# US 8,771,494 B2 · Synthesis of oil containing microcapsules and their use in functional composite coatings > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,771,494 B2 - Document ID: US8771494B2 - Status: Granted - Kind: B2 - Application number: 12/645,382 - Filed: 2009-12-22 - Published: 2010-06-24 - Granted: 2014-07-08 - Earliest claimed: 2008-12-22 - Assignees: Tenaris Connections Limited - Applicants: Maria Jose Churruca; Pablo Adrian Castro; Federico Jose Williams - Inventors: Maria Jose Churruca; Pablo Adrian Castro; Federico Jose Williams - Web page: https://patentgrep.com/patent/US8771494B2 ## CPC - C25D 15/00: Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires - C10M 105/36: of polycarboxylic acids - C25D 3/38: of copper - C25D 7/10: Bearings - E21B 17/042: Threaded - F16L 15/001: {with conical threads} - F16L 58/02: by means of internal or external coatings - C10M 2201/05: Metals; Alloys - C10M 2201/084: containing sulfur, selenium or tellurium - C10M 2207/2825: used as base material - C10M 2219/042: Sulfate esters - C10N 2010/02: Groups 1 or 11 - C10N 2010/14: Group 7 - C10N 2020/06: Particles of special shape or size - C10N 2050/10: semi-solid; greasy - C10N 2050/12: {Micro capsules} - C10N 2050/14: {Composite materials or sliding materials in which lubricants are integrally molded} - C10N 2080/00: Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal - C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS - F16L: PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL - C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS ## Abstract Systems and methods for the synthesis of lubricant-containing microcapsules are disclosed. Embodiments of composite nickel and copper coatings containing capsules with liquid lubricating oil cores are also disclosed. In certain embodiments, microcapsules can be incorporated into a metal plating solution to perform composite electrodeposition to obtain self lubricant metallic coatings. In some embodiments, much lower friction coefficient (˜0.8) and far better wear resistance was obtained with the copper/microcapsules composite. ## Claims ### Claim 1 A method of manufacturing a composite coating comprising: providing a mixture comprising microcapsules and electrolyte, wherein the microcapsules comprise a lubricant encapsulated within a shell, and the concentration of the microcapsules in the mixture is greater than zero and less than about 13 milliliters per liter; and electroplating a composite coating onto a threaded cathode surface using the mixture and a metal anode, wherein the composite coating comprises metal and at least some of the microcapsules, and wherein all the metal in the coating is a single element metal. ### Claim 2 (depends on 1) The method of claim 1, wherein the concentration of the microcapsules in the mixture is greater than zero and less than about 6.5 milliliters per liter. ### Claim 3 (depends on 1) The method of claim 1, wherein the concentration of the microcapsules in the mixture is greater than zero and less than about 3 milliliters per liter. ### Claim 4 (depends on 1) The method of claim 1, wherein the concentration of the microcapsules in the mixture is greater than zero and less than about 1.5 milliliters per liter. ### Claim 5 (depends on 1) The method of claim 1, wherein the electrolyte comprises CuSO4+ and H2SO4. ### Claim 6 (depends on 5) The method of claim 5, wherein the electrolyte further comprises sodium lauryl sulphate. ### Claim 7 (depends on 1) The method of claim 1, wherein a current density of about 15 to 65 mA/cm2 is used for the electroplating. ### Claim 8 (depends on 1) The method of claim 1, further comprising agitating the mixture. ### Claim 9 (depends on 8) The method of claim 8, wherein agitating the mixture includes rotating the anode. ### Claim 10 (depends on 1) The method of claim 1, wherein the cathode comprises steel. ### Claim 11 (depends on 1) The method of claim 1, further comprising plating the cathode surface with a metal prior to electroplating. ### Claim 12 (depends on 1) The method of claim 1, wherein the microcapsules are greater than about 1 μm in diameter. ### Claim 13 (depends on 1) The method of claim 1, wherein the microcapsules are manufactured by a method comprising: mixing a first solution having the lubricant and a first monomer that is soluble within the lubricant with a