JP7447021B2 - Discrete graphene sheet coated with anti-corrosion material and anti-corrosion coating composition containing the same - Google Patents

Description

CROSS-REFERENCES TO RELATED APPLICATIONS This application is filed in U.S. Patent Application No. 15/973,651, filed on May 8, 2018; No. 656, the contents of each of which are incorporated herein by reference for all purposes.

FIELD The present disclosure relates generally to the field of anticorrosive coatings, and specifically to graphene-enabled coating compositions and methods of use thereof.

Background Corrosion of metallic materials is an expensive problem. For example, the cost of problems caused by corrosion accounts for 2% to 5% of the annual gross domestic product (GDP) of the United States.

Corrosion occurs in both ferrous metals (eg, iron and steel) and non-ferrous metals (eg, aluminum, copper, etc.). These metal materials are commonly used in marine and offshore structures, bridges, containers, refineries, power plants, storage tanks, cranes, wind turbines, airports, petrochemical equipment, etc.

Corrosion-resistant coatings protect metal components from deterioration due to moisture, salt spray, oxidation, or exposure to various environmental or industrial chemicals. Anticorrosion coatings allow protection of metal surfaces and act as a barrier to contact between corrosive substances and the metal substrate to be protected. In addition to corrosion protection, many coatings also offer improved abrasion resistance, non-stick performance and chemical protection. A coating with anti-corrosion properties ensures the longest possible service life of the metal component.

As an example, anticorrosive coatings for protecting steel structures include zinc primers, where zinc is used as a conductive pigment to form the anode active coating. The zinc acts as a sacrificial anode material that protects the steel substrate that becomes the cathode. Resistance to corrosion appears to depend on the transmission of galvanic current by the zinc primer, and if the system remains conductive and enough zinc is present to act as an anode, the steel substrate will still be sensitive to direct current. protected. To meet these demands, zinc primers are typically formulated to include high loadings of zinc particles (e.g., up to 80% zinc by weight) such that the zinc pigment particles in the zinc primer are in close contact with each other. Densely packed. However, high zinc usage can result in very difficult dispersion of the solid contents in the liquid medium, difficulty in applying the primer onto the steel surface to be protected, and excessively thick and dense coatings. and high cost. Other coating systems for protecting other types of metal structures also have significant drawbacks.

Therefore, the development of improved corrosion protection coatings remains highly desirable. One particular object of the present disclosure is a new coating system that requires lower amounts of anode or sacrificial material.

SUMMARY The present disclosure provides a plurality of graphene sheets each having two opposite parallel surfaces (also referred to as major surfaces) and a corrosion protection coating covering at least 50% of the area of one of the two parallel surfaces and covering the same. A graphene-based coating suspension comprising a thin film coating of a pigment or sacrificial metal (having a thickness of 0.5 nm to 500 nm) and a binder resin dissolved or dispersed in a liquid medium, comprising: The graphene sheets are essentially single-layer or few-layer graphene sheets selected from pure graphene materials with 0% non-carbon elements or impure graphene materials with 0.001 wt.% to 47 wt.% non-carbon elements. Impure graphene includes graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, doped graphene, chemically functionalized graphene or combinations thereof. A graphene-based coating suspension selected from: Preferably, the graphene sheets have a weight fraction of 0.1% to 30% based on the total coating suspension weight excluding liquid medium. The impure graphene material can have from 1% to 30% by weight of non-carbon elements selected from O, H, N, F, Cl, Br, I, B, P or combinations thereof.

In certain embodiments, the anticorrosive pigment or sacrificial metal is selected from aluminum, chromium, zinc, beryllium, magnesium, alloys thereof, zinc phosphate, or combinations thereof. Such anti-corrosion material forms a thin coating layer deposited on one or both major surfaces of the graphene sheet. Such thin coatings are preferably deposited on single layer graphene sheets (0.34 nm thick) or on multilayer graphene sheets (approximately 0.68 nm to 3.4 nm thick) to a thickness of 1 nm to 100 nm. has. Both the graphene sheets and the anti-corrosion material coated on their surface are very thin. Anti-corrosion coating compositions comprising graphene sheets coated with these ultra-thin anti-corrosion materials are surprisingly effective in protecting metal surfaces against corrosion, with separate graphene sheets and discrete particles of anti-corrosion pigments or metals. and are separately dispersed in a liquid medium to form a coating suspension.

The binder resin is preferably a resin selected from epoxy resins, polyurethane resins, urethaneurea resins, phenolic resins, acrylic resins, alkyd resins, polyimides, thermosetting polyesters, vinyl ester resins, silicate adhesives or combinations thereof. can be included.

As will be apparent to those skilled in the art, the coating suspension may further include other coating/coating components. Examples of such ingredients are fillers, additives (e.g. surfactants, dispersants, defoamers, catalysts, promoters, stabilizers, coalescing aids, thixotropic agents, antisettling agents and dyes), coupling agents. agent, filler, conductive pigment, electronically conductive polymer, or a combination thereof. In this case too, the coating suspension does not contain microspheres such as glass, ceramic or polymers.

The conductive pigment may be selected from acetylene black, carbon black, expanded graphite flakes, carbon fibres, carbon nanotubes, mica coated with antimony doped tin oxide or indium tin oxide or mixtures thereof.

The electronically conductive polymer is preferably polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), polyheteroarylene vinylene (PArV) (herein , the heteroarylene group may be thiophene, furan or pyrrole), poly-p-phenylene (PpP), polyphthalocyanine (PPhc), etc., and derivatives thereof and combinations thereof.

In some embodiments, the chemical functional groups attached to the functionalized graphene sheets include alkyl or aryl silanes, alkyl or aralkyl groups, hydroxyl groups, carboxyl groups, amine groups, sulfonate groups (-SO ₃ H), aldehyde groups. , quinoids, fluorocarbons or combinations thereof.

Alternatively, the functional groups attached to the graphene sheets are 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-)-oxycarbonylnitrene (where R = the following group)
) and combinations thereof.

In certain embodiments, the functional group is selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde. In some embodiments, the functionalizing agent is 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 y is an integer of 3 or less, R' is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly(alkyl ether), and R'' is fluoroalkyl , fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate and combinations thereof.

Functional groups include amidoamine, polyamide, aliphatic amine, modified aliphatic amine, alicyclic amine, aromatic amine, anhydride, ketimine, diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA). , polyethylene polyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated hardeners, non-amine hardeners, and combinations thereof.

In some embodiments, the functional groups are OY, NHY, O=C-OY, P=C-NR'Y, O=C-SY, O=C-Y, -CR'1-OY, N' selected from Y or C'Y, and Y is a functional group of a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or transition state analog of an enzyme substrate; or 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 selected from 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 1 An integer greater than 200 and less than 200.

The present disclosure relates to an object or structure comprising a plurality of graphene sheets, particles of an anti-corrosion pigment or sacrificial metal, and an aqueous binder resin, the graphene sheets and the particles of an anti-corrosion pigment or sacrificial metal being bonded to each other and the particles of the sacrificial metal. There is also provided an object or structure at least partially coated with a coating comprising an aqueous binder resin bonded to a surface of the object or structure, wherein the plurality of graphene sheets are pure graphene having essentially 0% non-carbon elements. The impure graphene includes graphene oxide, reduced graphene oxide, graphene fluoride. selected from graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene or combinations thereof, the coating is dispersed in a silicate binder or Contains no microspheres.

The anti-corrosion pigment or sacrificial metal in the coating may be selected from aluminum, chromium, zinc, beryllium, magnesium, alloys thereof, zinc phosphate or combinations thereof. The coating applied onto an object or structure typically has a thickness of 1 nm to 10 mm, typically 10 nm to 1 mm. In some embodiments, the object or structure is metal.

Coatings applied over objects or structures include ester resins, neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid, terephthalic acid, urethane resins, urethane ester resins, urethane urea resins, acrylic resins, acrylics. An aqueous binder resin selected from urethane resins or combinations thereof can be included.

The aqueous binder resin may contain 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.

In the case of coatings applied onto objects or structures, the aqueous binder resin may be diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether or the like. The thermosetting resin may include a polyfunctional epoxy monomer selected from a combination of the following.

In some embodiments, the aqueous binder resin includes trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylmethane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylolethane triglycidyl ether, Glycidyl ether, tetraphenylolethane tetraglycidyl ether, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, Castor oil triglycidyl ether, propoxylated glycerin triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol diglycidyl ether , polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl carboxylate, derivatives thereof and mixtures thereof. thermoplastic resins comprising di- or trifunctional epoxy monomers selected from the group consisting of:

In some embodiments, the aqueous binder resin comprises acrylate and methacrylate oligomers, (meth)acrylates (acrylates and methacrylates), polyhydric alcohols having (meth)acrylate functional groups and their derivatives, such as ethoxylated trimethylolpropane tri(meth) ) acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylate, 1,6-hexanediol di(meth)acrylate or neopentyl glycol di(meth)acrylate and mixtures thereof and low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, UV radiation curable resins or lacquers selected from acrylate and methacrylate oligomers derived from epoxy acrylates, polybutadiene resins and polythiol-polyene resins.

