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WO2024172796A1 - Revêtement à efficacité anticorrosion élevée et procédé d'application dudit revêtement sur des substrats - Google Patents

Revêtement à efficacité anticorrosion élevée et procédé d'application dudit revêtement sur des substrats Download PDF

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Publication number
WO2024172796A1
WO2024172796A1 PCT/TR2023/051844 TR2023051844W WO2024172796A1 WO 2024172796 A1 WO2024172796 A1 WO 2024172796A1 TR 2023051844 W TR2023051844 W TR 2023051844W WO 2024172796 A1 WO2024172796 A1 WO 2024172796A1
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WO
WIPO (PCT)
Prior art keywords
coating
chemical
chromium
acid
prepared
Prior art date
Application number
PCT/TR2023/051844
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English (en)
Inventor
Etkin CAN
Nedim UZGUR
Huseyin AZAR
Original Assignee
Uysal Makina Sanayi Ithalat Ihracat Ve Ticaret Anonim Sirketi
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Publication date
Priority claimed from TR2023/001699 external-priority patent/TR2023001699A2/tr
Application filed by Uysal Makina Sanayi Ithalat Ihracat Ve Ticaret Anonim Sirketi filed Critical Uysal Makina Sanayi Ithalat Ihracat Ve Ticaret Anonim Sirketi
Publication of WO2024172796A1 publication Critical patent/WO2024172796A1/fr

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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • 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
    • C23C22/07—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 containing phosphates
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the invention relates to, but is not limited to, a coating with high anti-corrosive effectiveness and thin coating thickness, even in severe corrosive environments, for connecting elements in the automotive sector, and to a method for coating the said coating on a substrate product.
  • Corrosion is the deterioration and abrasion of metals and alloys thereof as a result of chemical and electrochemical reaction with the environment. The formation of corrosion occurs spontaneously at a certain speed without the need for any external energy.
  • Coating materials can be non-metal or metal (galvanizing, zinc, zinc-nickel, lead and chromium coating, tinning).
  • a film providing superficial protection is applied by processes such as coating, anodic protection methods and phosphating.
  • the thickness of the anti-corrosive coatings on the surface is increased to obtain higher corrosion resistance against aggressive chemicals and corrosive environments compared to the known coatings; however, especially in the automotive sector, it is not preferable to have too thick coatings since a high coating thickness will increase the volume of the connecting element coated, which may adversely affect the proper assembly of the connecting element. For this reason, a coating thickness in the range of a few microns is generally preferred as the coating thickness in the technical specifications.
  • the invention relates to a coating which overcomes the above-mentioned disadvantages, by increasing the anti-corrosive effectiveness of particularly metals or metal alloys exposed to severe corrosive environments.
  • the invention provides a coating with thin coating thicknesses for improving the corrosion resistance of metals or metal alloys.
  • the invention relates to a method for coating substrates with a coating with high anti-corrosive effectiveness.
  • the subject matter of the invention relates to a coating developed for substrates made of metals or metal alloys, which provides an anticorrosive effect even against severe corrosive environments and has thin coating thicknesses, and is described by way of non-limiting examples solely for a better understanding of the subject matter.
  • the phrase “corrosion” means the degradation of metals, metal alloys and similar substrates by certain mechanisms in ambient conditions.
  • the phrase “corrosion” in the invention can also refer to much more severe corrosive environments.
  • severe corrosive environments may mean environments containing ammonium nitrate, urea, potassium, diammonium phosphate, agricultural lime, ammonium thiosulfate, sodium chlorate, nitrate, ammonia, nitrogen ⁇ 28%, and atrazine.
  • anti-corrosive coatings for corrosive environments are available; however, it has been found that existing technical solutions are not particularly sufficient for connecting elements in the severe corrosive environments mentioned here.
  • the present inventors offer technical solutions and advantages to the relevant technical field, in particular for connecting elements, to provide a high anti-corrosive effect in severe corrosive environments.
  • the technical solutions and advantages realized are for connecting elements used in the automotive sector in order to further clarify the invention, the scope of protection of the invention is not limited thereto.
  • the technical solutions and advantages described in the invention can also be used in products, apparatus or elements other than connecting elements.
  • the phrase “substrate material” means products that are intended to be protected from corrosive environments and are expected to have mechanical strength and other assembly properties for the technical field in which they are used.
