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
  • 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
  • C23C18/16—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 reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1689—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • C23C18/16—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 reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
• • 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
  • C23C18/16—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 reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
• • 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
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/04—Electroplating: Baths therefor from solutions of chromium
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/04—Electroplating with moving electrodes
  • C25D5/06—Brush or pad plating
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/48—After-treatment of electroplated surfaces
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D7/00—Electroplating characterised by the article coated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
  • C09K2208/20—Hydrogen sulfide elimination
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
  • C09K2208/32—Anticorrosion additives
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

• the application relates generally to surface treatments and coatings to prevent scale build up and H2S and C02-induced corrosion and provide sweet gas and sour gas resistance and water/oil repellency.
• Sour gas is any gas, but often natural gas, containing significant amounts of ThS.
• ThS ThS
• Corrosion resistant alloy coatings are difficult to apply on the interior of pipelines and in inaccessible areas and the process is not scalable.
• Existing corrosion resistant coating technology lacks EbS and CO2 corrosion resistance.
• Most of the commercial solutions are based on a polymer or composite coating to prevent corrosion and H2S/CO2 attack but they provide minimal protection once the coating is damaged.
• the use of polymer-based coatings only provides a temporary resistance to these gases which is not maintained at high pressure and temperature.
• a novel corrosion resistant coating can sustain corrosion-resistance in high temperature, high pressure, corrosive, sweet or sour gas environments.
• the high-water repellency also assists in improving scale resistance and other beneficial results.
• This coating may include a base metallic corrosion resistant layer containing nickel, chromium, cobalt and/or any other corrosion resistant alloys and a top layer of polymer composite coating capable of providing a low surface energy to reduce drag in multiphase flow regimes.
• the coating is useful for oil and gas drilling and exploration, as well as for marine, aviation, automobile, electronics, domestic, construction, and transportation applications, etc.
• Benefits of the new coating include durable corrosion resistance for metal surfaces, easy application on intricate components and hard-to-reach areas, especially in pipeline, pump, and valve interiors, improved ThS and CO2 resistance, and durable performance at high pressure and high temperature.
• the coating involves a thin layer of corrosion resistant alloy coating applied to the surface using, for example, electroless, brush plating or electroplating approaches, followed by application of a composite coating of nanoparticle-embedded perfluorinated polymer that is resistant to water/oil and impermeable/inert to sweet and sour gases.
• corrosion resistant alloy coating is described in detail later.
• the top coating of the new multifunctional coating is omniphobic and may consist of fluorinated nanoparticles (such as fluorinated silica nanoparticles) in a known commercial polymer.
• Functional groups such as hydroxyl, epoxy, acrylic, amines etc may be applied to the corrosion-resistant alloy before application of the top coating to improve durability.
• Each layer has its own function- the inner, first alloy coating prevents sour gas attack, while the top composite layer functions as an oil and water repellant.
• the top layer can break down at high temperatures and pressures, leaving the surface below it exposed to the
• the multifunctional coating provides simple, scalable dual layer surface protection of H2S resistance and water and oil repellency.
• the corrosion resistant alloy layer may be used alone with sufficient strength to provide substantial corrosion protection.
• a new multifunctional coating method in embodiments includes the steps of cleaning a surface, applying a layer of corrosion-resistant alloy coating to the surface, and applying an oleo- hydrophobic composite coating over the corrosion-resistant alloy coating. In some embodiments the method also includes modifying and functionalizing the layer of corrosion-resistant alloy coating by chemical and/or electrochemical etching and attachment of functional groups, prior to application of the oleo-hydrophobic composite coating.
• the functional groups in various embodiments are hydroxyl, epoxy, acrylic, or amine functional groups.
• the surface cleaning in various embodiments includes shot blasting and/or acid/base washing.
• the corrosion-resistant alloy in various embodiments is applied by at least one of electroless plating, brush plating, and electroplating.
• the oleo-hydrophobic composite coating in some embodiments includes corrosion- resistant nanoparticles embedded in perfluorinated and/or fluorinated polymer.
• the surface in some embodiments is a metal surface, and in some embodiments part of a heat exchanger. In some embodiments the heat exchanger is located in a power plant.