In some embodiments, the object or structure is a metallic reinforcing material or member. The object or structure may be a concrete structure, a bridge.

The present disclosure provides a method for inhibiting corrosion of a structure or object having a surface comprising: (i) a plurality of graphene sheets coated with a thin film of an anticorrosion pigment or sacrificial metal having a thickness of 0.5 nm to 1 μm; , a resin binder dispersed or dissolved in a liquid medium; (ii) removing at least a portion of the liquid medium from the coating suspension at the end of the coating step; and forming a protective coating layer on the surface.

Preferably, the protective coating layer comprises graphene sheets coated with an anticorrosive pigment or sacrificial metal that are aligned substantially parallel to each other and parallel to the surface of the structure or object to be protected. Such orientation of the coated graphene sheets can be achieved by any of a variety of coating or casting procedures, including ultrasonic atomization, air-assisted atomization, or the application of shear stress to the coating suspension upon contact with the surface. For example, this can be achieved by using comma coating, slot die coating, reverse roll coating, etc.).

In this method, the anticorrosive pigment or sacrificial metal is selected from aluminum, chromium, zinc, beryllium, magnesium, alloys thereof, zinc phosphate or combinations thereof. In this method, the water-based binder resin is preferably a water-soluble or water-dispersible epoxy resin, a water-soluble or water-dispersible polyurethane resin, a water-soluble or water-dispersible phenolic resin, a water-soluble or water-dispersible acrylic resin, or a water-soluble or water-dispersible epoxy resin. water-based thermosetting resins selected from resins, water-soluble or water-dispersible alkyd resins, or combinations thereof. The impure graphene material preferably has from 1% to 30% by weight of non-carbon elements selected from O, H, N, F, Cl, Br, I, B, P or combinations thereof. This method includes carriers, fillers, dispersants, surfactants, defoamers, catalysts, promoters, stabilizers, coalescing aids, thixotropic agents, antisettling agents, colored dyes, coupling agents, extenders, conductive It can further include pigments, electronically conductive polymers, or combinations thereof.

The present disclosure also provides a method of making a graphene-based coating suspension comprising discrete graphene sheets coated with an anticorrosion material dispersed in a liquid medium (e.g., an organic solvent). The method includes (a) providing a continuous film of graphene sheets in a deposition zone; (b) introducing vapors or atoms of a precursor of an anticorrosive pigment or metal into the deposition zone; (c) mechanically applying the coating film to a plurality of pieces of the graphene sheet coated with the anti-corrosion material; (d) dispersing a plurality of pieces of graphene sheets coated with an anticorrosive material and a binder resin in a liquid medium to form a coating suspension.

In this method, a continuous film of graphene material is produced by spraying a graphene suspension onto a solid substrate, the graphene suspension comprising sheets of graphene material dispersed in a liquid medium. and by removing the liquid medium. In some embodiments, this continuous film of graphene sheets is formed by chemical vapor deposition of graphene material onto a solid substrate.

Preferably, the coating film has an anti-corrosion active material coating thickness of less than 100 nm.

In some embodiments, step (b) of forming a coating film of graphene sheets coated with an anti-corrosion material comprises chemical vapor deposition, physical vapor deposition, sputtering or laser assisted thin film deposition of an anti-corrosion pigment or metal onto the film of graphene sheets. Accompany.

Mechanically disrupting step (c) may involve air jet milling, impact milling, grinding, mechanical shearing, sonication, or combinations thereof.

In some embodiments, step (a) of providing a continuous film of graphene material includes feeding the continuous film from a feed roller into a deposition zone, and step (b) includes rolling a coated film. Further comprising collecting on a pick up roller.

Brief description of the drawing
1 is a flowchart showing the most commonly used method for producing graphene oxide sheets, involving chemical oxidation/intercalation, washing and high temperature exfoliation steps. This is a method of manufacturing a graphene sheet coated with an anti-corrosion material. Figure 2: Polarization current density versus voltage (electrochemical potential) for four anticorrosive coating compositions.

Description of Preferred Embodiments The present disclosure provides graphene-based coating suspensions for use in protecting metal surfaces against corrosion or oxidation. This coating suspension can be applied to the metal substrate surface as a primer, intermediate coating layer or surface coating layer (top coating layer).

In some embodiments, the coating suspension comprises a plurality of graphene sheets (coated with a thin coating layer of anticorrosion pigment or sacrificial metal) and a plurality of graphene sheets dissolved or dispersed in a liquid medium (e.g., an organic solvent or water). and a binder resin. Each graphene sheet has two opposing parallel surfaces (or "major surfaces"). In some embodiments, at least 50% of one of the two major surfaces is covered with a thin coating of anticorrosion pigment or sacrificial metal. This thin coating of anticorrosive material preferably has a thickness of 0.5 nm to 1 μm, more preferably 1 nm to 500 nm, most preferably 5 nm to 100 nm. Graphene sheets coated with anti-corrosion materials are discrete and discrete sheets with typical lengths or widths of 10 nm to 10 μm. The graphene sheets themselves (before being coated with anticorrosive pigments or metals) typically have a thickness of 0.34 nm to about 3.4 nm.

The plurality of graphene sheets are monolayer or few-layer graphene selected from pure graphene materials with essentially 0% non-carbon elements or impure graphene materials with 0.001 wt.% to 47 wt.% non-carbon elements. Impure graphene sheets include graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, doped graphene, chemically functionalized graphene or the like. selected from combinations. The impure graphene material can have from 1% to 30% by weight of non-carbon elements selected from O, H, N, F, Cl, Br, I, B, P or combinations thereof. Preferably, the coating suspension does not contain microspheres as fillers (such as glass, ceramic and polymeric microspheres). In some embodiments, the coating suspension does not include a silicate binder.

In a preferred or typical coating composition (on removal of the liquid medium), the resulting solid content is 0.1% to 30% by weight graphene sheets and 1% by weight coated on the surface of the graphene sheets. % to 70% by weight (preferably 5% to 60%, more preferably 10% to 40%) of an anticorrosive pigment or sacrificial metal and 1% to 10% by weight of a binder resin. Naturally, the sum of these three types must be 100% no matter how they are blended.

The present disclosure also provides a method of making a graphene-based coating suspension comprising discrete graphene sheets coated with an anticorrosion material dispersed in a liquid medium (e.g., an organic solvent). The method includes (a) providing a continuous film of graphene sheets in a deposition zone; (b) introducing vapors or atoms of a precursor of an anticorrosive pigment or metal into the deposition zone; (c) mechanically applying the coating film to a plurality of pieces of the graphene sheet coated with the anti-corrosion material; (d) dispersing a plurality of pieces of graphene sheets coated with an anticorrosive material and a binder resin in a liquid medium to form a coating suspension. Preferably, the coating film has an anti-corrosion active material coating thickness of less than 100 nm.

In this method, a continuous film of graphene sheets is produced by spraying a graphene suspension onto a solid substrate, the graphene suspension comprising sheets of graphene material dispersed in a liquid medium. and by removing the liquid medium. This liquid medium may be the same or different from the liquid medium of the final coating suspension. In some embodiments, this continuous film of graphene sheets is formed by chemical vapor deposition of graphene material onto a solid substrate. In some embodiments, step (a) of providing a continuous film of graphene material includes feeding the continuous film from a feed roller into a deposition zone, and step (b) includes rolling a coated film. Further comprising collecting on a pick up roller.

In some embodiments, step (b) of forming a coating film of graphene sheets coated with an anti-corrosion material comprises chemical vapor deposition, physical vapor deposition, sputtering or laser assisted thin film deposition of an anti-corrosion pigment or metal onto the film of graphene sheets. Accompany. Mechanically disrupting step (c) may involve air jet milling, impact milling, grinding, mechanical shearing, sonication, or combinations thereof.

Conventional anticorrosive coatings for protecting steel structures typically include zinc primers, where zinc is used as a conductive pigment to form the anode active coating. The steel or iron substrate to be protected functions as a cathode. Zinc acts as a sacrificial anode material that protects the steel or iron substrate. Resistance to corrosion appears to rely on galvanic current transfer by the zinc primer. If the electronic conduction path of the system is maintained and enough zinc is present to act as an anode, the steel substrate will still be protected by direct current. Unfortunately, zinc primers are typically formulated to include high loadings of zinc particles (eg, up to 80% by weight zinc). High zinc usage can result in very difficult dispersion of the solid contents in the liquid medium, difficulty in applying the primer onto the steel surface to be protected, excessively thick and dense coatings and means cost. Other coating systems for protecting other types of metal structures also have significant drawbacks.

In the present disclosure, we have surprisingly increased the Zn amount from 80 wt.% to 20 wt.% without compromising the anti-corrosion ability by adding 1 wt.% of selected functionalized graphene into the zinc primer. % (the amount of Zn is reduced to one-fourth). This is a significant improvement in performance and is completely unexpected. It is surprising and unprecedented that 1% by weight graphene can completely replace 60% by weight zinc.

