EP3420114B1 - Couche de patine sur un produit galvanisé et son procédé - Google Patents

Couche de patine sur un produit galvanisé et son procédé Download PDF

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Publication number
EP3420114B1
EP3420114B1 EP17707552.0A EP17707552A EP3420114B1 EP 3420114 B1 EP3420114 B1 EP 3420114B1 EP 17707552 A EP17707552 A EP 17707552A EP 3420114 B1 EP3420114 B1 EP 3420114B1
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Prior art keywords
zinc
product
patina layer
layer
artificially
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German (de)
English (en)
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EP3420114A1 (fr
Inventor
Ville SAARIMAA
Aaretti Kaleva
Pasi VÄISÄNEN
Antti Markkula
Erkki LEVÄNEN
Saara Heinonen
Juha-Pekka NIKKANEN
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Rautaruukki Oyj
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Rautaruukki Oyj
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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 product that has a coating comprising zinc, and a patina layer.
  • the product comprises iron or steel and has a coating comprising zinc, i.e. pure or high purity zinc or a zinc alloy, and a patina layer on top of the coating comprising zinc.
  • the present invention also concerns a method for artificially producing a patina layer on at least one part of a product having a coating comprising zinc.
  • 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 a 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 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 basic zinc carbonate, also known as hydrozincite, which is a white carbonate mineral consisting of Zn 5 (CO 3 ) 2 (OH) 6 .
  • a 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. contaminants picked up from its surroundings, such as dust, dirt, oil, grease and/or sea salt or trace elements from air pollution caused by industry or traffic for example.
  • impurities i.e. contaminants picked up from its surroundings, such as dust, dirt, oil, grease and/or sea salt or trace elements from air pollution caused by industry or traffic for example.
  • 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.
  • US 6,231,686 concerns a method of treating a metal object having an outer layer including zinc.
  • the method includes applying to the object a treating material in the form of an alkaline solution or a gas.
  • the treating material reacts to form a reaction layer on the outer layer.
  • the reaction layer includes a zinc reaction product.
  • a protective coating such as lubricant is applied to the object, wherein the reaction layer is present in an amount effective to increase a lubricity of the object.
  • the metal object includes an outer layer including zinc which may be substantially non-oxidized.
  • a reaction layer comprising zinc carbonate is disposed on the outer layer.
  • the reaction layer is present in an amount effective to increase a lubricity of the object during a forming process.
  • a protective coating may be in contact with the reaction layer.
  • the patina layer which consists of hydrozincite, is formed using a bicarbonate compound.
  • US 2005/003091 relates to the production of protective coatings with a dark color by pickling rolled flat objects, made from titanium zinc, for use in construction.
  • the flat objects are pickled in an aqueous pickling bath containing a mixed acid of sulphuric acid and nitric acid and passivated after rinsing by application of a protective layer.
  • Rolled flat objects such as those made from a titanium zinc alloy are used.
  • the alloy comprises mainly zinc of high purity with additionally a copper content of 1.0 to 2.0 wt. %, a titanium content of 0.06 to 0.2 wt. % and a maximum aluminum content of 0.015 wt. %.
  • An object of the invention is to provide an improved product comprising a coating comprising zinc and a patina layer, as defined in claim 1.
  • a product such as a product comprising iron or steel, which has coating containing zinc, i.e. said product comprises a coating containing pure zinc, high purity zinc (i.e. at least 95% zinc), or a zinc alloy, such as zinc alloyed with aluminium or magnesium.
  • the coating comprising zinc may be applied using any suitable method, such as galvanizing, hot-dip galvanizing, electro-galvanizing, spraying, thermal spray coating or mechanical plating.
  • the patina layer is an artificially-formed patina layer that comprises zinc carbonate having the chemical formula ZnCO 3 , i.e.
  • the artificially-formed patina layer also comprises at least one type of metallic ion of a metal that is more noble than zinc.
  • the at least one type of metallic ion of a metal that is more noble than zinc constitutes part of the structure of the artificially-formed patina layer.
  • the patina layer is not therefore a naturally formed patina layer, but it has been artificially-formed before it is delivered to an end user and put into use.
  • a naturally formed patina layer always contains or consists of basic zinc carbonate having the chemical formula Zn 5 (CO 3 ) 2 (OH) 6 , which is also known as hydrozincite.
  • a patina layer comprising zinc carbonate having the chemical formula ZnCO 3 will not form naturally during atmospheric exposure of a product having a coating comprising zinc.