second solution containing water and polyvinyl alcohol to provide an emulsion with the first solution dispersed within the second solution; mixing an aqueous solution having a second monomer and an inorganic basic into the emulsion; reacting at least some of the first monomer and the second monomer together to provide a polymeric shell around the lubricant. ### Claim 14 (depends on 13) The method of claim 13, wherein the first monomer comprises terephthaloyl dichloride and the second monomer comprises diethylenetriamine. ### Claim 15 (depends on 1) The method of claim 1, wherein the cathode comprises a threaded steel pipe. ### Claim 16 (depends on 1) The method of claim 1, wherein the composite coating forms a continuous uniform coating over all of the electroplated surfaces of a plurality of threads. ### Claim 17 A method of manufacturing a composite coating comprising: providing a mixture comprising microcapsules and electrolyte, wherein the microcapsules comprise a lubricant encapsulated within a shell, and the concentration of the microcapsules in the mixture is greater than zero and less than about 13 milliliters per liter; and electroplating a composite coating onto a threaded cathode surface using the mixture and a metal anode, wherein the composite coating comprises metal and at least some of the microcapsules, and wherein all of the metal in the coating is a single element metal and has a coefficient of friction of less than about 0.8; wherein for at least the portions of the threaded cathode surface where the composite coating is electroplated, the composite coating forms a substantially continuous uniform coating over all of the surfaces of a plurality of threads with a thickness of between about 10 to 100 μM. ### Claim 18 (depends on 17) The method of claim 17, wherein the coefficient of friction of the composite coating is approximately 60% less than an electroplated coating without microcapsules. ### Claim 19 (depends on 17) The method of claim 17, wherein the coefficient of friction of the composite coating is less than about 0.2 for about 100 seconds during a ball-on-cylinder test. ### Claim 20 (depends on 17) The method of claim 17, wherein the coefficient of friction of the composite coating is less than about 0.2 for about 1000 seconds during a ring-on-disc test. ### Claim 21 (depends on 17) The method of claim 17, wherein the coefficient of friction of the composite coating lasts about ten times as long as a coefficient of friction of an electroplated coating without microcapsules during a ring-on-disc test. ### Claim 22 (depends on 17) The method of claim 17, wherein the surfaces of a plurality of threads comprise crests, roots, and flanks. ### Claim 23 (depends on 17) The method of claim 17, wherein the threaded cathode surface is an internally threaded surface. ### Claim 24 (depends on 17) The method of claim 17, wherein the threaded cathode surface is a threaded steel pipe. ### Claim 25 (depends on 17) The method of claim 17, further comprising forming a strike coating between the threaded cathode surface and the composite coating. ### Claim 26 (depends on 17) The method of claim 17, wherein the microcapsules are manufactured by a method comprising: mixing a first solution having a lubricant and a first monomer that is soluble within the lubricant with a second solution containing water and polyvinyl alcohol to provide an emulsion with the first solution dispersed within the second solution; mixing an aqueous solution having a second monomer and inorganic basic into the emulsion; reacting at least some of the first monomer and the second monomer together to provide a polymeric shell around the lubricant. ### Claim 27 (depends on 17) The method of claim 17, wherein the threaded cathode surface comprises an external diameter of between about 2 to 25 inches having between about 2 to 10 threads per inch. ### Claim 28 (depends on 17) The method of claim 17, wherein the composite coating forms a continuous uniform coating over all of the electroplated surfaces of a plurality of threads. ### Claim 29 (depends on 1) The method of claim 1, wherein the single element metal is selected from the group consisting of copper, nickel, tin, and zinc. ### Claim 30 (depends on 17) The method of claim 17, wherein the single element metal is selected from the group consisting of copper, nickel, tin, and zinc.