In addition to (or as an alternative to) zinc, we also combined other elements or compounds such as aluminum, chromium, beryllium, magnesium, alloys thereof, zinc phosphate or combinations thereof with graphene sheets. It was further confirmed that it can be used as an anticorrosive pigment or as a sacrificial metal. Small amounts of graphene (typically 0.1% to 10% by weight) can be used to replace up to 70% by weight of these anticorrosive pigment materials.

The water-based binder resin is preferably a water-soluble or water-dispersible epoxy resin, a water-soluble or water-dispersible polyurethane resin, a water-soluble or water-dispersible phenol resin, a water-soluble or water-dispersible acrylic resin, or a water-soluble or water-dispersible acrylic resin. or a water-based thermosetting resin selected from water-dispersible alkyd resins or combinations thereof.

As will be apparent to those skilled in the art, the coating suspension may further include other coating/coating components. Examples of such ingredients are fillers, additives (e.g. surfactants, dispersants, defoamers, catalysts, promoters, stabilizers, coalescing aids, thixotropic agents, antisettling agents and dyes), coupling agents. agent, filler, conductive pigment, electronically conductive polymer, or a combination thereof. In this case too, the coating suspension does not contain microspheres such as glass, ceramic or polymers as fillers or additives.

The conductive pigment may be selected from acetylene black, carbon black, expanded graphite flakes, carbon fibres, carbon nanotubes, mica coated with antimony doped tin oxide or indium tin oxide or mixtures thereof.

The electronically conductive polymer is preferably polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), polyheteroarylene vinylene (PArV) (herein , the heteroarylene group may be thiophene, furan or pyrrole), poly-p-phenylene (PpP), polyphthalocyanine (PPhc), etc., and derivatives thereof and combinations thereof.

The coating suspension is prepared by combining the graphene sheets (to be coated with anti-corrosion pigment or sacrificial metal) and binder resin in a liquid medium using well-known methods and equipment, e.g. using a disperser/mixer/homogenizer or a sonicator. It can be easily produced by dispersing/mixing in

The coating suspension can be applied onto the substrate surface using one of the many well known coating/application methods such as air assisted spraying, ultrasonic spraying, painting, printing and dip coating. In some embodiments, the coated graphene sheets and binder are applied to the surface of the metal component by simply dipping or dipping the metal component into a graphene-based coating suspension and then removing the components from the graphene dispersion. The graphene sheets can be deposited onto the metal surface, where the graphene sheets are bonded to the metal surface to form a layer of bonded graphene sheets. Alternatively, the coating suspension can simply be sprayed onto the surface of the metal component, allowing the liquid medium components to evaporate and the binder resin to cure or solidify.

The binder resin can be formed from an adhesive composition that includes an adhesive resin as a major component. The adhesive resin composition can contain a curing agent and a coupling agent along with the adhesive resin. Examples of adhesive resins include ester resins, urethane resins, urethane ester resins, acrylic resins and acrylic urethane resins, in particular ester resins containing neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid and terephthalic acid. Can be done. The curing agent may be present in an amount of 1 to 30 parts by weight based on 100 parts by weight adhesive resin. Examples of coupling agents include epoxysilane compounds.

Curing of this binder resin can be done by heat, UV or ionizing radiation. This involves subjecting the thermosetting composition to a temperature of at least 70°C, preferably from 90°C to 150°C, for at least 1 minute (typically up to 2 hours, more typically 2 hours) to form a hard coating layer. (minutes to 30 minutes).

Dipping, coating (e.g. doctor blade coating, bar coating, slot die coating, comma coating, reverse roll coating, etc.), roll-to-roll process, inkjet printing, screen printing, microcontact, gravure coating, spray coating, ultrasonic spray coating , electrostatic spray coating and flexographic printing can be used to contact the surface of the metal member with the graphene dispersion. The thickness of the hard coating layer is generally about 1 nm to 1 mm, preferably 10 nm to 100 μm, most preferably 100 nm to 10 μm.

In the case of thermosetting resins, the polyfunctional epoxy monomers are preferably diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether (e.g. erythritol tetraglycidyl ether) or combinations thereof. Di- or trifunctional epoxy monomers include trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, and tetraphenylolethane triglycidyl ether. Ether, tetraglycidyl ether of tetraphenylolethane, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerin triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol diglycidyl ether, The group consisting of polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl carboxylate, derivatives thereof and mixtures thereof can be selected from.

In certain embodiments, the thermosetting compositions of the present disclosure advantageously further comprise a small amount, preferably 0.05-0.20% by weight, of at least one surface-active compound. Surfactants are important to obtain a sufficient final hard coating by good wetting of the substrate.

UV radiation curable resins and lacquers that can be used in the binder resins of the present disclosure include the multifunctional compounds acrylate and methacrylate oligomers (as used herein, the term "(meth)acrylate" refers to acrylates and methacrylates). ), e.g. polyhydric alcohols with (meth)acrylate functionality and their derivatives, e.g. ethoxylated trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol Di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate or neopentyl glycol di(meth)acrylate Derived from acrylates and mixtures thereof and low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, epoxy acrylates, polybutadiene resins, polythiol-polyene resins, derivatives thereof and combinations thereof. They are derived from photopolymerizable monomers and oligomers such as acrylate and methacrylate oligomers.

The UV polymerizable monomers and oligomers are coated (eg, after being removed from immersion), dried, and subsequently exposed to UV radiation to form an optically clear, crosslinked, wear-resistant layer. A preferred UV curing dose is 50-1000 mJ/cm ² .

UV curable resins are also typically ionizing radiation curable. Ionizing radiation curable resins can include relatively large amounts of reactive diluents. Reactive diluents that can be used herein include monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, vinyltoluene and N-vinylpyrrolidone, as well as polyfunctional monomers such as trifunctional monomers. Methylolpropane tri(meth)acrylate, hexanediol(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1, Examples include 6-hexanediol di(meth)acrylate or neopentylglycol di(meth)acrylate.

The aforementioned binder resins are usually solvent-based and are initially soluble in organic solvents (prior to curing or crosslinking). However, most of the monomers or polymers in these binder resins (before curing) can be made water soluble or dispersible by chemical modification (e.g. carboxylation, hydroxylation or some functionalization). can become. These then become components of the aqueous coating system. There are commercially available inherently water-soluble or water-dispersible resin systems.

The preparation of graphene sheets and graphene dispersions is described as follows: carbon can be diamond, fullerene (0D nanographite material), carbon nanotubes or carbon nanofibers (1D nanographite material), graphene (2D nanographite material). ) and graphite (3D graphite materials). Carbon nanotubes (CNTs) refer to tubular structures grown in a single or multilayer structure. Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have diameters on the order of several nanometers to several hundred nanometers. These longitudinal hollow structures impart unique mechanical, electrical and chemical properties to the material. CNTs or CNFs are one-dimensional nanocarbon or 1D nanographite materials.

Our research group pioneered the development of graphene materials and related manufacturing methods in 2002: (1) B. Z. Jang and W. C. Huang, “Nano-scaled Graphene Plates,” U.S. Pat. No. 7,071,258 (07/04/2006), filed October 21, 2002; (2) B. Z. Jang, et al. “Process for Producing Nano-scaled Graphene Plates”, U.S. Patent Application Publication No. 10/ No. 858,814 (06/03/2004) (U.S. Patent Application Publication No. 2005/0271574); and (3) B. Z. Jang, A. Zhamu, and J. Guo, “Process for Producing Nano-scaled Platelets and Nanocomposites” , U.S. Patent Application Publication No. 11/509,424 (08/25/2006) (U.S. Patent Application Publication No. 2008-0048152).

Single-layer graphene sheets are composed of carbon atoms occupying a two-dimensional hexagonal lattice. Multilayer graphene is a platelet composed of two or more graphene planes. Individual single-layer graphene sheets and multi-layer graphene platelets are collectively referred to herein as nanographene platelets (NGPs) or graphene materials. NGPs include pure graphene (substantially 99% carbon atoms), slightly oxidized graphene (<5 wt% oxygen), graphene oxide (≧5 wt% oxygen), slightly fluorinated graphene (<5 wt% fluorine), fluorinated graphene (≧5 wt% fluorine), other halogenated graphenes, and chemically functionalized graphenes.

NGP is known to have a unique set of physical, chemical and mechanical properties. For example, graphene has been found to exhibit the highest intrinsic strength and highest thermal conductivity of any existing material. Graphene's practical applications in electronic devices (e.g., replacing Si as a key element in transistors) are not expected to materialize within the next 5 to 10 years, but it is expected to be used in composite materials and in electrode materials for energy storage devices. Its application as a nanofiller is imminent. The availability of large quantities of processable graphene sheets is important for the successful development of composites, energy and other applications of graphene.

Methods for the production of NGP and NGP nanocomposites have been recently reviewed by the present inventors [Bor Z. Jang and A Zhamu, “Processing of Nano Graphene Platelets (NGPs) and NGP Nanocomposites: A Review,” J. Materials Sci. 43 (2008) 5092-5101].