  • a naturally-formed patina layer does not have a needle-like structure (like artificially-formed basic zinc carbonate having the chemical formula Zn 5 (CO 3 ) 2 (OH) 6 ,) or a ball-like structure (like artificially-formed zinc carbonate having the chemical formula ZnCO 3 ) or a combination of these structures.
  • a naturally-formed patina layer is a porous layer that does not have a needle-like and/or ball-like structure.
  • the artificially-formed patina layer comprises basic zinc carbonate having the chemical formula Zn 5 (CO 3 ) 2 (OH) 6 , i.e. hydrozincite, having a needle-like structure.
  • the patina layer also comprises one or more other zinc carbonate compounds.
  • the artificially-formed patina layer is produced under controlled conditions whereby impurities such as dust, dirt, oil, grease, sea salt, and/or any impurities from air pollution caused by industry or traffic for example, which are incorporated into the patina layer during its artificial formation, will be eliminated or substantially reduced compared to naturally formed patina layers.
  • impurities such as dust, dirt, oil, grease, sea salt, and/or any impurities from air pollution caused by industry or traffic for example
  • the product according to the present invention therefore comprises a patina layer that is more uniform and of a higher quality, i.e. more pure and ideal, than a naturally formed patina layer.
  • This artificially-formed patina layer is advantageously formed much more quickly than a naturally formed patina layer.
  • the artificially-formed patina layer will protect the product from corrosion during the transportation, the storage and the use of the 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 patina layer has been artificially-formed or as soon as the product is delivered to an end user, or as soon as the product has been mounted ready for use.
  • Such an artificially-formed 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 patina layer has equivalent or better chemical properties than a naturally formed patina layer but will exclude structural irregularities due to the lack of impurities such as dust, dirt, oil, grease, sea salt, and/or any impurities from air pollution. It is non-toxic, non-combustible and thereby environmentally friendly. Furthermore, zinc run-off will not take place during artificial patina formation (as it does during natural patina formation when a product having a coating comprising zinc is exposed to atmospheric elements.) This lack of run-off prolongs the useful lifetime of the product according to the invention since the product having an artificially-formed patina layer will consequently have a thicker coating comprising zinc and thereby prolonged corrosion resistance compared to a product having a natural formed patina layer.
  • the artificially-formed patina layer namely has fewer OH-groups and/or less absorbed water than the naturally formed patina layer.
  • the word "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, or the whole of a surface of a product.
  • a patina layer may namely be artificially-formed on at least part of a product's coating that comprises zinc in any desired manner or pattern depending on the end use of the product, or even for aesthetic reasons.
  • the coating comprising zinc may also be formed on at least part of, or the whole of any one or more surfaces of a product.
  • the 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 product may be used for any suitable application, such as applications in the automotive, construction, marine, engineering or metal-producing industries.
  • the 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 facade, a silo, a trailer, a monument, etc.
  • 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, tantalum, nickel, indium, cadmium or beryllium.
  • the present invention also concerns a method for artificially producing a patina layer on at least part of a surface of a product having a coating comprising zinc to thereby produce a product according to any of the embodiments of the invention.
  • artificially producing is intended to mean that the patina layer is not produced naturally by exposing at least part of the product having a coating comprising zinc to atmospheric elements).
  • the method is defined in claim 5 and comprises the step of treating at least part of surface of a product having a coating comprising zinc with carbon dioxide in solid, liquid, 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, as under controlled temperature, pressure and time, in order to provide an artificially-formed patina layer (rather than a naturally formed patina layer) on the surface of the product having a coating comprising zinc, whereby the patina layer comprises zinc carbonate having the chemical formula ZnCO 3 and basic zinc carbonate having the chemical formula Zn 5 (CO 3 ) 2 (OH) 6 having a needle-like structure.
  • the artificially-formed patina layer also comprises at least one type of metallic ion of a metal that is more noble than zinc.
  • the at least one type of metallic ion of a metal that is more noble than zinc constitutes part of the structure of the artificially-formed patina layer.