  • the substrate material is selected from the group consisting of metals and metal alloys, non-metals and non-metal alloys, polymers or composite materials.
  • the substrate material is a metal or metal alloy material selected from the group consisting of nickel, zinc, chromium, aluminum, vanadium, manganese, titanium, magnesium, tin, copper, iron, silicon, molybdenum or an alloy thereof.
  • the substrate material can be a connecting element or sheet metal, preferably made of metal or metal alloy. The scope of protection of the invention is not limited by the nature of the substrate.
  • the invention relates to a coating with an anti-corrosive effect to overcome technical disadvantages in the relevant technical field and to provide new technical solutions.
  • the coating according to the invention is essentially a hybrid coating.
  • the coating according to the invention comprises more than one layer and these layers show a synergistic effect when they are present together.
  • hybrid coating is used to refer to a coating in which a synergistic effect is achieved to exhibit anti-corrosive effectiveness by using separate layers with different technical effects together.
  • the coating according to the invention is preferably a hybrid coating consisting of at least two layers.
  • the coating according to the invention may be coated directly onto the substrate material.
  • the substrate material described above may be coated with a coating of any metal or metal alloy material, for example a coating containing zinc, such as zinc, zinc-nickel or zincphosphate, and the coating according to the invention may be applied on the substrate material coated with the said metal coatings.
  • a coating containing zinc, such as zinc, zinc-nickel or zinc-phosphate, which is applied to the substrate material prior to coating with the coating according to the invention, may preferably be applied to the substrate material by electrolytic coating.
  • electrolytic coating refers to a coating realized by forming a thin film layer on the surface of the substrate material by the electrolysis method.
  • electrolysis refers to the chemical changes that occur in the parts of the electrodes immersed in the liquid with the help of electrolytic conductivity by passing an electric current between two metal electrodes immersed in a salt solution or a molten salt with the help of a current source.
  • the coating according to the invention preferably comprises at least two layers. Each of these layers provides a technical solution to the final product.
  • the coating according to the invention comprises three layers, namely a bottom, a middle and a top layer.
  • the coating comprises at least one bottom layer comprising chromium or a chromium-based compound, at least one middle layer comprising phosphorus or a phosphorus-based compound and at least one top layer comprising a polymeric material.
  • the bottom and middle layers forming the coating are coated on the substrates by the electrolytic coating method.
  • chemical baths are prepared for the bottom and middle layers for performing electrolytic coating processes.
  • the substrate materials are placed in the said prepared chemical baths and subjected to coating processes.
  • the coating according to the invention comprises at least one bottom layer in contact with the substrate material surfaces and covering at least part of the bottom and/or lateral surfaces of the substrate materials.
  • the chemical bath prepared for coating the bottom layer on the substrate surface comprises at least one chromium or chromium-based compound and at least one corrosion.
  • water is preferably used in addition to the said chemical materials.
  • the said bottom layer comprises at least one chromium or chromium-based compound as the main component.
  • the bottom layer of the coating according to the invention comprises chromium or the chromium-based compound in order to delay rusting of the substrate and thereby increase its lifetime.
  • the bottom layer of the coating according to the invention comprises at least one chromium-based compound selected from the group consisting of chromic acid, chromium sulfate [Cr 2 (SC>4)2], chromium alum [KCr(SC>4)2], chromium chloride [CrC ], chromium bromide [CrBrs], chromium fluoride [CrFs], chromium (III) nitrate [CrNOs] compounds or any mixture thereof in certain ratios.
  • chromium-based compound selected from the group consisting of chromic acid, chromium sulfate [Cr 2 (SC>4)2], chromium alum [KCr(SC>4)2], chromium chloride [CrC ], chromium bromide [CrBrs], chromium fluoride [CrFs], chromium (III) nitrate [CrNOs] compounds or any mixture thereof in certain ratio
  • the bottom layer comprises at least one of chromium (III) nitrate [CrNOs] and/or chromium sulfate [Cr 2 (SC>4)2] compounds as a chromium-based compound.
  • the bottom layer comprises at least one corrosion inhibitor, if preferred.
  • the bottom layer comprises at least one compound selected from a group consisting of nitrate, sulfate and/or halogen salts as a corrosion inhibitor.