• the corrosion-resistant alloy in some embodiments includes at least one of nickel, nickel- phosphorous, nickel-cobalt, nickel-boron, nickel-PTFE, and chromium.
• the oleo-hydrophobic composite coating in some embodiments includes ceramic nanoparticles embedded in a coating matrix.
• the ceramic nanoparticles in some embodiments include at least one of silica, alumina, titania, and ceria nanoparticles.
• nanoparticles in some embodiments are functionalized by attaching at least one of perfluoro octyl trichloro silane, perfluoro octyl phosphonic acid, perfluoro polyhedral oligomeric silsesquioxanes (POSS), trichloro octa decyl, trichlor octyl silane, perfluorosiloxane,
• PES perfluoro polyhedral oligomeric silsesquioxanes
• fluorohydrocarbon fluorinated silane, fluorinated acid, amine, phosphoric acid, alcohol, acrylates, epoxy, ester, ethers, sulfonate, and/or fluorinated or non-fluorinated monomers.
• the oleo-hydrophobic composite coating in some embodiments includes metallic nanoparticles embedded in the coating matrix.
• the metallic nanoparticles in some embodiments include at least one of nickel, copper, and iron nanoparticles.
• the oleo-hydrophobic composite coating in some embodiments includes perfluorinated polymers.
• a new applicator for applying a multifunctional coating to a metal surface applies the multifunctional coating according to a method involving cleaning a surface, applying a layer of corrosion-resistant alloy coating to the surface, and applying an oleo-hydrophobic composite coating over the corrosion-resistant alloy coating.
• the applicator contains the oleo-hydrophobic composite coating.
• the oleo-hydrophobic composite coating in some embodiments includes metallic nanoparticles embedded in a coating matrix.
• the method also includes modifying and functionalizing the layer of corrosion-resistant alloy coating by chemical and/or electrochemical etching and attachment of functional groups, prior to application of the oleo-hydrophobic composite coating.
• the functional groups in various embodiments are hydroxyl, epoxy, acrylic, or amine functional groups.
• the surface cleaning in various embodiments includes shot blasting and/or acid/base washing.
• the corrosion-resistant alloy in various embodiments is applied by at least one of electroless plating, brush plating, and electroplating.
• the oleo-hydrophobic composite coating in some embodiments includes corrosion-resistant nanoparticles embedded in perfluorinated and/or fluorinated polymer.
• the surface in some embodiments is a metal surface, and in some embodiments part of a heat exchanger. In some embodiments the heat exchanger is located in a power plant.
• the corrosion- resistant alloy in some embodiments includes at least one of nickel, nickel-phosphorous, nickel- cobalt, nickel -boron, nickel -PTFE, and chromium.
• the oleo-hydrophobic composite coating in some embodiments includes ceramic nanoparticles embedded in a coating matrix.
• the ceramic nanoparticles in some embodiments include at least one of silica, alumina, titania, and ceria nanoparticles.
• nanoparticles in some embodiments are functionalized by attaching at least one of perfluoro octyl trichloro silane, perfluoro octyl phosphonic acid, perfluoro polyhedral oligomeric silsesquioxanes (POSS), trichloro octa decyl, trichlor octyl silane, perfluorosiloxane,
• PES perfluoro polyhedral oligomeric silsesquioxanes
• fluorohydrocarbon fluorinated silane, fluorinated acid, amine, phosphoric acid, alcohol, acrylates, epoxy, ester, ethers, sulfonate, and/or fluorinated or non-fluorinated monomers.
• the oleo-hydrophobic composite coating in some embodiments includes metallic nanoparticles embedded in the coating matrix.
• the metallic nanoparticles in some embodiments include at least one of nickel, copper, and iron nanoparticles.
• the oleo-hydrophobic composite coating in some embodiments includes perfluorinated polymers.
• the applicator contains the corrosion-resistant alloy coating.
• a new or existing oil and gas pipe has an inner surface with a multifunctional coating applied to the inside surface, which includes an inner oleo-hydrophobic composite coating, beneath the inner oleo-hydrophobic composite coating a corrosion-resistant alloy coating, and beneath the corrosion-resistant alloy coating untreated pipe material.