  • the step of treating at least part of a surface of a product involves subjecting at least part of the surface to a temperature of at least 273 K, or a temperature of 273-293 or 293-343 K, 300-340 K or 310-330 K, and to a pressure of 6-30 MPa, or 6-20 MPa or 6-20 MPa for a predetermined exposure time.
  • the artificial formation of a patina layer is initiated by the reduction of the metal that is more noble than zinc, such as copper (Cu 2+ to Cu), and the corresponding oxidation of the zinc in the coating comprising zinc (of Zn to Zn 2+ ).
  • controlled conditions means at any place where products having a coating comprising zinc are manufactured, such as a factory or steel plant. Controlled conditions ensure that the artificially-formed patina layer that is formed will comprise zinc carbonate having the chemical formula ZnCO 3 , i.e. a mineral ore of zinc also known as Smithsonite, or zinc carbonate having the chemical formula ZnCO 3 and basic zinc carbonate (Zn 5 (CO 3 ) 2 (OH) 6 ), also known as hydrozincite, and at least one type of metallic ion of a metal that is more noble than zinc.
  • the artificially-formed patina layer produced using such a method comprises basic zinc carbonate having the chemical formula (Zn 5 (CO 3 ) 2 (OH) 6 ), i.e. hydrozincite, having a needle-like structure.
  • the artificially-formed patina layer may also comprise one or more other zinc carbonate compounds.
  • the artificially-formed patina layer does not namely contain any or very little of the following impurities: dust, dirt, oil, grease, sea salt, and/or any impurity from air pollution.
  • This method is preferably performed before the 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 may however be performed at any suitable time during the manufacture, storage, delivery, use, repair and/or maintenance of the product.
  • the step of treating at least part of a surface of a product also comprises adding a surfactant, such as ethanol, to lower surface tension between the water and the carbon dioxide and thereby improve the emulsion forming of carbon dioxide.
  • a surfactant such as ethanol
  • the method is performed in a continuous line manufacturing process in which the product is produced without interruption, whereby a material is substantially continuously in motion while it undergoes a coating process to form a coating comprising zinc on at least part of the product, 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 products are created stage by stage over a series of workstations.
  • the step of treating at least part of a surface of a product involves subjecting at least part of the surface to a temperature of at least 273 K, or a temperature of 273-293 or 293-343 K, 300-340 K or 310-330 K, and to a pressure of 6-30 MPa, or 6-20 MPa or 6-20 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 patina layer having the desired properties has formed on at least part of the 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 10 minutes or per 20 minutes or per 30 minutes or longer, 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 product out of an artificial patination section of a continuous line manufacturing process at a predetermined rate.
  • said coating comprising zinc is applied using one of the following methods: galvanizing, hot-dip galvanizing, electro-galvanizing, spraying, thermal spray coating or mechanical plating.
  • 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, tantalum, nickel, indium, 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: 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. Carbon dioxide may be in a mixture of forms depending on the reaction time and desired structure of the patina layer.
  • Supercritical carbon dioxide has the density of a liquid but the properties of a gas. At high pressure and elevated temperature the carbon dioxide (CO 2 ) becomes dissolved in water (H 2 O). The pH of this carbonated water decreases because the chemical equilibrium CO 2 + H 2 O ⁇ H 2 CO 3 (carbonic acid) is shifted towards carbonic acid. While not wishing to be bound by theory, it appears as though carbonic acid plays an important role in dissolving metallic zinc prior to the formation of zinc carbonates. There is no carbonate formation in the absence of water or carbon dioxide. The metal that is more noble than zinc will boost the reaction since it will also cause the dissolution of metallic zinc.
  • a desired morphology of the artificially-formed patina layer such as a needle-like or ball-like structure, and/or a desired ratio of ZnCO 3 to other components of the artificially produced patina layer, such as Zn 5 (CO 3 ) 2 (OH) 6 and other zinc carbonate compounds can be tailored using different reaction times, temperatures, precursors and carbon dioxide pressures.
  • 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 patina layer.
  • the method preferably comprises at least one of the following steps: cleaning and/or roughening a surface of the product having a coating comprising zinc prior to artificially forming the patina layer on the coated surface. It is not however always necessary to clean and/or roughen the coated surface of the 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 coated surface of a 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.