  • the bottom layer comprises at least one compound selected from a group consisting of cobalt-based nitrate, sulfate and/or halogen salts as a corrosion inhibitor.
  • the bottom layer comprises at least one of cobalt sulfate and/or cobalt nitrate compounds as a corrosion inhibitor.
  • the coating according to the invention comprises at least one middle layer.
  • the middle layer is located in contact with and in the upper vicinity of the bottom layer of the coating.
  • the chemical bath prepared for coating the middle layer of the coating according to the invention on the substrate surface comprises at least one phosphorus or phosphorus- based compound, at least one corrosion inhibitor as chemical material.
  • water is preferably used in addition to the said chemical materials.
  • the middle layer of the coating according to the invention comprises at least one phosphorus or phosphorus-based compound.
  • phosphorus or a phosphorus- based compound herein provides phosphorus ions for the middle layer when dissolved in a suitable solvent, e.g. water.
  • the middle layer comprises at least one of dihydrogen phosphate [H2PO4]", ammonium dihydrogen phosphate [(NH 4 )(H 2 PO4)], monocalcium phosphate (Ca(H 2 PC>4)2) compounds or any mixture thereof in certain ratios as phosphorus-based compound.
  • the middle layer forms a tight bond with the bottom and top layers due to the strong bonding properties of the phosphate it contains. Through this strong interaction, the middle layer prevents the passage of corrosive substances and contributes to increasing the anti-corrosive effect of the coating.
  • the phosphate contained in the middle layer of the coating according to the invention is preferably fine-grained and forms a more compact structure, preventing the interaction of the substrate with the atmosphere and contributing to the minimization of oxygen-induced rust formation.
  • the middle layer preferably comprises at least one corrosion inhibitor.
  • the middle layer comprises at least one from a group consisting of nitrate, sulfate and/or halogen salts or any mixture thereof in certain ratios as a corrosion inhibitor.
  • the middle layer comprises at least one of calcium-based nitrate, sulfate and/or halogen salts or any mixture thereof in certain ratios as a corrosion inhibitor.
  • the middle layer comprises at least one of calcium sulfate, calcium nitrate and/or cobalt nitrate compounds as a corrosion inhibitor.
  • the coating according to the invention comprises at least one top layer.
  • the top layer is located in contact with and in the upper vicinity of the middle layer of the coating according to the invention
  • a chemical mixture comprising a polymeric material is prepared for coating the top layer of the coating according to the invention on the substrate surface.
  • the said chemical mixture comprises at least one polymeric material and/or at least one anti-corrosive additive.
  • the top layer of the coating according to the invention is applied to the substrate materials as at least one layer, preferably two layers, by the dip-spin or spraying method. Accordingly, the substrate materials are immersed in tanks with the polymeric material-based chemical mixture contained in the top layer and after removal from the tanks, centrifugation is applied to ensure homogeneous distribution of the top layer on the surface of the substrate material.
  • the top layer of the coating according to the invention comprises at least one polymeric material.
  • the polymeric material in the top layer creates an anti-corrosive barrier for the substrate and preferably for the coating components thereon and also creates mechanical resistance to impact and abrasion.
  • the top layer comprises at least one polymeric material selected from the group consisting of polymers obtained from polyhydroxyethylmethacrylate, 2-methoxyl-1 -methylethyl acetate, 1 -methoxy 2-acetoxy propane, 1 -methoxy 2-propyl acetate, 1 -methoxy-2-propanol acetate, 1 -methoxylpropyl acetate, 2-acetoxy- 1 -methoxypropane, 2-propanol, 1 -methoxy acetate, Dowanol PMA glycol ether acetate, methoxy propyl acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate monomers and/
  • the said top layer comprises a polymeric material obtained from 2- methoxyl-1 -methylethyl acetate monomer as the polymeric material.
  • the polymeric material contained in the top layer of the coating according to the invention forms a composite material with the anti-corrosive additive, if preferred.
  • the top layer comprises at least one of trizinc bis(orthophosphate), zinc orthophosphate, trizinc phosphate, zinc phosphate and trizinc diphosphate, NasSC , K2CO3, CaCOs, MgO, AI2O3, SiC>2, BN, TiC>2 compounds or any mixture thereof in certain ratios as the anti-corrosive additive.
