EP2803751A1 - Procédé d'application d'un revêtement anticorrosion - Google Patents

Procédé d'application d'un revêtement anticorrosion Download PDF

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Publication number
EP2803751A1
EP2803751A1 EP20130003971 EP13003971A EP2803751A1 EP 2803751 A1 EP2803751 A1 EP 2803751A1 EP 20130003971 EP20130003971 EP 20130003971 EP 13003971 A EP13003971 A EP 13003971A EP 2803751 A1 EP2803751 A1 EP 2803751A1
Authority
EP
European Patent Office
Prior art keywords
coating
aluminum
corrosion
corrosion coating
zinc
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Withdrawn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
EP20130003971
Other languages
German (de)
English (en)
Inventor
Werner Krömmer
Andreas Trautmann
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.)
Linde GmbH
Original Assignee
Linde GmbH
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
Priority claimed from DE102013012662.2A external-priority patent/DE102013012662A1/de
Application filed by Linde GmbH filed Critical Linde GmbH
Priority to EP20130003971 priority Critical patent/EP2803751A1/fr
Publication of EP2803751A1 publication Critical patent/EP2803751A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/087—Coating with metal alloys or metal elements only
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment

Definitions

  • the invention relates to a method for applying an anti-corrosion coating to components, wherein the anti-corrosion coating is at least partially formed as an aluminum-zinc coating; a use of a reducing gas-containing gas mixture for applying an anti-corrosion coating to components, and a use of an aluminum-zinc coating as part of an anti-corrosion coating for components.
  • a gas mixture for thermal spraying.
  • spray material is melted in the course of arc spraying in an arc and atomized into spray particles in a carrier gas.
  • a gas mixture is used as a carrier gas containing hydrogen.
  • the gas mixture contains 1 to 30% by volume of hydrogen.
  • hydrogen is used as a pure carrier gas to bind atmospheric oxygen.
  • the EP 2 186 593 A1 discloses a gas mixture comprising a mixture of argon, helium, nitrogen, carbon dioxide or hydrogen or mixtures thereof with a gaseous hydrocarbon under normal conditions.
  • the gas mixture is used inter alia for thermal spraying and / or surface treatment by means of an arc.
  • the mixtures are each used as a pure carrier gas.
  • nitrogen can be used as a carrier gas. Nitrogen reduces the oxidation of the spray particles. However, oxidation is insufficiently suppressed by the use of nitrogen, and the coatings often do not meet the quality requirements.
  • the invention has for its object to apply an anti-corrosion coating on workpieces or components, with the highest possible efficiency for the application of the anti-corrosion coating is to be made possible and oxidation of the anti-corrosion coating by the process of applying the anti-corrosion coating should be prevented.
  • an aluminum-zinc coating is used at least as part of an anti-corrosion coating.
  • This component of the anti-corrosion coating is applied by thermal spraying on the components, wherein for thermal spraying an inert carrier gas is used with a reducing gas component.
  • This coating is also referred to below as "spray-metallized coating”.
  • components are to be understood as meaning both individual components as components of larger systems or machines, as well as workpieces that are not (yet) installed in plants or machines and coated according to the invention in the course of their manufacturing process.
  • the aluminum-zinc coating goes into solution and protects the underlying material of the component, such as iron.
  • the electrochemical potential of an aluminum-zinc coating thermally sprayed with the reducing gas component is higher than that of an aluminum-zinc coating thermally sprayed without a reducing gas component, for example under conventional air.
  • the corrosion protection effect of the aluminum-zinc coating thermally sprayed with the reducing gas component is based on a combination of the cathodic protection of the aluminum-rich phases, a selective corrosion of the zinc associated with the formation of voluminous corrosion products (aluminum hydroxides and zinc hydroxides). These deposit in the pores, which increases the tightness of the coating.
  • the aluminum atoms in the outermost molecular layer are first oxidized because of their zinc-double affinity for oxygen.
  • a zinc oxide does not start at this time. It forms aluminum oxides, which are surrounded by zinc atoms.
  • zinc oxide is also formed, which is easily soluble and "flushed" out of the surface. What remains is a firmly adhering, dense and very stable aluminum oxide layer that protects the underlying aluminum-zinc coating. In addition, cathodic action can be realized across gaps in the injured aluminum-zinc coating.