  • Figure 1a shows a product 10, such as a galvanized product, which comprises a metal substrate 12, such as steel or iron, having a coating 14 comprising zinc.
  • a product 10 such as a galvanized product, which comprises a metal substrate 12, such as steel or iron, having a coating 14 comprising zinc.
  • oxygen in the air 16 illustrated as a free-flowing air flow, will react with the zinc in the galvanized surface to form zinc oxide (ZnO) 18.
  • 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 basic zinc carbonate 23 having the chemical formula Zn 5 (CO 3 ) 2 (OH) 6 .
  • a naturally formed patina 23 as illustrated in figures 1a ) 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 patina layer 23 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 patina layer 23 exposed to atmospheric elements is not formed under controlled conditions.
  • Figure 2 shows a product 10, such as a product 10 comprising iron or steel 12, i.e. an iron or steel substrate or body of any desired shape, thickness, cross-section and size having one or more surfaces that may be at least partly coated.
  • the product 10 comprises a uniform or non-uniform coating 14 containing zinc and an artificially-formed patina layer 24 that is formed on top of said coating 14, i.e. on top of at least part of said coating 14 or so as to cover the entire coating 14.
  • the artificially-formed patina layer 24 comprises zinc carbonate having the chemical formula ZnCO 3 , i.e.
  • the artificially-formed platina layer 24 comprises 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(s) as a consequence of the artificial patina formation.
  • a product 10 according to the present invention such as a hot-dip galvanized iron or steel sheet, will, on the contrary, have a coated surface comprising a patina layer 24 of better quality than a naturally formed patina layer since it has been artificially-formed under controlled conditions.
  • the artificially-formed patina 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 product 10 comprising an artificially-formed patina layer 24 according to an embodiment of the invention are illustrated in figure 3 , 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 coated surface of a product 10 prior and artificially forming the patina 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 coated surface, after galvanization for example, may be removed from the coated surface prior to artificial patination.
  • the coated surface may then be placed or moved into in a controlled environment.
  • the coated surface 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 coated surface is exposed to carbon dioxide, such as carbon dioxide having a purity of at least 99.8%, and may be heated to a temperature of at least 293 K, such as 293-343 K and 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 coated surface.
  • a solvent such as an organic solvent, such as ethanol
  • This process is easily adapted to production environments and is especially suited to complex surfaces found in grooved couplings and fittings of products 10 having a coating comprising zinc.
  • the coated surface 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 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 10 minutes or longer after the predetermined exposure time has elapsed. The rate at which the pressure is decreased will affect the structure of the artificially-formed patina layer 24.
  • the patina layer 24 will continue to form during the entire method until the coated surface 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 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 coated surface.
  • the artificially patinated product 10 may leave the factory where it is manufactured and be delivered to an end user or placed in storage.
  • the artificially-formed patina layer 24 is not water soluble and does not wash off the coated surface.
  • the at least one type of metallic ion acts as a catalyst in the formation of a patina layer 24, it speeds up the reaction time and will remain in the artificially-formed patina layer 24, which makes an artificially-formed patina layer 24 distinguishable from a naturally formed patina layer.
  • the artificially-formed patina 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 patina layer 24 will have superior properties as compared to a naturally formed patina layer since its structure will be more uniform (rather than randomly compact or porous) and it will adhere better to the underlying coated surface. Paint can be applied directly to the artificially-formed patina 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 patina 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 patina layer.
  • a naturally formed patina layer 24 may namely be non-uniform as regards its thickness and/or properties, and it may be loosely adhered to the underlying coated surface, it may be porous and contaminated with impurities.
  • the method according to the present invention may comprise the step of treating a galvanized surface 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 10 minutes.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
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Claims (13)