  • the said polymer-based composite material comprising the polymeric material and the anti-corrosive additive acts as an excellent protective barrier against hydrogen and oxygen as well as moisture and other gases.
  • the said polymer-based composite material also provides insulating properties to the top layer, contributing to the prevention of galvanic corrosion caused by rusting due to the electron transfer between two different materials of metal or metal alloys by preventing electron exchange.
  • the invention relates to a method for coating the characterized coating on substrate materials.
  • Each layer is coated on substrate materials by applying separate technical processes. The processes applied to coat each coating on the substrate surface are described in detail below.
  • the bottom layer is coated on the substrate materials by electrolyte coating or alternatively by the electroless coating method.
  • a chemical bath comprising the following chemical material mixture and a diluent is prepared.
  • the electroless coating method used for coating the bottom layer of the coating according to the invention on the substrate surface is the technique of coating ions obtained by autocatalytic chemical reduction method on substrate surfaces made of metal, ceramic or polymer without using electric current.
  • the temperature of the chemical bath prepared for the bottom layer is a value between 30 °C to 35 °C.
  • the substrate material is kept in the prepared chemical bath for at least 30 seconds.
  • the chemical bath prepared for coating the bottom layer of the coating according to the invention on the substrate surface comprises at least one chromium or chromium-based compound, at least one corrosion inhibitor and at least one electrolyte anodizing material as chemical material.
  • water is preferably used as a diluent in addition to the said chemical materials.
  • the coating according to the invention comprises at least one bottom layer in contact with the substrate material surfaces and covering at least part of the bottom and/or lateral surfaces of the substrate material.
  • the said bottom layer comprises chromium or a chromium-based compound as the main component.
  • the bottom layer of the coating according to the invention comprises chromium or a chromium-based compound to provide an anti-rust function in order to delay rusting of the substrate and thereby increase its lifetime.
  • the chemical bath prepared for the bottom layer of the coating according to the invention preferably comprises at least one chromium or chromium-based compound.
  • the chemical bath prepared for the bottom layer comprises chromic acid, chromium sulfate [Cr2(SO4)2], chromium alum [KCr(SO4)2], chromium chloride [CrCh], chromium bromide [CrBrs], chromium fluoride [CrFs], chromium (III) nitrate [CrNOs] compounds or any mixture thereof in certain ratios as the chromium-based compound.
  • the chemical bath prepared for the bottom layer comprises at least one of chromium (III) nitrate [CrNOs] and/or chromium sulfate [Cr 2 (SO4)2] compounds as the chromium-based compound.
  • the chemical bath prepared for coating the bottom layer of the coating according to the invention on the substrate surface comprises at least one chromium or chromium-based compound in the range of 5% to 40%, preferably 7% to 35%, more preferably 10% to 30% of the total weight of the chemical material contained therein.
  • the chemical bath prepared for the bottom layer comprises at least one corrosion inhibitor, if preferred.
  • the chemical bath prepared for the bottom layer comprises at least one compound selected from a group consisting of nitrate, sulfate and/or halogen salts as the corrosion inhibitor.
  • the chemical bath prepared for the bottom layer comprises at least one compound selected from a group consisting of cobalt-based nitrate, sulfate and/or halogen salts as the corrosion inhibitor.
  • the chemical bath prepared for the bottom layer comprises at least one of cobalt sulfate and/or cobalt nitrate compounds as the corrosion inhibitor.
  • the chemical bath prepared for coating the bottom layer of the coating according to the invention on the substrate surface comprises at least one corrosion inhibitor in the range of 1% to 20%, preferably 2% to 15%, more preferably 2.5% to 10% of the total weight of the chemical material contained therein.
  • the chemical bath prepared for the bottom layer of the coating according to the invention preferably comprises at least one electrolyte anodizing material.