  • a prerequisite for the occurrence of these anti-corrosive properties is that the applied aluminum-zinc coating is not already oxidized by the process of application and that the oxide can form on the surface to achieve its full effect.
  • each particle is already oxidized before impacting the component.
  • Aluminum-zinc coatings thermally sprayed with the reducing gas component form very pure aluminum-zinc coatings with a low oxide content.
  • Parameters of the thermal spraying determine to a greater extent the properties of the aluminum-zinc coating.
  • the choice of the nozzle system, as well as parameters such as voltage, current or the type of carrier gas influence the spray particles in the detachment of electrodes and in their flight phase and thereby the aluminum-zinc coating formed therefrom.
  • Finely atomised melt droplets mean at the same time a large specific surface and thus the promotion of the oxide content in the aluminum-zinc coating. This oxidation can be significantly reduced by using inert carrier gases with a reducing gas component.
  • a second coating in particular one or more color layers, is applied via the aluminum-zinc coating.
  • a corrosion protection system is produced from at least two layers.
  • the aluminum-zinc coating according to the invention forms the first layer, a so-called primer.
  • the second coating forms the second layer.
  • the resistance of the corrosion protection can be further increased by the interaction of the first anti-corrosion coating and the second coating.
  • the adhesion of the second coating is significantly improved by the presence of the anti-corrosion coating of the present invention, firstly compared to a "second" coating without an underlying anti-corrosion coating and secondly compared to an anti-corrosion coating which was not thermally sprayed with the reducing gas component.
  • the first layer "heals” by flowing damage, such as cracks.
  • the second layer limits this flow of the first layer so that this "healing" can take place and the loss of material from the first layer is limited by the flow.
  • an anticorrosive coating containing an injection-metallized layer applied to workpieces or components, which is in particular carried out so (process) technically that on this injection-metallized anticorrosive coating more (color) layers in downstream or upstream process steps be / were applied, so that from the interaction of spray-metallized layer and the other (color) layers, a high quality corrosion protection for the so coated workpieces or components results, which withstands the most challenging corrosive media and environmental conditions.
  • the injection-metallized layer the highest possible efficiency for application by the invention is made possible, and an oxidation of the anti-corrosion coating by the process of applying the anti-corrosion coating is prevented according to the invention.
  • hydrogen is used as the reducing gas component.
  • nitrogen is used as the carrier gas.
  • a hydrogen-nitrogen mixture is used.
  • the proportion of the reducing gas component in the gas mixture is preferably between 0.1 and 10%, in particular between 2 and 4%.
  • a gas mixture according to the EP 2 186 593 A1 is conceivable.
  • a gas mixture comprises a mixture of argon, helium, nitrogen, carbon dioxide or hydrogen or mixtures thereof with a gaseous hydrocarbon under normal conditions.
  • this gas mixture contains doping amounts of NO and / or NO 2 .
  • the mixtures are each used as a pure carrier gas.
  • an arc spraying is used for thermal spraying. In arc spraying two wires are melted in an arc and atomized by means of a carrier gas to spray particles and then transported to the component.
  • the electric arc burns between the two wires, which are formed as anode and cathode.
  • the two wires can be made of the same or different materials. Instead of wires, two metallic tubes can also be used.
  • the arc is normally generated between the two wire ends, which are fed to each other in the spray gun, by the application of a voltage with a contact ignition.
  • Cored wires can also be processed, which makes it possible to additionally apply hard-wearing layers for wear protection, which contain, for example, oxides, nitrides, carbides or borides.
  • an aluminum-zinc coating can process up to 20kg per hour.
  • Arc spraying has ideal conditions for the application of metallic anti-corrosion coating. Easy handling, use of favorable materials (through the use of wire), high application rate with high efficiency, as well as detection of large surfaces in a short time.
  • a thickness of the spray-metallized coating is preferably between 50 ⁇ m and 150 ⁇ m, in particular between 75 ⁇ m and 120 ⁇ m, more particularly 100 ⁇ m.
