alternatively be soluble in water.
  • the carbon dioxide is in at least one of the following forms: gaseous, liquid phase, solid form, supercritical, i.e. at a temperature and pressure above its critical point (304.25 K and 7.39 MPa), where distinct liquid and gas phases do not exist.
  • the carbon dioxide may namely be in any form or a mixture of forms depending on the reaction speed and zinc carbonate layer structure which are desired. Different reaction speeds and different zinc carbonate layer structures, such as needle-like or ball-like structures, may namely be obtained depending on the form of carbon dioxide that is used.
  • the water is de-ionized water, tap water, sea water, lake water or any other suitable aqueous electrolyte which allows a zinc hydroxide layer to form during the artificial formation of a zinc carbonate layer.
  • the method preferably comprises at least one of the following steps: cleaning and/or roughening a galvanized surface of the galvanized product prior to artificially forming the zinc carbonate layer on the galvanized surface. It is not however always necessary to clean and/or roughen the galvanized surface of the galvanized product.
  • the method comprises the steps of dissolving a metal precursor comprising the at least one type of metallic ion of a metal that is more noble than zinc, which may be soluble or non-soluble in water, in a solvent, and then mixing the solvent containing the metal precursor with the water to treat the galvanized surface of a galvanized product.
  • the solvent can be an organic solvent, such as ethanol, methanol or another alcohol or an aldehyde or a ketone. It should be noted that the expression "solvent" is intended to include a single solvent, or any mixture of solvents.
  • FIG. 1a shows a galvanized product 10 comprising a metal substrate 12, such as steel or iron, having a galvanized surface 14.
  • a metal substrate 12 such as steel or iron
  • FIG. 1a shows a galvanized product 10 comprising a metal substrate 12, such as steel or iron, having a galvanized surface 14.
  • oxygen in the air 16 illustrated as a free-flowing air flow, will react with the zinc in the galvanized surface 14 to form zinc oxide (ZnO) 18.
  • ZnO zinc oxide
  • Figure 1b shows that water and/or moisture from atmospheric precipitation 20 reacts with the zinc oxide 18 to form zinc hydroxide 22 (Zn(OH) 2 ).
  • Figure 1c shows that oxygen and carbon dioxide in the air 16 reacts with the zinc hydroxide 22 to form zinc carbonate (2ZnCO 3 ⁇ Zn(OH) 2 ) 24.
  • a naturally formed zinc carbonate layer 24 as illustrated in figures 1 a) to c) can take years depending on the atmospheric conditions to which a galvanized product 10 is subjected during its use, transportation and/or storage. Furthermore, a naturally formed zinc carbonate layer 24 may not be uniform and it may contain impurities from its surroundings, such as dust, dirt, oil, grease, sea salt and/or trace elements of contaminants present in its surroundings, since a zinc carbonate layer 24 exposed to atmospheric elements is not formed under controlled conditions.
  • a galvanized product 10 according to the present invention such as a hot-dip galvanized iron or steel sheet, will, on the contrary, have a galvanized surface comprising a zinc carbonate layer 24 of better quality than a naturally formed zinc carbonate layer since it has been artificially formed under controlled conditions.
  • the zinc carbonate layer 24 will however comprise at least one type of metallic ion of a metal that is more noble than zinc, such as copper (Cu 2+ ), iron (Fe 2+ ) or silver (Ag 2+ ) which remain as a consequence of the artificial formation.
  • the artificially formed zinc carbonate layer 24 will not however contain avoidable impurities, such as dust, dirt, oil, grease, sea salt etc. when it is delivered to an end user.
  • the steps of a method for manufacturing a galvanized product 10 comprising an artificially formed zinc carbonate layer 24 according to an embodiment of the invention are illustrated in figure 2 , wherein non-essential method steps are shown in rectangles drawn with dashed lines and essential method steps are shown in rectangles drawn with continuous lines.
  • the method comprises the steps of optionally cleaning and/or roughening at least part of a galvanized surface 14 of the galvanized product 10 prior to artificially forming the zinc carbonate layer 24 thereon in order to provide a more adhesive surface for subsequent treatments, such as painting.
  • One or more impurities, such as an aluminium oxide, which may be formed on top of the zinc layer after galvanization, may for example be removed from the metallic zinc layer prior to artificial patination.
  • the galvanized surface 14 may then be placed or moved into in a controlled environment.
  • the galvanized surface 14 may be placed into a pressure chamber or an artificial patination workstation during batch production or into it may be moved into an artificial patination section at a controlled feed rate during a continuous line manufacturing process.