• Multifunctional corrosion resistant coatings can also be applied to metallic surfaces (e.g. aluminum, copper, and/or chromium-based alloys) other than steel or stainless-steel alloys.
• metallic surfaces e.g. aluminum, copper, and/or chromium-based alloys
• FIG. l is a flowchart of a corrosion resistant multifunctional coating process, in an embodiment.
• FIGS. 2A-2E are schematics illustrating the changes occurring on a metal surface during a corrosion resistant multifunctional coating process, in an embodiment.
• FIG. 2F is a detail view of area A of FIG. 2E.
• FIG. 3 A-F are schematics illustrating the changes occurring on a metal surface during a corrosion resistant multifunctional coating process, in another embodiment.
• FIG. 3G is a detail view of area B of FIG. 3F.
• FIGS. 4A-C are a series of images showing a steel sample undergoing a corrosion resistant multifunctional coating process, in an embodiment.
• FIGS. 5 A-5B illustrate a method of applying a corrosion resistant alloy coating.
• FIG. l is a flowchart of a corrosion resistant multifunctional coating process, in an embodiment.
• the surface to be coated is cleaned 100, for example by shot blasting, acid/base washing, and/or other known techniques.
• a corrosion-resistant alloy coating is applied 102, for example using a technique such as electroless plating, brush plating,
• the corrosion-resistant alloy coating is modified and functionalized 104 using chemical and/or electrochemical etching and functional group attachment.
• a multifunctional oil/water repellant polymer composite coating is applied 106, for example corrosion-resistant nanoparticles embedded in perfluorinated polymer.
• FIGS. 2A-F are schematics illustrating the changes occurring on a metal surface 200 during a corrosion resistant multifunctional coating process, in an embodiment.
• a metal surface 200 as shown I FIG. 2A
• first that surface is cleaned 201, leaving a clean top surface 202 of the metal as shown in FIG. 2B for application of the coating.
• the corrosion resistant alloy is deposited 203 onto the clean top surface, resulting in a metal surface having a top layer of corrosion-resistant alloy 204 as shown in FIG. 2C.
• a multifunctional composite oleo-hydrophobic coating 206 is applied 207 to the corrosion-resistant alloy layer, forming the final top layer on the surface as shown in FIG. 2D.
• the final surface comprises a bottom layer of unchanged metal 200, a middle layer of corrosion-resistant alloy coating 204, and a top layer of multifunctional composite oleo-hydrophobic coating 206 as shown in FIG. 2E and detail FIG.
• FIGS. 3 A-G are schematics illustrating the changes occurring on a metal surface 200 during a corrosion resistant multifunctional coating process, in an embodiment. This schematic is similar to FIGS. 2A-F, but with the addition of a functional group attachment step shown in FIG. 3D, in which functional groups 205 are attached to the corrosion-resistant alloy as a nanoparticle coating prior to application of the multifunctional composite oleo-hydrophobic coating 206 as shown in FIG. 3E for enhanced adhesion and durability.
• FIGS. 4A-C are a series of images showing a steel sample undergoing a corrosion resistant multifunctional coating process, in an embodiment. First FIG. 4A shows a bare steel sample 400 two inches in width. Next, FIG.
• FIG. 4B shows the steel after an electroless nickel deposition has been performed on it, giving it a top layer of corrosion-resistant nickel alloy 402.
• FIG. 4C shows the steel sample with a top layer of corrosion-resistant composite coating 404 after a multifunctional composite oleo-hydrophobic coating has been applied.
• the coatings described herein may be applied to various metal surfaces in industrial environments, including, but not limited to, geometrically complex surfaces located in inaccessible or hard-to-reach areas. Such surfaces include, purely as a non limiting example, the interior and exterior surfaces of heat exchangers inside power plants. It should further be appreciated that one or more methods may be used to apply the coatings that embody the invention to a given surface, such as, for example, spraying, brushing, and the like.
• One good method of applying the corrosion resistant alloy coating is a brush plating process that involves packaging ionic and/or nonionic electrolytes, such as a copper
• electroplating solution in moldable solid form, eliminating the need for electrolyte recirculation or dipping of the brush plating wand in the electrolyte solution.