  • the adhesion of the spray-metallized aluminum-zinc coating is on average between 7.0 and 8.0 MPa and the adhesion of the further (paint) layers on the spray-metallized layer itself or the anti-corrosion coating on the coated material is also on average between 7, 0 and 8.0 MPa.
  • the anticorrosive coating is applied to components exposed to a seawater atmosphere (C5-M) or to a marine atmosphere (Im2), eg on oil rigs or on shore systems, and / or to components that have other corrosive chemical atmospheres (C5-I). are exposed, eg in chemical plants.
  • C5-M seawater atmosphere
  • Im2 marine atmosphere
  • the anti-corrosion coating is also suitable for components that are exposed to extreme climate, especially tropical climate, such as metallization of propane bottles for tropical climate.
  • the anti-corrosion coating is applied to components of a wind turbine, in particular an offshore wind turbine.
  • the anti-corrosion coating is particularly suitable for application to wind towers of wind turbines or offshore wind turbines.
  • the anticorrosive coating can be applied in a particularly simple manner to components that are subject to high mechanical stress, such as flanges, ribs and attachment surfaces, according to the invention. Due to the adhesive strength and the longevity of the anti-corrosion coating applied according to the invention, maintenance intervals can be kept as long as possible.
  • the invention further relates to a use of a gas mixture containing a reducing gas component for applying an anti-corrosion coating to components, and to using an aluminum-zinc coating as an anti-corrosion coating for components.
  • FIGS. 1 to 4 show the results of the laboratory tests and test series on which the invention is based.
  • a sealer is used in the pore-rich arc sprayed anti-corrosion coatings to seal the anti-corrosion coating to prevent the ingress of moisture.
  • the different anticorrosive coatings were prepared for laboratory testing in accordance with ISO 20340 with an artificial breach (Ritz) of 30mm length and 2mm width (horizontal) to simulate damage to the anticorrosive system and subjected to a 25 week cyclic aging test.
  • Assessment criteria for the quality of the different anti-corrosion coatings were the degree of corrosion of the scribe, as well as degree of blistering, degree of rust, degree of cracking, degree of exfoliation and degree of undercutting of the scribe.
  • the arc-sprayed aluminum-zinc coating with a coating thickness of 75 ⁇ m showed the best results in the tests. Red rust formed here only near the Ritz. An arc-sprayed aluminum-zinc coating with a layer thickness of 50 ⁇ m, however, begins after about 16 weeks with the formation of red rust.
  • FIG. 1 shows a component without anti-corrosion coating, which has also been subjected to the laboratory tests described above.
  • the component is coated without anticorrosive coating after 25 weeks with strong and deeply penetrating into the base material, emanating from the Ritz red rust.
  • FIG. 2 is a 75 ⁇ m thick aluminum-zinc coating shown, which was applied with air as the carrier gas by arc spraying and was also subjected to the laboratory tests described above.
  • the protective aluminum-zinc coating shows (also after 25 weeks) an improvement over the component without anti-corrosion coating FIG. 1 , Although the aluminum-zinc coating protects the flat areas of the component, the Ritz still shows strong red rust formation, which continues into the area.
  • FIG. 3 shows the using a hydrogen-nitrogen gas mixture arc sprayed aluminum-zinc coating with 75 ⁇ m layer thickness according to the invention, which has been subjected to the laboratory tests described above. It can be clearly seen that the Ritz is completely protected after 25 weeks and only slight oxide formation is present in some places.
  • FIG. 4 is a cut through the Ritz FIG. 3 shown. The almost white oxide layer on the surface washes into the defect and protects it. Also visible is the aluminum oxide layer protecting the underlying aluminum-zinc coating.
  • the different anti-corrosion coatings were subjected to tear tests to assess adhesion.
  • the bond strength is at a mean of 3.4MPa.
  • the aluminum-zinc coating applied by air as the carrier gas has an adhesive strength of 4.8 MPa.
  • the best values are achieved by the aluminum-zinc coating applied by means of the hydrogen-nitrogen gas mixture.
  • the adhesive strength of said aluminum-zinc coating is on average 7.6 MPa. The cause of these higher values is the better anchoring of the organic coating.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
EP20130003971 2013-05-16 2013-08-08 Procédé d'application d'un revêtement anticorrosion Withdrawn EP2803751A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20130003971 EP2803751A1 (fr) 2013-05-16 2013-08-08 Procédé d'application d'un revêtement anticorrosion