  • the galvanized surface 14 is exposed to carbon dioxide in any suitable form, such as carbon dioxide having a purity of at least 99.8%, and may optionally be heated to a temperature of at least 293 K, such as 293-343 K and/or subjected to a pressure of 6-30 MPa.
  • water containing a metal precursor i.e. any compound comprising at least one type of metal ion that is more noble than zinc
  • a metal precursor i.e. any compound comprising at least one type of metal ion that is more noble than zinc
  • the metal precursor may be Cu(hfac) 2 or Ag(cod)(hfac) or Cu(NO 3 ) 2 or Fe(NO 3 ) 3 .
  • the precursor is non-soluble in water, such as Cu(hfac) 2 or Ag(cod)(hfac), and may firstly be dissolved in a solvent, such as an organic solvent, such as ethanol and then mixed with water before it is applied and/or sprayed and/or injected onto the galvanized surface 14.
  • a solvent such as an organic solvent, such as ethanol
  • This process is easily adapted to production environments and is especially suited to complicated surfaces found in grooved couplings and fittings of galvanized products 10.
  • the galvanized surface 14 may remain in the controlled environment for a predetermined exposure time, such from a fraction of a second (which may be sufficient during a continuous line manufacturing process) up to 60 minutes. If the galvanized product 10 is being manufactured using batch production, in a pressure chamber for example, the pressure may be decreased at a predetermined rate, such as at a rate of 6-30 MPa per minute, after the predetermined exposure time has elapsed. The rate at which the pressure is decreased will affect the structure of the artificially formed zinc carbonate layer 24.
  • the zinc carbonate layer 24 will continue to form during the entire method until the galvanized surface 14 is removed from the pressure chamber, or from an application section of a continuous line manufacturing process, where carbon dioxide at a desired temperature and/or pressure, water and at least one metallic ion of a metal that is more noble than zinc is applied and/or injected and/or sprayed onto the galvanized surface 14.
  • the galvanized product 10 may leave the factory where it is manufactured and be delivered to an end user or placed in storage.
  • the artificially formed zinc carbonate layer 24 is not water soluble and does not wash off the galvanized surface 14.
  • the at least one type of metallic ion acts as a catalyst in the formation of a zinc carbonate layer 24, it speeds up the reaction time and will remain in the artificially formed zinc carbonate layer 24, which makes an artificially formed zinc carbonate layer 24 distinguishable from a naturally formed zinc carbonate layer.
  • the artificially formed zinc carbonate layer 24 may contain one or more copper compounds if a metal precursor containing copper ions has been used in its manufacturing method.
  • the artificially formed zinc carbonate layer 24 will have superior properties as compared to a naturally formed zinc carbonate layer since its structure will be more uniform (rather than randomly compact or porous) and it will adhere better to the underlying galvanized surface. Paint can be applied directly to the artificially formed zinc carbonate layer 24 and no adhesion problems have been encountered.
  • the method according to the present invention bypasses the different stages of the natural formation of a zinc carbonate layer 24 as illustrated in figures 1a ) to c) and will form a more pure and ideal and more tightly adhered layer as compared to a naturally formed zinc carbonate layer.
  • a naturally formed zinc carbonate layer 24 may namely be non-uniform as regards its thickness and/or properties, and it may be loosely adhered to the underlying galvanized layer, it may be porous and contaminated with impurities.
  • the method according to the present invention may comprise the step of treating a galvanized surface 14 of a hot-dip galvanized steel sheet 10 with supercritical carbon dioxide and 0.53 m-% copper solution (including water) at a temperature of 323 K and at a pressure of 30 MPa for 30 minutes, and then decreasing the pressure at a rate of 10 MPa per minute.
EP16157254.0A 2016-02-25 2016-02-25 Produit galvanisé et procédé Withdrawn EP3211113A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP16157254.0A EP3211113A1 (fr) 2016-02-25 2016-02-25 Produit galvanisé et procédé
PL17707552T PL3420114T3 (pl) 2016-02-25 2017-02-27 Warstwa patyny na galwanizowanym produkcie i sposób jej wytwarzania
EP17707552.0A EP3420114B1 (fr) 2016-02-25 2017-02-27 Couche de patine sur un produit galvanisé et son procédé
PCT/EP2017/054509 WO2017144721A1 (fr) 2016-02-25 2017-02-27 Couche de patine sur produit galvanisé et procédé associé
ES17707552T ES2853205T3 (es) 2016-02-25 2017-02-27 Capa de pátina sobre producto galvanizado y método para ello
DK17707552.0T DK3420114T3 (da) 2016-02-25 2017-02-27 Patinalag på galvaniseret produkt og fremgangsmåde derfor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16157254.0A EP3211113A1 (fr) 2016-02-25 2016-02-25 Produit galvanisé et procédé