  1. Produit (10) présentant un revêtement (14) comprenant du zinc, et une couche de patine (24), caractérisé en ce que ladite couche de patine (24) est une couche de patine (24) formée artificiellement et comprend un carbonate de zinc présentant la formule chimique ZnCO3, ou un carbonate de zinc présentant la formule chimique ZnCO3 et un carbonate de zinc basique présentant la formule chimique Zn5(CO3)2(OH)6, selon lequel ledit carbonate de zinc présentant la formule chimique Zn5(CO3)2(OH)6 présente une structure en aiguille, et au moins un type d'ion métallique d'un métal qui est plus noble que le zinc.
  2. Produit (10) selon la revendication 1, caractérisé en ce que ladite couche de patine (24) comprend également un ou plusieurs autres composés de carbonate de zinc.
  3. Produit (10) selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que ledit revêtement (14) comprenant du zinc est appliqué en utilisant l'un des procédés suivants : la galvanisation, la galvanisation à chaud au trempé, l'électro-galvanisation, la pulvérisation, le revêtement par pulvérisation thermique, le placage mécanique.
  4. Produit (10) selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit au moins un type d'ion métallique d'un métal est un ion d'au moins l'un des éléments suivants : le cuivre, le fer, l'argent, le palladium, le platine, l'or, le titane, le molybdène, le tungstène, l'étain, le plomb, le tantale, le nickel, l'indium, le cadmium ou le béryllium.
  5. Procédé pour produire artificiellement une couche de patine (24) sur au moins une partie d'une surface d'un produit (10) présentant un revêtement (14) comprenant du zinc, caractérisé en ce que ledit procédé comprend l'étape de traitement d'au moins une partie d'une surface d'un produit (10) avec du dioxyde de carbone qui est au moins sous l'une des formes suivantes : liquide, solide, supercritique, de l'eau, et au moins un type d'ion métallique d'un métal qui est plus noble que le zinc dans des conditions contrôlées à une température, une pression et pendant une durée contrôlées afin de fournir ladite couche de patine (24) formée artificiellement sur ladite surface dudit produit (10), selon lequel ladite ladite couche de patine (24) comprend un carbonate de zinc présentant la formule chimique ZnCO3, ou un carbonate de zinc présentant la formule chimique ZnCO3 et un carbonate de zinc basique présentant la formule chimique Zn5(CO3)2(OH)6, selon lequel ledit carbonate de zinc présentant la formule chimique Zn5(CO3)2(OH)6 présente une structure en aiguille, et au moins un type d'ion métallique d'un métal qui est plus noble que le zinc, selon lequel ladite étape de traitement d'au moins une partie de ladite surface d'un produit (10) implique la soumission d'au moins une partie de ladite surface à une température d'au moins 273 K et une pression de 6-30 MPa pendant une durée d'exposition prédéterminée.
  6. Procédé selon la revendication 5, caractérisé en ce que ladite étape de traitement d'au moins une partie d'une surface d'un produit (10) comprend également l'ajout d'un tensioactif pour diminuer la tension superficielle entre ladite eau et ledit dioxyde de carbone.
  7. Procédé selon l'une quelconque des revendications 5 ou 6, caractérisé en ce qu'il est mis en œuvre dans un procédé de fabrication continue en ligne, ou en utilisant une production discontinue.
  8. Procédé selon l'une quelconque des revendications 5-7, caractérisé en ce que ladite durée d'exposition prédéterminée va d'une fraction de seconde à 60 minutes.
  9. Procédé selon l'une quelconque des revendications 5-8, caractérisé en ce que ledit revêtement (14) comprenant du zinc est appliqué en utilisant l'un des procédés suivants : la galvanisation, la galvanisation à chaud au trempé, l'électro-galvanisation, la pulvérisation, le revêtement par pulvérisation thermique, le placage mécanique.
  10. Procédé selon l'une quelconque des revendications 5-9, caractérisé en ce que ledit au moins un type d'ion métallique est un ion d'au moins l'un des suivants : le cuivre, le fer, l'argent, le palladium, le platine, l'or, le titane, le molybdène, le tungstène, l'étain, le plomb, le tantale, le nickel, l'indium, le cadmium ou le béryllium.
  11. Procédé selon l'une quelconque des revendications 5-10, caractérisé en ce que ladite eau est au moins l'une des suivantes : eau désionisée, eau du robinet, eau de mer, eau de lac.
  12. Procédé selon l'une quelconque des revendications 5-11, caractérisé en ce qu'il comprend au moins l'une des étapes suivantes : le nettoyage et/ou la rugosification d'une surface dudit produit (10) avant de former artificiellement ladite couche de patine (24) sur ladite surface dudit produit (10).
  13. Procédé selon l'une quelconque des revendications 5-12, caractérisé en ce qu'il comprend les étapes de dissolution d'un précurseur de métal comprenant ledit au moins un type d'ion métallique d'un métal qui est plus noble que le zinc et qui est non soluble dans l'eau dans un solvant et ensuite de mélange dudit solvant contenant ledit précurseur de métal avec ladite eau pour traiter ladite surface d'un produit (10).
EP17707552.0A 2016-02-25 2017-02-27 Couche de patine sur un produit galvanisé et son procédé Active EP3420114B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL17707552T PL3420114T3 (pl) 2016-02-25 2017-02-27 Warstwa patyny na galwanizowanym produkcie i sposób jej wytwarzania

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16157254.0A EP3211113A1 (fr) 2016-02-25 2016-02-25 Produit galvanisé et procédé
PCT/EP2017/054509 WO2017144721A1 (fr) 2016-02-25 2017-02-27 Couche de patine sur produit galvanisé et procédé associé

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EP3420114A1 EP3420114A1 (fr) 2019-01-02
EP3420114B1 true EP3420114B1 (fr) 2020-12-09

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

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DK (1) DK3420114T3 (fr)
ES (1) ES2853205T3 (fr)
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NL2022279B1 (en) * 2018-12-21 2020-07-15 Aquacare Europe B V Method for patinating zinc surfaces and system therefor
US12077866B2 (en) * 2019-03-08 2024-09-03 Koos Jan Baas Methods and systems for patinating zinc surfaces

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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
DE10156475A1 (de) * 2001-11-16 2003-06-05 Rheinzink Gmbh Verfahren zur Herstellung von dunklen Schutzschichten auf Flacherzeugnissen aus Titanzink

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ES2853205T3 (es) 2021-09-15
EP3211113A1 (fr) 2017-08-30
PL3420114T3 (pl) 2021-06-28
WO2017144721A1 (fr) 2017-08-31
EP3420114A1 (fr) 2019-01-02

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