Anti-corrosion material-coated discrete graphene sheets and anti-corrosion coating composition containing same

Patent metadata

Field	Value
Publication number	US-11945971-B2
Application number	US-201815973651-A
Country	US
Kind code	B2
Filing date	May 8, 2018
Priority date	May 8, 2018
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

Provided is a graphene-based coating suspension comprising multiple graphene sheets, thin film coating of an anti-corrosive pigment or sacrificial metal deposited on graphene sheets, and a binder resin dissolved or dispersed in a liquid medium, wherein the multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 47% by weight of non-carbon elements wherein the non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof. The invention also provides a process for producing this coating suspension. Also provided is an object or structure coated at least in part with such a coating.

First claim

We claim:

1. A graphene-based coating suspension comprising multiple graphene sheets each having two opposed parallel surfaces, thin film coating having a thickness from 0.5 nm to 100 nm of an anti-corrosive pigment or sacrificial metal coated on and covering at least 50% area of one of said two parallel surfaces, and a binder resin dissolved or dispersed in a liquid medium, wherein said multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 47% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof and wherein said graphene sheets have a weight fraction from 0.1% to 30% based on the total coating suspension weight excluding the liquid medium, wherein said anti-corrosive pigment or sacrificial metal is selected from zinc phosphate;
wherein said binder resin contains a resin selected from urethane-urea resin, acrylic alkyd resin, polyimide, thermoset polyester, vinyl ester resin, silicate adhesive, or a combination thereof.

2. The coating suspension of claim 1 , wherein said anti-corrosive pigment or sacrificial metal covers at least 80% area of one of said parallel surfaces.

3. The coating suspension of claim 1 , wherein said non-pristine graphene material has 1% to 30% by weight of non-carbon elements selected from O, H, N, F, Cl, Br, I, B, P, or a combination thereof.

4. The coating suspension of claim 1 , wherein said conductive pigment is selected from acetylene black, carbon black, expanded graphite flake, carbon fibers, carbon nanotubes, mica coated with antimony-doped tin oxide or indium tin oxide, or a mixture thereof.

5. The coating suspension of claim 1 , wherein said chemically functionalized graphene comprises graphene sheets having a chemical functional group selected from alkyl or aryl silane, alkyl or aralkyl group, hydroxyl group, carboxyl group, amine group, sulfonate group (—SO 3 H), aldehydic group, quinoidal, fluorocarbon, or a combination thereof.

6. The coating suspension of claim 1 , wherein said chemically functionalized graphene comprises graphene sheets having a chemical functional group selected from a derivative of an azide compound selected from the group consisting of 2-azidoethanol, 3-azidopropan-1-amine, 4-(2-azidoethoxy)-4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropanoate, chlorocarbonate, azidocarbonate, dichlorocarbene, carbene, aryne, nitrene, (R-)-oxycarbonyl nitrenes, where R=any one of the following groups,

and combinations thereof.

7. The coating suspension of claim 1 , wherein said chemically functionalized graphene comprises graphene sheets having a chemical functional group selected from an oxygenated group selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde.

8. The coating suspension of claim 1 , wherein said chemically functionalized graphene comprises graphene sheets having a chemical functional group selected from the group consisting of SO 3 H, COOH, NH 2 , OH, R′CHOH, CHO, CN, COCl, halide, COSH, SH, COOR′, SR′, SiR′ 3 , Si(—OR′—) y R′ 3 -y, Si(—O—SiR′ 2 —)OR′, R″, Li, AlR′ 2 , Hg—X, TlZ 2 and Mg—X; wherein y is an integer equal to or less than 3, R′ is hydrogen, alkyl, aryl, cycloalkyl, or aralkyl, cycloaryl, or poly(alkylether), R″ is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate, and combinations thereof.

9. The coating suspension of claim 1 , wherein said chemically functionalized graphene comprises graphene sheets having a chemical functional group selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylene-tetramine (TETA), tetraethylene-pentamine (TEPA), polyethylene polyamine, polyamine epoxy adduct, phenolic hardener, non-brominated curing agent, non-amine curatives, and combinations thereof.

10. The coating suspension of claim 1 , wherein said chemically functionalized graphene comprises graphene sheets having a chemical functional group selected from OY, NHY, O═C—OY, P═C—NR′Y, O═C—SY, O═C—Y, —CR′1-OY, N′Y or C′Y, and Y is a functional group of a protein, a peptide, an amino acid, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of an enzyme substrate or is selected from R′—OH, R′—NR′ 2 , R′SH, R′CHO, R′CN, R′X, R′N + (R′) 3 X − , R′SiR′ 3 , R′Si(—OR′—) y R′ 3-y , R′Si(—O—SiR′ 2 —)OR′, R′—R″, R′—N—CO, (C 2 H 4 O—) w H, (—C 3 H 6 O—) w H, (—C 2 H 4 O) w —R′, (C 3 H 6 O) w —R′, R′, and w is an integer greater than one and less than 200.

11. An object or structure coated at least in part with a coating comprising multiple graphene sheets, thin coating of an anti-corrosive pigment or sacrificial metal deposited on graphene surfaces, and a binder resin that bonds said coated graphene sheets together and to a surface of said object or structure, wherein said multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 47% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof and wherein said graphene sheets have a weight fraction from 0.1% to 30% based on the total coating weight, wherein said anti-corrosive pigment or sacrificial metal is selected from zinc phosphate; and wherein said binder resin contains a resin selected from polyimide, thermoset polyester, vinyl ester resin, silicate adhesive, or a combination thereof.

12. The object or structure of claim 11 , wherein said coating has a thickness from 1 nm to 1.0 mm.

13. The object or structure of claim 11 , wherein said object or structure is metallic.

14. The object or structure of claim 11 , wherein said binder resin includes an ester resin, a neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid, a terephthalic acid, a urethane resin, a urethane ester resin, an acrylic resin, an acrylic urethane resin, or a combination thereof.

15. The object or structure of claim 11 , wherein said binder resin contains a curing agent and/or a coupling agent in an amount of 1 to 30 parts by weight based on 100 parts by weight of the binder resin.

16. The object or structure of claim 11 , wherein said binder resin contains a thermally curable resin containing a polyfunctional epoxy monomer selected from diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, or a combination thereof.

17. The object or structure of claim 11 , wherein said binder resin contains a thermally curable resin containing a bi- or tri-functional epoxy monomer selected from the group consisting of trimethylol

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Meng fan-chun
• Lin Yi-Jun
• Lee Shaio-Yen
• Chiu Wen Y
• Zhamu Aruna
• Jang Bor Z

Classifications

• C09D5/084 Primary

  Inorganic compounds · CPC title

• C09D149/00

  Coating compositions based on homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Coating compositions based on derivatives of such polymers · CPC title

• C09D163/00

  Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins · CPC title

• C09D175/02

  Polyureas · CPC title

• C09D175/04

  Polyurethanes · CPC title