• electrolyte in a solid form, there is no need for liquid electrolytes to be used in the brush plating process. Water is sprayed on to the electrode to maintain conductivity.
• a solid electrolyte having precursor, binder and medium in solid or semisolid form and a tool having the product combined in an electrode/electrolyte assembly for electrochemical treatment of a substrate may be used.
• the solid electrolyte may include metal salts,
• the binder may include polymers polyethylene oxide, polyvinyl pyrolidone, silicones, inorganic binders, silicate, and surfactants or cetyltrimethyl ammonium bromide.
• the medium may include aqueous or non-aqueous solvent, ionic liquid or aprotic solvent.
• the solid electrolyte is a moldable or conformable solid or semisolid in moldable form.
• the electrode may be a conducting metallic or nonmetallic wire, rods, tube foil, plate, sheet, foam or mesh and further has a DC power connection to the electrode. A handle is connected to the electrode. A DC power connection also is connected to the substrate.
• the solid electrolyte material is an electroplating, electropolishing, electrowinning, electroetching or anodizing electrochemical, and the electrochemical treatment includes electroplating, electropolishing, electrowinning, electrochemical etching or anodization.
• the invention provides an ionic or nonionic electrolyte in a moldable solid or semisolid form.
• the ionic or nonionic electrolyte is a mixture of precursor, binder and medium.
• the solid electrode is formed with a mixture of electrochemical material and binder.
• the solid electrolyte may be attached to an electrode, a DC connector applied to the electrode and a handle provided on the electrode. A DC connector is applied to a substrate and the substrate is wetted with solvent. Holding the electrode and solid electrolyte with the handle and moving the solid electrolyte in contact with the wetted surface of the substrate completes the process.
• the wetting may involve spraying a solvent mist on the substrate.
• the precursor may be a metal salt, copper chloride, chromium chloride, nickel sulfate, organic compounds, pyridine, pyrrole, aniline, organometallic compounds, trimethylgallium, trimethylindium or trimethylaluminum, as examples.
• the solid electrolyte precursor and the precursors are transferred from the solid electrolyte to a surface of the substrate by using the handle to move the solid electrolyte over the surface of the substrate when the surface or the electrolyte is slightly wetted with solvent.
• a solid electrolyte containing high concentration of metal may be used which can release metal ions upon rubbing and applying electrical potential between electrode and the substrate only when the electrolyte is sufficiently hydrated. It is possible to store sufficient quantities of metal ions in the form of electrolyte and to deliver them to the necessary location as desired during the plating process.
• the solid electrolyte can be attached to the existing wand and can be covered with the cloth and brush plating, which can be performed similar to existing practices.
• Figs 5A and 5B commercial copper surfactant solution containing nearly 10wt% of copper octanoate is used without any purification.
• a known amount of a polymer binder polyethylene oxide
• copper octanoate solution in water for 30 minutes.
• the homogenized solution is poured in to plastic 2"x2"x2" cube molds and dried in a vacuum oven at 80°C for two days.
• the fabricated solid copper electrolyte polymer 1 is used for brush plating copper on steel coupons 3.
• a DC potential is applied between the steel plate 3 and a copper wand, i.e., brushing electrode 4 covered with the solid copper electrolyte 1 as shown in FIGS. 5A and 5B.
• the copper electrolyte 1 is hydrated occasionally with few drops (l-2mL) of water to maintain electrical conductivity. Alternatively, a mist of water is sprayed on the substrate. Copper is deposited on the steel plate 3 by brushing the copper electrolyte 1 over the steel plate 3.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Metallurgy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Inorganic Chemistry (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Paints Or Removers (AREA)
• Electroplating Methods And Accessories (AREA)

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• 2019
  • 2019-06-12 JP JP2021573340A patent/JP7457039B2/ja active Active
  • 2019-06-12 WO PCT/US2019/036858 patent/WO2020251573A1/en not_active Ceased
  • 2019-06-12 EP EP19933017.6A patent/EP3983579A4/de active Pending
  • 2019-06-12 KR KR1020227000092A patent/KR20220020330A/ko active Pending

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