A very useful method (Figure 1) uses an intercalant and an oxidizing agent (e.g. concentrated sulfuric acid and nitric acid, respectively) to obtain a graphite intercalation compound (GIC) or indeed graphite oxide (GO). It involves the treatment of natural graphite powder [William S. Hummers, Jr., et al., Preparation of Graphitic Oxide, Journal of the American Chemical Society, 1958, p. 1339]. Before intercalation or oxidation, graphite has a graphene interplanar spacing of approximately 0.335 nm (L _d =1/2 d ₀₀₂ =0.335 nm). Upon intercalation and oxidation treatments, graphene spacing typically increases to values greater than 0.6 nm. This is the first expansion step that occurs in the graphite material during this chemical pathway. The resulting GIC or GO is then further expanded (often referred to as exfoliation) using either thermal shock exposure or solution-based ultrasound-assisted graphene exfoliation methods.

Thermal shock exposure methods involve subjecting GIC or GO to high temperatures (typically (800-1,050°C) for a short period of time (typically 15-60 seconds) to exfoliate or swell the GIC or GO. This thermal shock procedure can produce partially separated graphite flakes or graphene sheets, but typically the majority of graphite flakes remain interconnected. Typically, the exfoliated graphite or graphite worms are then subjected to a flake separation process using air milling, mechanical shearing, or underwater sonication. Thus, method 1 basically involves three different steps: a first expansion (oxidation or intercalation), a further expansion (or "exfoliation"), and separation.

In the solution-based separation method, expanded or exfoliated GO powder is dispersed in water or a hydroalcoholic solution, and then subjected to ultrasonication. In these methods, sonication is performed after intercalation and oxidation of the graphite (i.e. after the first expansion) and typically after thermal shock exposure of the resulting GIC or GO (after the second expansion). It is important to note that when using Alternatively, ion exchange or long-term purification of GO powder dispersed in water such that the repulsive forces between the ions present in the interplane space overcome the inter-graphene van der Waals forces, resulting in separation of the graphene layers. The procedure takes place.

In the aforementioned examples, the starting material for the preparation of graphene sheets or NGP is natural graphite, artificial graphite, oxidized graphite, fluorinated graphite, graphite fibers, carbon fibers, carbon nanofibers, carbon nanotubes, mesophase carbon microbeads (MCMB) or The graphite material may be selected from the group consisting of carbonaceous microspheres (CMS), soft carbon, hard carbon, and combinations thereof.

Oxidized graphite is produced by combining a layered graphite material (e.g., natural flake graphite or synthetic graphite powder) with an intercalant (e.g., concentrated sulfuric acid) and an oxidizing agent (e.g., nitric acid, hydrogen peroxide, sodium perchlorate, peroxide, etc.). (potassium manganate) at the desired temperature (typically 0-70°C) for a sufficient length of time (typically 4 hours to 5 days). It can be prepared by The resulting oxidized graphite particles are then adjusted to a pH value typically between 2 and 5 by washing several times with water. The resulting suspension of graphite oxide particles dispersed in water is then subjected to ultrasonication to obtain a dispersion of graphene oxide sheets dispersed and separated in water. A small amount of reducing agent (eg, Na ₄ B) can be added to obtain reduced graphene oxide (RDO) sheets.

In order to reduce the time required to obtain the precursor solution or suspension, the graphite is partially oxidized for a shorter period of time (e.g., 30 minutes to 4 hours) to obtain the graphite intercalation compound (GIC). You can choose that. The GIC particles are preferably exposed to thermal shock within a temperature range of 600 to 1,100° C., typically for 15 to 60 seconds to obtain exfoliated graphite or graphite worms, whereas optionally ( However, preferably) mechanical shearing is performed (e.g. using a mechanical shearer or an ultrasonicator) to break up the graphite flakes that make up the graphite worm. Either the already separated graphene sheets (after mechanical shearing) or the unbroken graphite worms or individual graphite flakes are then redispersed in water, acid or organic solvents and sonicated to form graphene. A dispersion is obtained.

Pure graphene materials are preferably produced by one of the following three methods: (A) intercalation of graphite materials with non-oxidizing substances, followed by thermal or chemical treatment in a non-oxidizing environment; (B) exposing the graphite material to a supercritical fluid environment for infiltration and exfoliation between the graphene layers; or (C) subjecting the graphite material in powder form to a surfactant or dispersant. Graphene is dispersed in an aqueous solution containing the graphene to obtain a suspension, and the suspension is directly subjected to ultrasonic treatment to obtain a graphene dispersion.

In procedure (A), particularly preferred steps include (i) treating the graphite material with an alkali metal (e.g. potassium, sodium, lithium or cesium), an alkaline earth metal or an alkali metal or alkali metal alloy, mixture or eutectic; (ii) a chemical exfoliation treatment (eg, by soaking the potassium intercalated graphite in an ethanol solution).

In procedure (B), the preferred steps include converting the graphite material into carbon dioxide (e.g. at a temperature T>31°C and a pressure P>7.4 MPa) and water (e.g. at a T>374°C and a pressure P>22.1 MPa), etc. in a supercritical fluid for a time sufficient to allow penetration between the graphene layers (temporary intercalation). Following this step, a rapid vacuum is then applied to exfoliate the individual graphene layers. Other suitable supercritical fluids include methane, ethane, ethylene, hydrogen peroxide, ozone, water oxidation (water with high concentrations of dissolved oxygen), or mixtures thereof.

In procedure (C), the preferred steps are (a) dispersing particles of graphite material in a liquid medium comprising a surfactant or dispersant therein to obtain a suspension or slurry; (b) Ultrasound at an energy level for a length of time sufficient to obtain a graphene dispersion of dispersed and separated graphene sheets (unoxidized NGP) in a liquid medium (e.g. water, alcohol or organic solvent). (a process commonly referred to as sonication).

NGP can be produced with an oxygen content of 25% by weight or less, preferably less than 20%, more preferably less than 5%. Typically the oxygen content is between 5% and 20% by weight. Oxygen content can be determined using chemical elemental analysis and/or X-ray photoelectron spectroscopy (XPS).

The layered graphite material used in prior art methods for producing GIC, oxidized graphite, and subsequently exfoliated graphite, flexible graphite sheets, and graphene platelets, was often natural graphite. However, the present disclosure is not limited to natural graphite. The starting material can be natural graphite, artificial graphite (e.g. highly oriented pyrolytic graphite, HOPG), oxidized graphite, fluorinated graphite, graphite fibers, carbon fibers, carbon nanofibers, carbon nanotubes, mesophase carbon microbeads (MCMB) or carbon The material may be selected from the group consisting of solid carbon microspheres (CMS), soft carbon, hard carbon, and combinations thereof. All of these materials contain graphite crystallites composed of layers of graphene planes stacked or bonded together by van der Waals forces. In natural graphite, multiple stacks of graphene planes in which the orientation of the graphene planes differs between stacks form clusters with each other. In carbon fibers, the graphene planes are typically oriented along one preferred direction. Generally speaking, soft carbon is a carbonaceous material obtained by carbonization of aromatic molecules in the liquid state. Their aromatic rings or graphene structures are parallel to each other to some extent and further graphitization is possible. Hard carbon is a carbonaceous material obtained from aromatic solid materials, such as phenolic resins and polymers such as polyfurfuryl alcohol. Their graphene structures are relatively randomly oriented and therefore further graphitization is difficult to achieve even at temperatures above 2,500°C. However, graphene sheets are present in these carbons.

Fluorinated graphene or fluorinated graphene is used herein as an example of a group of halogenated graphene materials. There are two different methods used to produce fluorinated graphene: (1) Fluorination of pre-synthesized graphene: This method involves the fluorination of graphene prepared by mechanical exfoliation or CVD growth, such as _XeF2 . involves treatment with a fluorinating agent or F-based plasma; (2) exfoliation of multilayer fluorinated graphite: both mechanical exfoliation and liquid-phase exfoliation of fluorinated graphite are easily realized [F. Karlicky, et al. “Halogenated Graphenes: Rapidly Growing Family of Graphene Derivatives” ACS Nano, 2013, 7 (8), pp 6434-6464].

Intercalation of F ₂ with graphite at high temperatures yields covalent graphite fluoride (CF) _n or (C ₂ F) _n , while at low temperatures graphite intercalation compounds (GICs) C _x F ( 2≦x≦24) is obtained. In (CF) _n , the carbon atoms are sp3-hybridized, so the fluorocarbon layer becomes corrugated, consisting of trans-bonded chair cyclohexane. In (C ₂ F) _n , only half of the C atoms are fluorinated and each set of adjacent carbon sheets are bonded to each other by covalent CC bonds. Systematic studies on fluorination reactions have shown that the resulting F/C ratio depends on the fluorination temperature, the partial pressure of fluorine in the fluorination gas, and the physical properties of the graphite precursor, such as the degree of graphitization, particle size, and specific surface area. It has been shown that there is a strong dependence on Most of the available literature involves fluorination with _F2 gas, optionally in the presence of fluoride, but in addition to fluorine ( _F2 ), other fluorinating agents can be used. .