  • the chemical bath prepared for the bottom layer comprises at least one of methanoic acid [HCOOH], ethanoic acid [CH 3 COOH], propanoic acid [CH3CH2COOH], butanoic acid [CH 3 (CH 2 ) 2 COOH], pentanoic acid [CH 3 (CH 2 ) 3 COOH], hexanoic acid [CH 3 (CH 2 ) 4 COOH], heptanoic acid [CH 3 (CH 2 ) 5 COOH], octanoic acid [CH 3 (CH 2 ) 6 COOH], nonanoic acid [CH 3 (CH 2 ) 7 COOH], decanoic acid [CH 3 (CH 2 ) 8 COOH], dodecanoic acid [CH 3 (CH 2 )I 0 COOH], tetradecanoic acid [CH 3 (CH 2 )I 2 COOH
  • the chemical bath prepared for coating the bottom layer of the coating according to the invention on the substrate surface comprises the electrolyte anodizing material in the range of 1% to 20%, preferably 2% to 15%, more preferably 5% to 10% of the total weight of the chemical material contained therein.
  • the chemical bath prepared for coating the bottom layer on the substrate surface comprises the chromium or chromium-based compound at a value in the range of 10% to 30%, the electrolyte anodizing material at a value in the range of 5% to 10%, and the corrosion inhibitor at a value in the range of 2.5% to 10% of the total weight of the chemical material contained therein.
  • the middle layer is coated on the substrate materials by electrolyte coating or alternatively by the electroless coating method.
  • a chemical bath comprising the chemical material mixture stated below for the middle layer and a diluent is prepared and the coating process of the middle layer is carried out for a period between 10 and 15 minutes with a bath temperature at a temperature value between 55 °C and 80 °C.
  • the electroless coating method also used for coating the middle layer on the substrate surface as in the bottom layer of the coating according to the invention is the technique of coating ions obtained by autocatalytic chemical reduction method on substrate surfaces made of metal, ceramic or polymer without using electric current.
  • the chemical bath prepared for coating the middle layer of the coating according to the invention on the substrate surface comprises at least one phosphorus or phosphorus providing compound, at least one corrosion inhibitor, at least one electrolyte salt, and at least one conductive agent as the chemical material.
  • water is preferably used as a diluent in addition to the said chemical materials.
  • the chemical bath prepared for the middle layer of the coating according to the invention comprises at least one phosphorus or phosphorus-based compound.
  • the phosphorus providing compound herein provides phosphorus ions for the middle layer when dissolved in a suitable solvent, e.g. water.
  • the chemical bath prepared for the middle layer comprises at least one of dihydrogen phosphate [H2PO4]", ammonium dihydrogen phosphate [(NH 4 )(H 2 PO4)], monocalcium phosphate (Ca(H 2 PC>4)2) compounds or any mixture thereof in certain ratios as the phosphorus-based compound.
  • the chemical bath prepared for coating the middle layer of the coating according to the invention on the substrate surface comprises at least one phosphate providing compound in the range of 5% to 75%, preferably 8% to 60%, more preferably 10% to 50% of the total weight of the chemical material contained therein.
  • the chemical bath prepared for the middle layer preferably comprises at least one corrosion inhibitor.
  • the chemical bath prepared for the middle layer comprises at least one compound selected from a group consisting of nitrate, sulfate and/or halogen salts as the corrosion inhibitor.
  • the chemical bath prepared for the middle layer comprises at least one of calcium-based nitrate, sulfate and/or halogen salts or any mixture thereof in certain ratios as a corrosion inhibitor.
  • the chemical bath prepared for the middle layer comprises at least one of calcium sulfate, calcium nitrate and/or cobalt nitrate compounds as a corrosion inhibitor.
  • the chemical bath prepared for coating the middle layer of the coating according to the invention on the substrate surface comprises at least one corrosion inhibitor in the range of 5% to 35%, preferably 8% to 30%, more preferably 10% to 25% of the total weight of the chemical material contained therein.
  • the chemical bath prepared for the middle layer comprises at least one electrolyte salt.
  • the chemical bath prepared for the middle layer preferably uses zinc- based compounds as the electrolyte salt.
  • the chemical bath prepared for the said middle layer comprises at least one of zinc nitrate, zinc chlorate, zinc sulfate, zinc phosphate, zinc molybdate, zinc chromate, zinc ricinoleate compounds or any mixture thereof in certain ratios as the electrolyte salt.
  • the chemical bath prepared for coating the middle layer of the coating according to the invention on the substrate surface comprises at least one electrolyte salt in the range of 2.5% to 10% of the total weight of the chemical material contained therein.
  • the chemical bath prepared for the middle layer comprises at least one conductive agent.