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102013008517 2013-05-16
EP13003229 2013-06-25
DE102013012662.2A DE102013012662A1 (de) 2013-05-16 2013-07-30 Verfahren zum Aufbringen einer Antikorrosionsbeschichtung
EP20130003971 EP2803751A1 (fr) 2013-05-16 2013-08-08 Procédé d'application d'un revêtement anticorrosion

Publications (1)

Publication Number Publication Date
EP2803751A1 true EP2803751A1 (fr) 2014-11-19

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EP20130003971 Withdrawn EP2803751A1 (fr) 2013-05-16 2013-08-08 Procédé d'application d'un revêtement anticorrosion

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0943695A1 (fr) * 1998-03-17 1999-09-22 Grillo-Werke AG Fil à base de zinc et d'aluminium et son usage en projection thermique comme protection contre la corrosion
WO2002010470A1 (fr) * 2000-07-31 2002-02-07 Linde Ag Surface plastique comportant un revetement thermo-injecte et procede de fabrication de ce revetement
DE10052404A1 (de) * 2000-10-20 2002-05-02 Rwth Aachen Inst Fuer Werkstof Verfahren und Herstellen einer Verbundstruktur mit einem zellularen Werkstück sowie mit diesem hergestellte Verbundstruktur
EP1674590A1 (fr) 2004-12-21 2006-06-28 Linde Aktiengesellschaft Utilisation d'un mélange gazeux et procédé de pulvérisation à arc électrique
EP1995345A1 (fr) * 2007-05-25 2008-11-26 InnCoa GmbH Procédé de fabrication d'une matière première résistante à de hautes températures
EP2186593A1 (fr) 2008-11-17 2010-05-19 Linde Aktiengesellschaft Mélange gazeux
DE102008057686A1 (de) * 2008-11-17 2010-05-20 Linde Aktiengesellschaft Gasgemisch

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0943695A1 (fr) * 1998-03-17 1999-09-22 Grillo-Werke AG Fil à base de zinc et d'aluminium et son usage en projection thermique comme protection contre la corrosion
WO2002010470A1 (fr) * 2000-07-31 2002-02-07 Linde Ag Surface plastique comportant un revetement thermo-injecte et procede de fabrication de ce revetement
DE10052404A1 (de) * 2000-10-20 2002-05-02 Rwth Aachen Inst Fuer Werkstof Verfahren und Herstellen einer Verbundstruktur mit einem zellularen Werkstück sowie mit diesem hergestellte Verbundstruktur
EP1674590A1 (fr) 2004-12-21 2006-06-28 Linde Aktiengesellschaft Utilisation d'un mélange gazeux et procédé de pulvérisation à arc électrique
EP1995345A1 (fr) * 2007-05-25 2008-11-26 InnCoa GmbH Procédé de fabrication d'une matière première résistante à de hautes températures
EP2186593A1 (fr) 2008-11-17 2010-05-19 Linde Aktiengesellschaft Mélange gazeux
DE102008057686A1 (de) * 2008-11-17 2010-05-20 Linde Aktiengesellschaft Gasgemisch

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