In order to exfoliate the layered precursor material into individual graphene layers or layers, it is necessary to overcome the attractive forces between adjacent layers and further stabilize the layers. This can be achieved either by covalent modification of the graphene surface with functional groups or non-covalent modification using specific solvents, surfactants, polymers or donor-acceptor aromatic molecules. The liquid phase exfoliation method involves sonicating fluorinated graphite in a liquid medium to form fluorinated graphene sheets dispersed in the liquid medium. The resulting dispersion can be used directly for graphene deposition on the surface of polymeric parts.

Nitrogenation of graphene can be performed by exposing graphene materials, such as graphene oxide, to ammonia at high temperatures (200-400° C.). Nitrogenated graphene can also be formed at lower temperatures, for example, by hydrothermal methods by sealing GO and ammonia in an autoclave and then increasing the temperature to 150-250°C. Alternative synthesis methods for nitrogen-doped graphene include nitrogen plasma treatment on graphene, arc discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions and synthesis of graphene oxide and urea at various temperatures. Examples include hydrothermal treatment.

For the purpose of defining the claims of this application, NGP or graphene materials include pure graphene, single and multilayer (typically fewer than 10 layers of graphene), graphene oxide, reduced graphene oxide (RGO), Discrete sheets/platelets of graphene chloride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, chemically functionalized graphene, doped graphene (e.g. doped with B or N) include. Pure graphene has essentially 0% oxygen. RGO typically has an oxygen content of 0.001% to 5% by weight. Graphene oxide (including RGO) can have from 0.001% to 50% by weight oxygen. All graphene materials other than pure graphene have 0.001% to 50% by weight of non-carbon elements (eg, O, H, N, B, F, Cl, Br, I, etc.). These materials are referred to herein as impure graphene materials. Graphene according to the invention can include pure graphene or impure graphene, and the method according to the invention allows this flexibility. All of these graphene sheets can be chemically functionalized.

Graphene sheets have a large proportion of edges corresponding to the edge planes of graphite crystals. The carbon atoms in the edge plane are reactive and need to contain some heteroatoms or groups to satisfy the valence of the carbon. Additionally, there are many types of functional groups (eg, hydroxyl and carboxylic acid) that are naturally present at the edges or surfaces of graphene sheets produced by chemical or electrochemical methods. Many chemical functional groups (eg, _-NH2 , etc.) can be easily attached to the edges and/or surfaces of graphene using methods well known in the art.

In one preferred embodiment, the resulting functionalized graphene sheets (NGPs) can be roughly represented by the formula: [NGP]-R _m , where m is the number of different functional group types ( Typically 1 to 5), R is 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. , where y is an integer of 3 or less, R' is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly(alkyl ether), and R'' is fluoroalkyl, fluoroaryl, Fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide and Z is carboxylate or trifluoroacetate.

One of the commonly used curing agents for epoxy resins is diethylenetriamine (DETA), which has three _-NH2 groups. When DETA is included in the collision chamber, one of its three _-NH2 groups can be bonded to the edge or surface of the graphene sheet, and the remaining two unreacted _-NH2 groups are then transferred to the epoxy It can be used for reaction with resin. Such an arrangement forms a good interfacial bond between the NGP (graphene sheet) and the epoxy-based binder resin.

Other useful chemical functional groups or reactive molecules include amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylenetetramine (TETA). ), tetraethylene pentamine (TEPA), hexamethylenetetramine, polyethylene polyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated hardeners, non-amine hardeners, and combinations thereof. These functional groups are polyfunctional and can react with at least two chemical species from at least two ends. Most importantly, they can be attached to the edge or surface of graphene with one of their terminal ends and reacted with an epoxide or epoxy resin at one or two other terminals during the epoxy curing step. It is.

The above [NGP]-R _m can be further functionalized. The resulting graphene sheet has the formula: [NGP]-A _m (where A is 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 protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or enzyme a suitable functional group of a transition state analog of the substrate, or R'-OH, R'-NR' ₂ , R'SH, R'CHO, R'CN, R'X, R'N ⁺ (R' ⁾ _{3 ​ ​ ​ ​} -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 1 and less than 200. CNTs can be similarly functionalized.

NGP and a _conductive additive ( For example, carbon nanofibers) can also be functionalized. The compositions of the present disclosure also include NGP on which certain cyclic compounds are adsorbed. These have the formula: [NGP]-[X-R _a ] _m (where a is 0 or a number less than 10, and X is a polycyclic aromatic, a heteropolyaromatic, or a metal hetero polycyclic aromatic moieties, and R is as defined above. Preferred cyclic compounds are planar. More preferred cyclic compounds for adsorption are porphyrins and phthalocyanines. Adsorbed cyclic compounds can be functionalized. Such compositions include a compound of the formula [NGP]-[XA _a ] _m , where m, a, X and A are as defined above.

The functionalized NGPs of the present disclosure can be prepared directly by electrophilic addition to sulfonated or deoxygenated graphene platelet surfaces. The graphene platelets can be treated prior to contacting with the functionalizing agent. Such treatments can include dispersing graphene platelets in a solvent. In some cases, the platelets can then be filtered and dried before contacting. One particularly useful class of functional groups are carboxylic acid moieties, which are naturally present on the NGP surface when the NGP is prepared from the acid intercalation route described above. If carboxylic acid functionalization is required, NGP can be subjected to chlorate, nitric acid or ammonium persulfate oxidation.

Carboxylic acid-functionalized graphene sheets or platelets are particularly useful because they can serve as a starting point for preparing other types of functionalized NGPs. For example, alcohols or amides can be easily combined with acids to yield stable esters or amides. If the alcohol or amine is part of a di- or polyfunctional molecule, the bond via O- or NH- leaves another functional group as a pendant group. These reactions can be carried out using any method developed for the esterification or amination of carboxylic acids with alcohols or amines as is well known in the art. Examples of these methods can be found in G. W. Anderson, et al., J. Amer. Chem. Soc. 86, 1839 (1964), which is incorporated herein by reference in its entirety. By treating the platelets with nitric acid and sulfuric acid to obtain nitrated platelets, and then chemically reducing the nitrated form with a reducing agent such as sodium dithionite to obtain amino-functionalized platelets. Amino groups can be introduced directly onto the graphite platelets.

In some embodiments, the chemically functionalized graphene sheets include alkyl or aryl silanes, alkyl or aralkyl groups, hydroxyl groups, carboxyl groups, amine groups, sulfonate groups (-SO ₃ H), aldehyde groups, quinoids, fluorocarbons, or including chemical functional groups selected from combinations thereof. Alternatively, the functional group is 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-)-oxycarbonylnitrene (where R = the following group)
) and combinations thereof.

In certain embodiments, the functionalizing agent is _SO3H , COOH, _NH2 , 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 (where y is , an integer of 3 or less, R' is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly(alkyl ether), and R'' is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl. or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate) and combinations thereof.

Functional groups include amidoamine, polyamide, aliphatic amine, modified aliphatic amine, alicyclic amine, aromatic amine, anhydride, ketimine, diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA). , polyethylene polyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated hardeners, non-amine hardeners, derivatives thereof, and combinations thereof.

In some embodiments, the functional groups are OY, NHY, O=C-OY, P=C-NR'Y, O=C-SY, O=C-Y, -CR'1-OY, N' may be selected from Y or C'Y, and Y is a functional group of a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or transition state analog of an enzyme substrate. , or 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-) selected from _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 It is an integer greater than 1 and less than 200.

After the chemically functionalized or non-functionalized graphene sheets are produced, they can be coated with a thin layer of anti-corrosion material on at least one of the two major surfaces. A method of producing a graphene-based coating suspension includes (a) providing a continuous film of graphene sheets in a deposition zone; (b) vapor or atoms of an anticorrosive pigment or metal precursor in the deposition zone. (c) coating the graphene sheet with an anticorrosive material; (c) coating the graphene sheet with an anticorrosion material; (d) dispersing the plurality of graphene sheet fragments coated with the anticorrosive material and a binder resin in a liquid medium to form a coating suspension; including forming.

In step (a), a continuous film of graphene sheets can be produced by chemical vapor deposition (CVD) of graphene onto a solid substrate. However, CVD is an expensive process. Alternatively, this continuous film is preferably prepared by preparing a suspension of a graphene material sheet (e.g., a graphene oxide sheet) in a liquid medium (e.g., water), as shown in FIG. It can be produced by spraying a liquid onto the surface of a solid substrate to form a graphene film. Preferably, an ultrasonic atomization or electrostatic spraying device is used to transfer and deposit the graphene sheets onto the substrate surface, whereby a plurality of graphene sheets are overlapped to a thickness of about 0.5 nm to several microns. A cohesive film of diameter (preferably 1 nm to 20 nm) is formed.