  • the chemical bath prepared for the middle layer comprises at least one of 3- (benzthiazoyl-2-thio)-propylsulfonic acid sodium salt, 3-mercaptopropane-1 -sulfonic acid sodium salt, ethylenedithiodipropylsulfonic acid sodium salt, disulfide disodium salt, bis(w-sulfobutyl)-disulfide disodium salt, bis-(w-sulfohydroxypropyl)-disulfide disodium salt, bis(w-sulfopropyl)-disulfide disodium salt, bis-(w-sulfopropyl)-sulfide disodium salt, methyl-(w-sulfopropyl) sodium salt, methyl-(w-sulfopropyl)-trisulfide disodium salt, O- ethyl-dithiocarbonic acid-S
  • the chemical bath prepared for the middle layer comprises a second electrolyte salt, if preferred.
  • the chemical bath prepared for the middle layer comprises at least one of orthophosphoric acid, oligophosphoric acids, polyphosphoric acids, cyclo- or metaphosphoric acids, branched polyphosphates, paraphosphoric acid, thiophosphoric acid, perphosphoric acid, superphosphoric acid, hyperphosphoric acid or any mixture thereof in certain ratios as the second electrolyte salt.
  • the middle layer of the coating according to the invention preferably comprises a second electrolyte salt
  • the chemical bath prepared for coating the middle layer on the substrate surface comprises a second electrolyte salt in the range of 2.5% to 5% of the total weight of the chemical material contained therein.
  • the chemical bath prepared for coating the middle layer on the substrate surface comprises phosphorus or a phosphorus-based compound at a value in the range of 10% to 50% of the total weight of the chemical material contained therein, an electrolyte salt at a value in the range of 2.5% to 10% by weight thereof, preferably a second electrolyte salt at a value in the range of 2.5% to 5% by weight thereof, a corrosion inhibitor at a value in the range of 10% to 25% by weight thereof and a conductive agent at a value between 2.5% and 10% thereof.
  • the top layer of the coating according to the invention is applied to the substrate materials as at least one layer, preferably two layers, by the dip-spin or spraying method. Accordingly, the substrate materials are immersed in tanks with the polymeric material-based chemical mixture contained in the top layer and after removal from the tanks, centrifugation is applied to ensure homogeneous distribution of the top layer on the surface of the substrate material.
  • the coating processes are carried out over a period between 90 and 270 minutes.
  • the temperature of the chemical mixture is at a temperature value between 20 °C to 45 °C.
  • the substrate material coated with the top layer is subjected to a curing process at a temperature value between 70 to 80 °C for a period between 10 to 15 minutes.
  • the top layer is applied to the substrate materials twice successively.
  • a chemical mixture comprising a polymeric material is prepared for coating the top layer of the coating according to the invention on the substrate surface.
  • the said chemical mixture comprises at least one polymeric material, at least one anti-corrosive additive, and at least one diluent.
  • the chemical mixture prepared for the top layer of the coating according to the invention comprises at least one polymeric material.
  • the polymeric material matrix component in the chemical mixture prepared for the top layer forms a composite with an anti-corrosive additive as a reinforcing component, forming an anti-corrosive barrier and also contributing to the impact and abrasion resistance of the substrate.
  • the chemical mixture prepared for the top layer comprises at least one polymeric material selected from the group consisting of polymers obtained from polyhydroxyethylmethacrylate, 2-methoxyl- 1 -methylethyl acetate, 1 -methoxy 2-acetoxy propane, 1 -methoxy 2-propyl acetate, 1 - methoxy-2-propanol acetate, 1 -methoxy-2-propyl acetate, 2-acetoxy-1 - methoxypropane, 2-propanol, 1 -methoxy acetate, Dowanol PMA glycol ether acetate, methoxy propyl acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate monomers and PGMEA, PGMA polymers or any mixture thereof in certain ratios as the polymeric material.
  • polymeric material selected from the group consisting of polymers obtained from polyhydroxyethylmethacrylate, 2-methoxyl- 1 -
  • the chemical mixture prepared for the top layer comprises a polymeric material obtained from the 2-methoxyl-1 -methylethyl acetate monomer as the polymeric material.
  • the chemical mixture prepared for coating the top layer of the coating according to the invention on the substrate surface comprises at least one polymeric material in the range of 30% to 85%, preferably 40% to 75%, more preferably 50% to 70% of the total weight thereof.
