Submerged underwater electroless, electrochemical deposition of metal on conductive and nonconductive surfaces

Abstract

Electroless underwater metal plating of a surface of fixed or floating structure is accomplished by transferring to the surface metal ions from a metal precursor in a solid or semisolid electrolyte that is pressed against and moved over a submerged surface. Metal ions from a metal salt blended in the solid or semisolid material plate the underwater substrate.

Claims

1. A method comprising: underwater deposition of a metal on an underwater metal substrate in an underwater environment, further comprising: blending a metal precursor and a binder, molding the blended metal precursor and the binder, forming a block of the blended metal precursor and the binder having a desired shape, extending a handle from the molded block, pressing the block underwater against the underwater substrate in presence of fresh or saltwater in the underwater environment, moving the block underwater on the underwater substrate, transferring metal ions underwater from the metal precursor to the substrate, and plating the underwater substrate with the metal from the blended metal precursor without using an electrical power supply to trigger an electrochemical reaction while applying and attaching coatings underwater.

2. The method of claim 1, wherein the blending further comprises blending a fatty acid surfactant with the metal precursor and the binder before the molding.

3. The method of claim 1, wherein the blending further comprises blending a solvent with the metal precursor and the binder before the molding.

4. The method of claim 1, wherein the substrate is a non-conductive substrate, and further comprising placing a charge on the non-conductive substrate before pressing and moving the block underwater on the non-conductive substrate.

5. The method of claim 1, wherein the substrate is a non-conductive substrate, and further comprising providing a thin conductive layer on the underwater substrate before pressing and moving the block underwater on the non-conductive substrate.

6. The method of claim 1, wherein the underwater substrate is a fixture and further comprises the metal deposition on the underwater substrate is selected from the group consisting of surface modification, selective metal coating, surface refurbishment, surface protection, corrosion and foul resistant coating.

7. The method of claim 1, wherein the underwater substrate is a floating hull and the underwater metal deposition is selected from the group consisting of electroless plating, surface modification, surface preparation, selective metal coating, surface refurbishment, surface protection, corrosion and foul resistant coating on the floating hull.

8. The method of claim 1, wherein the precursor includes metal ions.

9. The method of claim 1, wherein the precursor is a metal salt.

10. The method of claim 1, wherein the binder is a polymer.

11. The method of claim 1, wherein blending a metal precursor and a binder further comprises blending with a medium which is a solvent.

12. The method of claim 1, wherein the precursor is a metal salt selected from the group consisting of copper chloride, copper sulfate chromium chloride, chromium sulfate, nickel sulfate, nickel acetate, nickel chloride, nickel formate, zinc sulfate, organic compounds, pyridine, pyrrole, aniline, organometallic compounds, trimethylgallium, trimethylindium and trimethylaluminum.

13. The method of claim 1, wherein the substrate is a metal, a polymer or a ceramic surface.

14. The method of claim 1, wherein the binder is selecting from the group consisting of polymers, polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, silicones, inorganic binders, silicate, surfactants and cetyltrimethyl ammonium bromide.

15. The method of claim 1, further comprising: wherein the molded block is an underwater electroless metal deposition block, and the plating is electroless plating, further comprising: a solid electrolyte having metal salts, nanoparticles, organometallic precursor, polymer or ionic organic compounds with the binder having polymers, polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, silicones, inorganic binders, silicate, surfactants or cetyltrimethyl ammonium bromide.

16. The method of claim 1, wherein blending a metal precursor and a binder further comprising blending with an ionic liquid or aprotic solvent.

17. The method of claim 1, wherein the molded block is a solid or semisolid molded block.

18. The method of claim 1, wherein the substrate is metal, and the metal plating further comprises creating autonomous bimetallic currents between the underwater metal substrate and the transferring metal.

19. A method comprising: electroless plating a substrate with a metal underwater in an underwater environment by: blending a metal precursor and a polymer binder, molding the blended metal precursor and polymer binder into a block of solid or semisolid electrolyte predetermined shape, extending a handle from the molded block; pressing the block against an underwater substrate in presence of fresh or saltwater in the underwater environment, moving the block along the substrate, transferring the solid or semisolid electrolyte to the underwater substrate, and plating the underwater substrate with metal from the blended metal precursor with no electrical power supply.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a photograph of a steel coupon and a new solid electrolyte prior to underwater application of the copper coating on the steel coupon.

(2) FIG. 2 is a photograph of solid electrolyte before application on the underwater surface of the steel coupon.

(3) FIG. 3 is a photograph of submerged solid electrolyte being brushed against the underwater surface of the steel coupon, resulting in copper coating.

(4) FIG. 4 is a photograph of the steel coupon being lifted and showing the copper deposited underwater on the steel coupon using the solid electrolyte.

DETAILED DESCRIPTION

(5) FIG. 1 is a photograph of a steel coupon 10 and a new solid electrolyte 20 prior to underwater application of a copper coating on the steel coupon. One example of the invention shows a steel coupon 10 and a new solid electrolyte block 20 for coating the steel coupon 10 with copper from the solid electrolyte block 20. Block 20 is shown to be round or oval. Any shape may be used. Handle 30 extends from the solid electrolyte block 20 for holding and controlling the electrolyte block 20 as it is brushed or rubbed on the surface 12 of the steel coupon 10

(6) FIG. 2 is a photograph of solid electrolyte 20 before application on the underwater surface 12 of the steel coupon 10. The steel coupon 10 and electrolyte block 20 are submerged in seawater 40. Solid electrolyte block 20 is shown before being rubbed on to the submerged underwater surface 12 of the low carbon steel coupon 10.