This graphene film, with or without a supporting substrate, is then introduced into a deposition zone (e.g., a vacuum chamber or a CVD chamber), where a stream of vapor or atoms of the anticorrosion material is applied to one of the graphene films. A coating film (eg, a Zn-coated graphene film) is formed by depositing on the surface. This deposition can be performed by physical vapor deposition (PVD), sputtering, laser assisted deposition, chemical vapor deposition such as plasma enhanced CVD and hot wire CVD, atomic layer deposition and deposition from solution. The thickness of the anticorrosive material coating is preferably less than 500 nm thick, more preferably less than 100 nm, even more preferably less than 50 nm, and most preferably less than 20 nm.

Referring again to FIG. 2, the graphene film coated with the anti-corrosion material is then mechanically fractured to form an anti-corrosion material having a lateral dimension preferably in the range of 10 nm to 10 μm, more preferably 100 nm to 3 μm. Pieces of graphene sheets coated with the material are obtained.

As shown at the top of Figure 2, the use of graphene films made by depositing from graphene suspensions is difficult because the film needs to be broken into small pieces of coated graphene sheets after being coated with anti-corrosion material. It is preferable to CVD graphene film. A continuous graphene film made of overlapping graphene sheets can be easily fractured along the boundaries of the original graphene sheets. The resulting coated graphene sheet is comparable in size to the original graphene material sheet. Suspension-derived graphene films are much more fragile than CVD graphene films. However, the inventors converted this fragility into an advantageous feature for producing coated graphene sheets of desired size.

In order to prepare a more reactive dispersion for use in graphene coating compositions that protect metal parts, the produced graphene dispersion may be combined with other ingredients (fillers, dispersants, color pigments, extenders, antifoaming agents). , catalysts, promoters, stabilizers, coalescing aids, thixotropic agents, antisettling agents, etc.) can be further added. The metal part can be simply immersed in the graphene suspension for a period of seconds to minutes (preferably 5 seconds to 15 minutes) and then the polymer part can be pulled out of the graphene liquid dispersion. After removing the liquid (eg, naturally or by forced evaporation), the graphene sheets spontaneously coat and bond onto the surface of the polymeric part.

The anticorrosive coating system is tested using methods well known in the art, such as the salt spray test (SST) according to ASTM B117 (ISO 9277) and the cyclic voltammetry test (current density versus voltage) to determine the cathode and anode polarization currents. Characteristics were determined using methods such as

The following examples are used to illustrate some specific details of the best mode of carrying out the disclosure and should not be construed as limiting the scope of the disclosure.

Example 1: Graphene oxide from sulfuric acid intercalation and exfoliation of MCMB MCMB (mesocarbon microbeads) was supplied by China Steel Chemical Co. This material has a density of about 2.24 g/cm ³ and a median particle size of about 16 μm. MCMB (10 grams) was intercalated with an acid solution (4:1:0.05 ratio of sulfuric acid, nitric acid and potassium permanganate) for 48 hours. After the reaction was completed, the mixture was poured into deionized water and filtered. The intercalated MCMB was washed repeatedly with a 5% solution of HCl to remove most of the sulfate ions. The sample was then washed repeatedly with deionized water until the pH of the filtrate was neutral. The resulting slurry was dried in a vacuum oven at 60° C. for 24 hours and stored. The dried powder sample was placed in a quartz tube and inserted into a horizontal tubular furnace preset at the desired temperature of 800° C. to 1,100° C. for 30 to 90 seconds to obtain a graphene sheet. A certain amount of graphene sheets were mixed with water and sonicated for 10 minutes at a power of 60 W to obtain a graphene dispersion.

A graphene-water dispersion was cast onto a glass substrate to form a graphene film, onto which Zn and Al were separately deposited using physical vapor deposition and sputtering. This anti-corrosion material coated film was then cut into small pieces and air-jet milled to obtain discrete coated graphene sheets.

A small sample was taken, dried, and examined by TEM, which showed that most of the NGP had 1 to 10 layers. The oxygen content of the resulting graphene powder (GO or RGO) was between 0.1% and about 25%, depending on the temperature and time of exfoliation.

Various other pigments and ingredients were added separately to several suspensions of coated graphene sheets to create various anticorrosive coating compositions.

Example 2: Oxidation and exfoliation of natural graphite
According to the method of Hummers [U.S. Pat. No. 2,798,878, July 9, 1957], 48% Oxidized graphite was prepared by oxidizing graphite flakes with time. After the reaction was completed, the mixture was poured into deionized water and filtered. The samples were then washed with a 5% HCl solution to remove most of the sulfate ions and residual salts, and then repeatedly with deionized water until the pH of the filtrate was approximately 4. The purpose of this was to remove all sulfuric and nitric acid residues from the interstitial spaces of the graphite. The resulting slurry was dried in a vacuum oven at 60° C. for 24 hours and stored.

The sample is placed in a quartz tube, and this is inserted into a horizontal tube furnace preset at 1,050°C to obtain highly exfoliated graphite, thereby intercalating (oxidizing) and exfoliating the dried compound. went. The obtained exfoliated graphite was dispersed in 45°C water containing 1% surfactant in a flat bottom flask, and the resulting suspension was subjected to ultrasonication for 15 minutes to form graphene oxide (GO). A sheet dispersion was obtained.

A graphene-water dispersion was cast onto a glass substrate to form a graphene film, onto which Zn was deposited using physical vapor deposition. The Zn-coated film was then cut into small pieces and air jet milled on them to obtain discrete coated graphene sheets. Various other pigments and ingredients were added separately to several suspensions of coated graphene sheets to create various anticorrosive coating compositions. The coating suspension is applied to the steel using ultrasonic atomization or compressed air assisted spray painting to promote alignment such that the coated graphene sheets are parallel to each other and substantially parallel to the surface of the steel structure. applied to the surface of the structure.

Example 3: Preparation of pure graphene sheets Pure graphene sheets were prepared by using direct sonication or liquid phase exfoliation process. In one typical procedure, 5 grams of graphite flakes ground to a size of approximately 20 μm are dissolved in 1,000 mL of deionized water (containing 0.1% by weight of DuPont's dispersant Zonyl® FSO). to obtain a suspension. An ultrasonic energy level of 85 W (Branson S450 Ultrasonicator) was used for exfoliation, separation and crushing of graphene sheets for times ranging from 15 minutes to 2 hours. The resulting graphene sheet was completely unoxidized, oxygen-free, and relatively defect-free pure graphene.

Example 4: Preparation of fluorinated graphene To produce GF, we used several methods, but only one method is described here as an example. In one typical procedure, highly exfoliated graphite ( _HEG ) was prepared from the intercalated compound _С2F.xClF3 . HEG was further fluorinated with chlorine trifluoride vapor to obtain fluorinated highly exfoliated graphite (FHEG). The pre-chilled Teflon reactor was filled with 20-30 mL of pre-chilled liquid ClF ₃ and then the reactor was closed and cooled to liquid nitrogen temperature. Subsequently, up to 1 g of HEG was placed in a container with holes for ClF ₃ gas to reach the reactor. After 7-10 days, a gray-beige product was formed with the approximate formula C ₂ F. The GF sheets were then dispersed in a halogenated solvent to form a suspension.

Example 5: Preparation of nitrogenated graphene Graphene oxide (GO) synthesized in Example 2 was pulverized with various proportions of urea, and the pelletized mixture was heated in a microwave reactor (900 W) for 30 seconds. The product was washed several times with deionized water and dried under vacuum. In this method, reduction of graphene oxide and nitrogen doping are performed simultaneously. The products obtained with graphene/urea mass ratios of 1/0.5, 1/1, and 1/2 are called N-1, N-2, and N-3, respectively, and the values of these samples determined by elemental analysis are The nitrogen content was 14.7, 18.2 and 17.5% by weight, respectively. These nitrogenated graphene sheets are still dispersible in water.

Example 6: Functionalized graphene as an anti-corrosion component The chemical functional groups involved in this study are azide compounds (2-azidoethanol), alkylsilanes, hydroxyl groups, carboxyl groups, amine groups, sulfonate groups (-SO ₃ H) and diethylenetriamine (DETA). These functionalized graphene sheets are supplied by Taiwan Graphene Co., Taipei, Taiwan. After removing water and curing at 150° C. for 15 minutes, the graphene sheets bonded well to the metal surface.

The inventors have confirmed that, in general, metal component surfaces can be well bonded to functionalized graphene sheets according to the present invention with aqueous binder resins. When a functionalized graphene sheet is included as an anticorrosion pigment along with an anode metal such as Zn or Al, the coated surface is generally smoother than when using the metal pigment alone.

Example 7: Polyurethane-based aqueous binder resin Several hydroxyl/carboxyl functional polyurethane dispersions were prepared by a non-isocyanate method according to Scheme 1 shown below.

The polymer was synthesized by first reacting the diester and polyol in the presence of an organometallic catalyst at 200° C. to 220° C. under reduced pressure. Methanol was a byproduct of the transesterification reaction. Subsequently, hydroxyl-functional urethane diol was added and propylene glycol was removed under reduced pressure at 180°C. This hydroxyl-functional urethane diol was prepared by a non-isocyanate method utilizing a reaction between a cyclic carbonate and a diamine. The resin was then carboxyl functionalized and dispersed in water using a tertiary amine for neutralization. The number average molecular weight of the polyurethane dispersion was in the range of about 3000-4000 g/mol.