  • the chemical mixture prepared for the top layer comprises at least one anti-corrosive additive.
  • the chemical mixture prepared for the top layer comprises at least one of trizinc bis(orthophosphate), zinc orthophosphate, trizinc phosphate, zinc phosphate and trizinc diphosphate, NasSOzi, K2CO3, CaCOs, MgO, AI2O3, SiO2, BN, Ti ⁇ 2 compounds or any mixture thereof in certain ratios as the anti-corrosive additive.
  • the chemical mixture prepared for the top layer comprises trizinc bis(orthophosphate) as the anti-corrosive additive.
  • the chemical mixture prepared for coating the top layer of the coating according to the invention on the substrate surface comprises at least one anti-corrosive additive in the range of 2% to 20%, preferably 4% to 15%, more preferably 5% to 10% of the total weight thereof.
  • the chemical mixture prepared for the top layer comprises at least one diluent.
  • the said diluent in the chemical mixture prepared for the top layer is added to determine the fluidity of the chemical mixture and to perform the function of preventing early polymerization processes.
  • the top layer of the coating according to the invention comprises a diluent of between 5% to 10% of the total weight of the chemical mixture prepared for coating the top layer on the substrate surface.
  • the said chemical mixture comprises at least one diluent selected from the group consisting of ethane, propane, butane, n-alkanes such as normal- and isopentane, cycloalkanes such as cyclopentane and cyclohexane, gas plant condensates (n-alkanes, naphthenes, aromatics, etc.) or any mixture thereof in certain ratios as the diluent.
  • diluent selected from the group consisting of ethane, propane, butane, n-alkanes such as normal- and isopentane, cycloalkanes such as cyclopentane and cyclohexane, gas plant condensates (n-alkanes, naphthenes, aromatics, etc.) or any mixture thereof in certain ratios as the diluent.
  • the chemical mixture prepared for the top layer comprises at least one second diluent, if preferred.
  • the chemical mixture prepared for the top layer preferably comprises butanol as the second diluent.
  • the second diluent in the chemical mixture is also included to provide the functions of determining the fluidity of the chemical mixture and preventing early polymerization processes.
  • the chemical mixture prepared for coating the top layer of the coating according to the invention on the substrate surface comprises a second diluent of between 5% and 10% of the total weight thereof.
  • the chemical mixture prepared for the top layer comprises a third diluent, if preferred.
  • the said chemical mixture preferably comprises at least one third diluent selected from the group consisting of 1 -Cyclohexanol, cyclohexyl alcohol, hexahydrophenol, hydroxycyclohexane, hexaline or any mixture thereof in certain ratios as the third diluent.
  • the chemical mixture prepared for coating the top layer of the coating according to the invention on the substrate surface comprises a third diluent of between 5% and 10% of the total weight thereof.
  • each of the layers within the coating according to the invention provides technical solutions and advantages to the final product in order to realize the objects of the invention mentioned above.
  • the coating having a hybrid structure in this way particularly shows high anti-corrosive effects even in aggressive corrosive environments due to the layers contained therein.
  • the anti-corrosive effectiveness of a sample coating according to the invention for which the contents of the chemical baths used for coating the bottom, middle and top layers are given in Table 1 , was assayed in tests in accordance with DIN EN ISO 4628- 5 standards.
  • the results of the test performed according to the DIN EN ISO 4628-5 standard on M10 and M20 substrate material coated with a sample coating according to the said invention are given in Table 2.
  • M10 and M20 refer to the dimensions of the substrate material (connecting element) and “M” refers to the major thread diameter and the unit is millimeter.
  • the major thread diameters for the M10 and M20 substrate materials (connecting elements) used in the tests are 10 and 20 millimeters respectively.
  • the column entitled “ISO 4628-5 Classification” in T able 2 indicates the degree of rusting of the tested substrate material coated with the sample coating according to the invention when exposed to the relevant corrosive substances.
  • a range of 0-5 is given as the degree of rusting and grading is made in the range of 0-5 according to the size of the detected rust. For example, if the rust evaluated under a microscope is magnified 10 times (1 Ox) and there is no visible rust, the degree of rust is classified as 0.