(7) FIG. 3 is a photograph of solid electrolyte block 20 being rubbed or brushed on to the submerged underwater surface 12 of the steel coupon 10, resulting in copper deposition. A copper coating 22 is deposited on the surface 12 of the coupon 20, producing a copper coated surface on the coupon 10.

(8) FIG. 4 is a photograph the steel coupon 10 being lifted and showing the copper 22 deposited underwater on the steel coupon from the solid electrolyte. A copper coating 22 has been deposited on the steel coupon underwater using solid electrolyte. A copper coating 22 has been deposited on the surface of the coupon 20 which has been touched by the electrolyte block, producing a copper coated surface 24 on the coupon 10. The low carbon steel remains exposed in the part 14 of the surface which had not been brushed by the solid electrolyte block 20.

(9) A handle 30 or a handle with a rigid or flexible blade or other shaped body is embedded in the block 20 when the block is molded. In one form, fine copper precursor solution is embedded in a polymer binder, which is molded in a rigid mold or softened and formed into a desired shape, forming a block. The block is pressed and moved along a submerged underwater surface plating the surface with the copper. The electrolyte block could be composed of water soluble salts of transition metals such as copper, iron, nickel, chromium, gold, platinum, silver, etc. dispersed in a polymer solution such as polyethylene oxide, poly acrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, etc.

(10) Examples of the metal salts that could be used to make electrolyte blocks could be copper sulfate, nickel sulfate, nickel acetate, chromium trioxide, silver nitrate, hydrogen tetrachloroaurate, gold cyanide, platinum chloride, etc. The metal salt content in the electrolyte block could be from 0 to 95 weight % and remaining could be the polymer solution acting as a binder to hold the salt solution.

(11) Depending upon the electrolyte salt and content, the polymer content could also be varied from 0 to 75 weight % dispersed in water or alkaline medium (potassium hydroxide, sodium hydroxide) or in acidic medium (sulfuric acid, nitric acid, chromic acid, hydrochloric acid, etc.) and could contain additional ion conducting materials 0 to 25 weight % such as ionic liquids, e.g. 1-butyl-3-methylimidazolium chloride (BMIMC1) or ionic salts such as sodium chloride, potassium chloride, sodium sulfate as supporting electrolytes.

(12) Depending upon the nature of the metal, the electrolyte block would show a fading in color, suggesting the depletion of metal ions in the electrolyte block.

(13) The method of manufacturing these electrolyte blocks could be performed using standard polymer mixing and extrusion processes or can be blended and heated together in large polymer mixers and cast into blocks or poured into molds of any desired size and shape.

(14) This invention provides using the electrode electrolyte assemblies as well as solid or semisolid composite electrolyte materials for standard electrochemical operations on submerged underwater structures or vessels for electroplating, electropolishing, electrowinning, electrochemical etching or anodization. A simple, scalable synthetic route fabricates and uses the highly moldable, solidified electrolyte for potential use in underwater electrochemical applications, especially electroplating of submerged underwater structures and vessels, anodization, etching, etc. The novel electrode/electrolyte assemblies are used in novel underwater surface applications for the above-mentioned electrochemical procedures.

(15) Oceanit has developed revolutionary underwater treatment of submerged surfaces of the new ionic and nonionic electrolytes in moldable solid form, making the electrochemical process easily applicable on differently shaped underwater substrates.

(16) The conformable electrolyte is molded in to any desired shape for hard to reach areas to fill large cracks and crevices and to provide a uniform and smooth underwater surface finish.

(17) Oceanit's invention uses a moldable electrode/electrolyte containing the required metal ion and the ability to perform plating underwater. The underwater approach of using the moldable electrode/electrolyte also significantly improves the ability to perform plating and surface finishes operation on previously unplatable underwater surfaces.

(18) The invention uses a new solid electrolyte having precursor, binder and medium in solid or semisolid form as a tool having the product combined in an electrode/electrolyte assembly for electrochemical treatment of submerged underwater substrates. The solid electrolyte includes metal salts, nanoparticles, organometallic precursor, polymer or ionic organic compounds. The binder includes polymers polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, silicones, inorganic binders, silicate, surfactants or cetyltrimethyl ammonium bromide. The medium includes aqueous or non-aqueous solvent, ionic liquid or aprotic solvent. The solid electrolyte is a moldable or conformable solid or semisolid in moldable form.

(19) The solid electrolyte material is an electroplating, polishing, winning, etching or anodizing electrochemical, and the underwater chemical treatment includes plating, polishing, winning, chemical etching or anodization and electroless plating.

(20) The invention treats submerged underwater surfaces with a solid electrolyte block having a metal salt mixed with polymer solution as a binder solidified around a handle and formed as a solid electrolyte block with the mixed metal salt and the binder by pressing and moving the solid electrolyte block along a surface submerged underwater and plating the surfaces with a metal from the metal salt from the solid electrolyte. While the invention has been described with reference to specific embodiments, modifications and variations of the invention may be constructed without departing from the scope of the invention, which is defined in the following claims.