Solvent-based polyurethane resins are widely available from commercial sources.

Example 8: Aqueous Binder Resin Based on Polyurethane-Urea Copolymer Two polyurethane-urea dispersions were prepared by the prepolymer isocyanate method shown in Scheme 2. This method actually produces polyurethane-urea polymers. The urea moiety is formed by a chain extension reaction between the isocyanate-terminated polyurethane and the diamine.

The melamine resin used as a crosslinking agent was a commercially available type hexakis(methoxymethyl)melamine (HMMM) having a degree of polymerization of approximately 1.5, an average molecular weight of 554, and an average theoretical functionality of 8.3. The aqueous acrylic dispersion used in the formulation was Acrysol WS-68 from Rohm and Haas, a hydroxyl/carboxyl functional resin. A water-dispersible polyisocyanate (Bayhydur XP-7007, modified aliphatic isocyanate trimer) from Bayer Corporation was used for crosslinking.

Example 9: Water-Soluble Alkyd Resin In one typical procedure, the following raw materials were charged into a container fitted with a stirring device, a temperature control device and a decanter, and the charge was heated while stirring: Soy fatty acid ( 33% by weight), trimethylolpropane (33%), trimellitic anhydride (8.5%), isophthalic acid 24%, dibutyltin oxide (0.5%) and xylene (1%). As the reaction proceeded, water was produced and was removed by azeotroping with xylene. Heating was continued until an acid number of 39 and a hydroxyl number of 140 were obtained. Next, the reaction was stopped. The reaction mixture was diluted with butylcellulose to a non-volatile content of 70% by weight to obtain an alkyd resin varnish. This resin varnish was neutralized with triethylamine and adjusted with deionized water until the nonvolatile content was 40% by weight to obtain a water-soluble alkyd resin varnish. This varnish had an effective acid number of 33.

Example 10: Epoxy Resin The waterborne epoxy used in this study was based on a "Type 1" (approximately 500-600 epoxy equivalent weight) solid epoxy dispersion and a hydrophobic amine adduct curing agent. Both components utilize nonionic surfactants that are pre-reacted in the epoxy and amine components. An example of such a waterborne epoxy was EPI-REZ 6520 (Hexion Specialty Chemicals Co.) with EPIKURE 6870 (modified polyamine adduct). Solvent-based epoxy resins are widely available from commercial sources.

Some representative test results are summarized in Figure 2, which shows that adding 1 wt% of selected functionalized graphene sheets (monolayer graphene) into zinc primer impairs the anti-corrosion ability. This shows that the required amount of Zn can be reduced from 80% by weight to 20% by weight (the amount of Zn is reduced to one-fourth). It is surprising and unprecedented that 1% by weight single layer graphene can completely replace 60% by weight zinc. The sum of Zn particles and graphene sheets is about 21% by weight in this sample. In contrast, only 15% by weight (14% Zn coated on 1% graphene sheet) would be sufficient to achieve the same level of protection against corrosion.

Also, 10% by weight of few-layer graphene can be effectively replaced by 70% by weight of Zn particles. The sum of Zn particles and few-layer graphene sheets is about 20% by weight in this sample. If Zn is coated on the graphene surface, a total of 17% will be sufficient (10% Zn coated on 7% graphene sheet). These significant improvements in performance are truly unexpected.

In addition to (or in place of) zinc, the inventors also found that other elements or compounds, such as aluminum, chromium, beryllium, magnesium, alloys thereof, zinc phosphate or combinations thereof, can be used in various types. It was further confirmed that the material can be used as an anticorrosion pigment or a sacrificial metal to be paired with a graphene sheet. The use of small amounts of graphene (typically 0.1% to 10% by weight) can replace up to 70% by weight of these anticorrosive pigment materials.

Claims (52)

a plurality of graphene sheets each having two opposite parallel surfaces and an anti-corrosion pigment with a thickness of 0.5 nm to 100 nm covering and overlying at least 80 % of the area of one of said two parallel surfaces; or a graphene-based coating suspension comprising a thin film coating with a sacrificial metal and a binder resin dissolved or dispersed in a liquid medium, wherein the plurality of graphene sheets contain essentially 0% comprising a single-layer or few-layer graphene sheet selected from pure graphene material with non-carbon elements or impure graphene material with 0.001% to 47% by weight of non-carbon elements, said impure graphene being graphene oxide, selected from reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, doped graphene, chemically functionalized graphene or a combination thereof; Graphene-based coating suspension having a weight fraction of 0.1% to 30%, based on the total coating suspension weight excluding liquid medium. Coating suspension according to claim 1, wherein the anti-corrosion pigment or sacrificial metal is selected from aluminum, chromium, zinc, beryllium, magnesium, alloys thereof, zinc phosphate or combinations thereof. The binder resin includes a resin selected from epoxy resins, polyurethane resins, urethaneurea resins, phenolic resins, acrylic resins, alkyd resins, polyimides, thermosetting polyesters, vinyl ester resins, silicate adhesives, or combinations thereof. Coating suspension according to claim 1. 2. The impure graphene material according to claim 1, wherein the impure graphene material has from 1% to 30% by weight of non-carbon elements selected from O, H, N, F, Cl, Br, I, B, P or combinations thereof. Coating suspension as described. Carriers, fillers, dispersants, surfactants, antifoaming agents, catalysts, promoters, stabilizers, coalescence aids, thixotropic agents, antisettling agents, colored dyes, coupling agents, extenders, conductive pigments, electronic conductors 2. The coating suspension of claim 1, further comprising a polymer or a combination thereof. 4. The conductive pigment is selected from acetylene black, carbon black, expanded graphite flakes, carbon fibers, carbon nanotubes, antimony doped tin oxide or indium tin oxide coated mica or mixtures thereof. Coating suspension according to 5 . The electronically conductive polymers include polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), polyheteroarylene vinylene (PArV) (herein, hetero 5. The arylene group is selected from the group consisting of thiophene, furan or pyrrole), poly-p-phenylene (PpP), polyphthalocyanine (PPhc), etc., and derivatives thereof and combinations thereof. Coating suspension as described in. The chemically functionalized graphene is selected from alkyl or arylsilanes, alkyl or aralkyl groups, hydroxyl groups, carboxyl groups, amine groups, sulfonate groups ( _-SO H), aldehyde groups, quinoids, fluorocarbons or combinations thereof. Coating suspension according to claim 1, comprising graphene sheets with chemical functional groups. The chemically functionalized graphene includes 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-)-oxycarbonylnitrene (where R = the following group)