  • Table 2 the substrate material coated with the sample coating according to the invention, which was tested according to DIN EN ISO 4628-5 standard, the content of which is given in Table 1 , was classified as 0 since no rust formation was observed.
  • the substrate material coated with the sample coating according to the invention for which the contents of the chemical baths used for coating the bottom, middle and top layer are given in Table 1 , was also subjected to Drop tests and it was found that the said coating showed high anti-corrosive effectiveness.
  • Table 1 the contents of the chemical baths used for coating the bottom, middle and top layers of a sample coating within the scope of the coating according to the invention are given.
  • the said coating was coated on M10 and M20 substrate material using the methods described in detail above regarding the application of the bottom layer, the middle layer and the top layer, and then tests were carried out to determine the anticorrosive effectiveness.
  • the contents described in Table 1 for the bottom layer and middle layer are the contents of the chemical baths used for coating the bottom and middle layers, and the chemical bath prepared for coating the said bottom and middle layers on the substrate preferably uses water in addition to the chemical materials.
  • a top layer a mixture of chemical materials comprising polymeric material is applied and the full content of this mixture of chemical materials is shared in Table 1 .
  • Table 1 Chemical content of the coating according to the invention. Table 2. Test results and qualitative evaluations with DIN EN ISO 4628-5 standards in various severe corrosion environments of the product obtained by coating M10 and M20 substrates with the coating material according to the invention, for which the contents of the chemical baths used for coating the bottom, middle and top layers are given in Table 1.
  • the coating according to the invention shows high anti-corrosive effectiveness even at low thicknesses. Accordingly, the coating according to the invention is able to provide the expected high anti-corrosive effectiveness even at coating ranges of between 5 to 15 microns preferred in the present art.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne, sans s'y limiter, un revêtement présentant une efficacité anticorrosion élevée dans des environnements corrosifs sévères et une épaisseur de revêtement mince pour le revêtement d'éléments de connexion utilisés dans le secteur automobile, et un procédé de d'application dudit revêtement sur le matériau de substrat.
PCT/TR2023/051844 2023-02-14 2023-12-29 Revêtement à efficacité anticorrosion élevée et procédé d'application dudit revêtement sur des substrats WO2024172796A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2023001699 2023-02-14
TR2023/001699 TR2023001699A2 (tr) 2023-02-14 Yüksek anti̇-korozi̇f etki̇nli̇ğe sahi̇p bi̇r kaplama ve bu kaplamanin substratlara kaplanmasi i̇çi̇n bi̇r yöntem

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004046264A1 (fr) * 2002-11-15 2004-06-03 Enter-Eko Sp. Z O.O. Revetement de protection pour surfaces metalliques, notamment pour tubes a parois en contact avec l'eau utilises dans des chaudieres industrielles
JP2006316342A (ja) * 2005-04-15 2006-11-24 Nippon Steel Corp 金属部材、防錆処理剤、及び防錆処理方法
US20090324938A1 (en) * 2007-01-04 2009-12-31 Henkel Ag & Co. Kgaa Conductive, organic coatings with low layer thickness and good plasticity
EP2325353A1 (fr) * 2009-10-29 2011-05-25 Van Merksteijn Quality Wire NV Procédé de production d'un fil métallique revêtu
WO2015150850A1 (fr) * 2014-04-04 2015-10-08 Arcelormittal Investigación Y Desarrollo Sl Substrat multicouche et procédé de fabrication

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004046264A1 (fr) * 2002-11-15 2004-06-03 Enter-Eko Sp. Z O.O. Revetement de protection pour surfaces metalliques, notamment pour tubes a parois en contact avec l'eau utilises dans des chaudieres industrielles
JP2006316342A (ja) * 2005-04-15 2006-11-24 Nippon Steel Corp 金属部材、防錆処理剤、及び防錆処理方法
US20090324938A1 (en) * 2007-01-04 2009-12-31 Henkel Ag & Co. Kgaa Conductive, organic coatings with low layer thickness and good plasticity
EP2325353A1 (fr) * 2009-10-29 2011-05-25 Van Merksteijn Quality Wire NV Procédé de production d'un fil métallique revêtu
WO2015150850A1 (fr) * 2014-04-04 2015-10-08 Arcelormittal Investigación Y Desarrollo Sl Substrat multicouche et procédé de fabrication

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