Publications (1)

Publication Number Publication Date
EP3211113A1 true EP3211113A1 (fr) 2017-08-30

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP16157254.0A Withdrawn EP3211113A1 (fr) 2016-02-25 2016-02-25 Produit galvanisé et procédé
EP17707552.0A Active EP3420114B1 (fr) 2016-02-25 2017-02-27 Couche de patine sur un produit galvanisé et son procédé

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP17707552.0A Active EP3420114B1 (fr) 2016-02-25 2017-02-27 Couche de patine sur un produit galvanisé et son procédé

Country Status (5)

Country Link
EP (2) EP3211113A1 (fr)
DK (1) DK3420114T3 (fr)
ES (1) ES2853205T3 (fr)
PL (1) PL3420114T3 (fr)
WO (1) WO2017144721A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020130833A1 (fr) * 2018-12-21 2020-06-25 Aquacare Europe B.V. Procédé pour patiner des surfaces en zinc et système associé

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767478A (en) 1971-09-14 1973-10-23 Ball Corp Method for producing patina on a zinc surface and article so formed
US6231686B1 (en) * 1997-11-10 2001-05-15 Ltv Steel Company, Inc. Formability of metal having a zinc layer
US20050003091A1 (en) * 2001-11-16 2005-01-06 Marianne Schoennenbeck Method for the production of dark protective layers on flat objects made from titanium zinc

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767478A (en) 1971-09-14 1973-10-23 Ball Corp Method for producing patina on a zinc surface and article so formed
US6231686B1 (en) * 1997-11-10 2001-05-15 Ltv Steel Company, Inc. Formability of metal having a zinc layer
US20050003091A1 (en) * 2001-11-16 2005-01-06 Marianne Schoennenbeck Method for the production of dark protective layers on flat objects made from titanium zinc

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DAVID LINDSTRÃM ET AL: "Long-term use of galvanized steel in external applications. Aspects of patina formation, zinc runoff, barrier properties of surface treatments, and coatings and environmental fate", ENVIRONMENTAL MONITORING AND ASSESSMENT ; AN INTERNATIONAL JOURNAL DEVOTED TO PROGRESS IN THE USE OF MONITORING DATA IN ASSESSINGENVIRONMENTAL RISKS TO MAN AND THE ENVIRONMENT, KLUWER ACADEMIC PUBLISHERS, DO, vol. 173, no. 1 - 4, 7 March 2010 (2010-03-07), pages 139 - 153, XP019872054, ISSN: 1573-2959, DOI: 10.1007/S10661-010-1377-8 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020130833A1 (fr) * 2018-12-21 2020-06-25 Aquacare Europe B.V. Procédé pour patiner des surfaces en zinc et système associé
NL2022279B1 (en) * 2018-12-21 2020-07-15 Aquacare Europe B V Method for patinating zinc surfaces and system therefor
CN113474480A (zh) * 2018-12-21 2021-10-01 艾库卡尔欧洲有限公司 用于使锌表面锈化的方法及其系统
US20220074037A1 (en) * 2018-12-21 2022-03-10 Aquacare Europe B.V. Method for patinating zinc surfaces and system therefor

Also Published As

Publication number Publication date
ES2853205T3 (es) 2021-09-15
WO2017144721A1 (fr) 2017-08-31
EP3420114A1 (fr) 2019-01-02
DK3420114T3 (da) 2021-02-15
EP3420114B1 (fr) 2020-12-09
PL3420114T3 (pl) 2021-06-28

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