2. The coating suspension of claim 1, comprising graphene sheets having chemical functional groups selected from the group consisting of azide compounds selected from the group consisting of: (1) and combinations thereof. Coating suspension according to claim 1, wherein the chemically functionalized graphene comprises graphene sheets having chemical functional groups selected from oxygenated groups selected from the group consisting of hydroxyl, peroxide, ether, keto and aldehyde. . The chemically functionalized graphene includes 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. where y is an integer less than or equal to 3, R' is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly(alkyl ether), and R'' is The coating suspension of claim 1, wherein fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate and combinations thereof. Turbid liquid. The chemically functionalized graphene includes amidoamine, polyamide, aliphatic amine, modified aliphatic amine, cycloaliphatic amine, aromatic amine, anhydride, ketimine, diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine. (TEPA), polyethylene polyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated hardeners, non-amine hardeners, and combinations thereof. Coating suspension according to 1. The chemically functionalized graphene may be OY, NHY, O=C-OY, P=C-NR'Y, O=C-SY, O=C-Y, -CR'1-OY, N'Y or C' comprises a graphene sheet with a chemical functional group selected from Y, and Y is a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or transition state analog of the enzyme substrate. is a functional group, or 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 selected from 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 are integers greater than 1 and less than 200. An object or structure comprising a plurality of graphene sheets, a thin coating of an anti-corrosion pigment or sacrificial metal deposited on the graphene surface, and bonding the coated graphene sheets to each other and to the surface of the object or structure. a binder resin, wherein the plurality of graphene sheets are pure graphene material having essentially 0% non-carbon elements or 0.001% to 47% by weight non-carbon elements. The impure graphene includes graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, selected from nitrogenated graphene, doped graphene, chemically functionalized graphene or a combination thereof, the graphene sheets having a weight fraction of 0.1% to 30% based on the total coating weight;
Object or structure , wherein said thin coating of anti-corrosion pigment or sacrificial metal covers an area of at least 80% of one of two parallel surfaces of the graphene sheet . 15. An object or structure according to claim 14 , wherein the anti-corrosion pigment or sacrificial metal is selected from aluminum, chromium, zinc, beryllium, magnesium, alloys thereof, zinc phosphate or combinations thereof. 15. Object or structure according to claim 14 , wherein the coating has a thickness of 1 nm to 1.0 mm. 15. An object or structure according to claim 14 , which is made of metal. 14. The binder resin comprises an ester resin, neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid, terephthalic acid, urethane resin, urethane ester resin, acrylic resin, acrylic urethane resin, or a combination thereof. Objects or structures described in . 15. The object or structure according to claim 14 , wherein the 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. The binder resin comprises a thermoplastic polyfunctional epoxy monomer selected from diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, or combinations thereof. 15. The object or structure of claim 14 , comprising a curable resin. The binder resin includes trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylolethane triglycidyl ether, and tetraphenylene triglycidyl ether. Tetraglycidyl ether of roll ethane, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether , propoxylated glycerin triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Di- or trifunctional selected from the group consisting of ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl carboxylate and mixtures thereof. 15. The object or structure of claim 14 , comprising a thermosetting resin containing a polypropylene epoxy monomer. The binder resins include acrylate and methacrylate oligomers, (meth)acrylates (acrylates and methacrylates), polyhydric alcohols having (meth)acrylate functional groups and derivatives thereof, such as ethoxylated trimethylolpropane tri(meth)acrylate, tripropylene. Glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1, 6-hexanediol di(meth)acrylate or neopentyl glycol di(meth)acrylate and mixtures thereof, and low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, epoxy acrylates, polybutadiene resins 15. An object or structure according to claim 14 , comprising a UV radiation curable resin or lacquer selected from acrylate and methacrylate oligomers derived from polythiol-polyene resins. 15. An object or structure according to claim 14 , which is a reinforcing material or member made of metal. 15. An object or structure according to claim 14 , which is a concrete structure. 15. The object or structure according to claim 14 , which is a bridge. A method for producing a graphene-based coating suspension according to claim 1, comprising:
a) providing a continuous film of graphene sheets in the deposition zone;
b) introducing a vapor or atoms of an anti-corrosion pigment or metal into the deposition zone and depositing the vapor or atoms on the surface of the graphene sheet to form a coating film of the graphene sheet coated with anti-corrosion material; Koto;
c) mechanically breaking the coating film into a plurality of pieces of graphene sheets coated with anti-corrosion material;
d) dispersing a plurality of pieces of graphene sheets coated with an anti-corrosion material and a binder resin in a liquid medium to form said coating suspension. The continuous film of graphene sheets is produced by spraying a graphene suspension onto a solid substrate, the graphene suspension comprising graphene sheets dispersed in a liquid medium; 27. The method of claim 26 , wherein the method is produced by removing the liquid medium. 27. The method of claim 26 , wherein the continuous film of graphene sheets is produced by chemical vapor deposition of graphene material onto a solid substrate. 27. The method of claim 26 , wherein the coated film has an anti-corrosion active material coating thickness of less than 100 nm. 5. Said step (b) of forming a coating film of graphene sheets coated with an anti-corrosion material involves chemical vapor deposition, physical vapor deposition, sputtering or laser assisted thin film deposition of an anti-corrosion pigment or metal onto said film of graphene sheets. The method according to item 26 . 27. The method of claim 26 , wherein step (c) of mechanically disrupting involves air jet milling, impact milling, grinding, mechanical shearing, sonication, or a combination thereof. Step (a) of providing a continuous film of graphene sheets includes feeding the continuous film from a feed roller into the deposition zone, and step (b) includes feeding the coated film onto a take-up roller. 27. The method of claim 26 , further comprising collecting. A method for inhibiting corrosion of a structure or object having a surface comprising: (i) a plurality of graphene sheets coated with a thin film of an anticorrosive pigment or sacrificial metal having a thickness of 0.5 nm to 1 μm; coating at least a portion of said surface with a coating suspension comprising a resin binder dispersed or dissolved in; (ii) at the end of said coating step at least partially draining said liquid medium from said coating suspension; forming a protective coating layer on the surface ;
The method , wherein said thin film of anti-corrosion pigment or sacrificial metal covers an area of at least 80% of one of two parallel surfaces of a graphene sheet . 34. The method of claim 33 , wherein the anticorrosion pigment or sacrificial metal is selected from aluminum, chromium, zinc, beryllium, magnesium, alloys thereof, zinc phosphate, or combinations thereof. The plurality of graphene sheets are a single layer or several layers selected from pure graphene material with essentially 0% non-carbon elements or impure graphene material with 0.001% to 47% by weight non-carbon elements. The impure graphene includes graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, doped graphene, chemically functionalized graphene, or 34. The method of claim 33 , selected from a combination thereof, wherein the graphene sheets have a weight fraction of 0.1% to 30% based on the total coating suspension weight excluding the liquid medium. 36. The impure graphene material has from 1% to 30% by weight of non-carbon elements selected from O, H, N, F, Cl, Br, I, B, P or combinations thereof. Method described. The binder resin includes a resin selected from epoxy resins, polyurethane resins, urethaneurea resins, phenolic resins, acrylic resins, alkyd resins, polyimides, thermosetting polyesters, vinyl ester resins, silicate adhesives, or combinations thereof. 34. The method of claim 33 . 33. The protective coating layer comprises graphene sheets coated with an anti-corrosion pigment or sacrificial metal that are aligned substantially parallel to each other and parallel to the surface of the structure or object . The method described in. Carriers, fillers, dispersants, surfactants, antifoaming agents, catalysts, promoters, stabilizers, coalescence aids, thixotropic agents, antisettling agents, colored dyes, coupling agents, extenders, conductive pigments, electronic conductors 34. The method of claim 33 , further comprising a polymer or a combination thereof. 33. The thin film of anti-corrosion pigment or sacrificial metal has a thickness of 0.5 nm to 100 nm and is coated on and covers an area of at least 50% of one of the two parallel surfaces of the graphene sheet. The method described in. 39. The conductive pigment is selected from acetylene black, carbon black, expanded graphite flakes, carbon fibers, carbon nanotubes, antimony doped tin oxide or indium tin oxide coated mica or mixtures thereof. The method described in. Electronically conductive polymers include polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), polyheteroarylene vinylene (PArV) (where heteroarylene 40. The group is selected from the group consisting of thiophene, furan or pyrrole), poly-p-phenylene (PpP), polyphthalocyanine (PPhc), etc., and derivatives thereof and combinations thereof. Method described. Chemically functionalized graphene is a chemically functionalized graphene selected from alkyl or aryl silanes, alkyl or aralkyl groups, hydroxyl groups, carboxyl groups, amine groups, sulfonate groups (-SO ₃ H), aldehyde groups, quinoids, fluorocarbons or combinations thereof. 34. The method of claim 33 , comprising graphene sheets having functional groups. Chemically functionalized graphene contains 2-azidoethanol, 3-azidopropan-1-amine, 4-(2-azidoethoxy)-4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropanoate, chloro carbonate, azidocarbonate, dichlorocarbene, carbene, aryne, nitrene, (R-)-oxycarbonylnitrene (where R = the following group)

34. The method of claim 33 , comprising a graphene sheet having a chemical functional group selected from the group consisting of azide compounds selected from the group consisting of: (1) and combinations thereof. 34. The method of claim 33 , wherein the chemically functionalized graphene comprises graphene sheets having chemical functional groups selected from oxygenated groups selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde. Chemically functionalized graphene includes SO ₃ H, COOH, NH ₂ , OH, R'CHOH, CHO, CN, COCl, halide, COSH, SH, COOR', SR', SiR' ₃ , Si(-OR'-) a chemical functional group selected from the group consisting of _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 less than or equal to 3, R' is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly(alkyl ether), and R'' is a fluorocarbon 34. The method of claim 33 , wherein alkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl, or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate and combinations thereof. Chemically functionalized graphene can be synthesized from amidoamine, polyamide, aliphatic amine, modified aliphatic amine, cycloaliphatic amine, aromatic amine, anhydride, ketimine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine ( 33. Graphene sheets having chemical functional groups selected from the group consisting of TEPA), polyethylene polyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated hardeners, non-amine hardeners, and combinations thereof. The method described in. Chemically functionalized graphene can be 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, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or transition state analog of the enzyme substrate. or 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', 34. The method of claim 33 , wherein and w are integers greater than 1 and less than 200. 34. The method of claim 33 , wherein the binder resin comprises 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. The binder resin comprises a thermoplastic polyfunctional epoxy monomer selected from diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, or combinations thereof. 34. The method of claim 33 , comprising a curable resin. The binder resin includes trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylolethane triglycidyl ether, and tetraphenylene triglycidyl ether. Tetraglycidyl ether of roll ethane, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether , propoxylated glycerin triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Di- or trifunctional selected from the group consisting of ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl carboxylate and mixtures thereof. 34. The method of claim 33 , comprising a thermoset resin comprising a polypropylene epoxy monomer. The binder resins include acrylate and methacrylate oligomers, (meth)acrylates (acrylates and methacrylates), polyhydric alcohols having (meth)acrylate functional groups and derivatives thereof, such as ethoxylated trimethylolpropane tri(meth)acrylate, tripropylene. Glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1, 6-hexanediol di(meth)acrylate or neopentyl glycol di(meth)acrylate and mixtures thereof, and low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, epoxy acrylates, polybutadiene resins and acrylate and methacrylate oligomers derived from polythiol - polyene resins.