(12) Patent Application Publication (10) Pub. No.: US 2017/0037257 A1 YANG Et Al

US 20170037257A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2017/0037257 A1 YANG et al. (43) Pub. Date: Feb. 9, 2017

(54) GRAPHENE-BASED COATINGS Publication Classification Applicant: Board of Regents, the University of (51) Int. C. (71) C09D 5/08 (2006.01) Texas System, Austin, TX (US) C09D 7/12 (2006.01) (72) Inventors: Duck J. YANG, Flower Mound, TX C09D 5/16 (2006.01) (US); Daniel N. TRAN, Carrollton, TX (52) U.S. C. (US); Sangmin LEE, McKinney, TX CPC ...... C09D 5/084 (2013.01); C09D 5/1618 (US) (2013.01); C09D 7/1225 (2013.01); C08K 3/04 (2013.01) (21) Appl. No.: 15/304,260 (22) PCT Fed: Apr. 14, 2015 (57) ABSTRACT (86) PCT No.: PCT/US 15/25693 The present disclosure relates to coatings comprising func tionalized graphene(s) and polymers (resins). In accordance S 371 (c)(1), with the disclosure, graphene can be used with functional (2) Date: Oct. 14, 2016 ization with polymers (resins) with or without pigments, fillers, reactive catalysts or accelerators as finishes to protect Related U.S. Application Data roll steel, galvanized roll steel, equipment, automobiles, (60) Provisional application No. 61/979,341, filed on Apr. ships, construction and marine structures from corrosion, 14, 2014. fouling and UV deterioration. Patent Application Publication Feb. 9, 2017. Sheet 1 of 7 US 2017/0037257 A1

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Patent Application Publication Feb. 9, 2017. Sheet 4 of 7 US 2017/0037257 A1

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GRAPHENE-BASED COATINGS wherein the composition is used as a coating. In some embodiments, the binder is a polymeric binder. In some 0001. The present application is a national phase appli embodiments, the binder is an urethane resin, an epoxy cation under 35 U.S.C. S371 of International Application resin, acrylic resin, or an alkyd resin. In some embodiments, No. PCT/US2015/025693, filed Apr. 14, 2015, which claims the binder comprises two or more components. The binder benefit of priority to U.S. Provisional Application Ser. No. may also further comprise two components wherein at least 61/979,341, filed Apr. 14, 2014, the entire contents of each one of the components is a resin further comprising a of which are hereby incorporated by reference. catalyst. In some embodiments, the resin further comprising BACKGROUND a catalyst is DPX 1 with DPX 2. The binder may be DPX-170, DPX-171, DPX-172, or DPX-173. 0002 A. Field 0013. In some embodiments, the functionalized graphene 0003. The present disclosure relates to coatings compris is present in a layer consisting of a depth of 1 to 10 sheets ing graphene and polymers (resins) and potentially fillers of functionalized graphene. In some embodiments, the depth and pigments. In accordance with the description, graphene of the functionalized graphene consists of 1, 2, 3, or 4 sheets can be used with functionalization with polymers (resins) through more than 50% of the coating. The coating may including reactive catalysts or accelerators as finishes to comprise from about 0.5-20 wt % of functionalized gra protect roll steel, galvanized roll Steel, automobiles, equip phene. In some embodiments, the coating comprises 0.5-10 ment, ships, construction and marine structures from corro wt % of functionalized graphene. The coating may comprise sion, fouling and UV deterioration. 1-5 wt % of functionalized graphene. In some embodiments, 0004 B. Background the coating comprises 0.5,0.75, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 0005. The technology encompasses the combination of 12.5, or 15 wt %, or any range derivable thereof. In some graphene with polymers to perform as corrosion and fouling embodiments, the coating comprises functionalized gra resistant and UV absorbing and hydrophobic finishes for roll phene present in a layer from about 0.001 to 10 um. The steel, galvanized roll steel, automobiles, ships, construction layer may be from about 0.01 to 5 um or from about 0.05 to and marine structures. The multi-functional properties of 2 Lum. graphene Such as hydrophobicity. It to It stacking (self 0014. In some embodiments, the functionalized graphene assembly), UV absorption and barrier with a high surface comprises one or more functional groups selected from: area (2,630 sqm/gram) provide the finishes with anti-cor amino, cyano, hydroxyl, carboxylic acid, isocyanate, alde rosion, anti-fouling, hydrophobic and UV absorbing func hyde, epoxide, urea, or anhydride. tions in finishes. 0015. In some embodiments, the compositions further 0006 Surface coatings can used to impart articles with comprise a carrier. The carrier may be water or an organic desirable properties that are not possessed by the articles Solvent selected from an aliphatic compound; an aromatic themselves or not possessed in a sufficient degree. Many of compound; mineral spirits; methyl ethyl ketone; n-butyl these drawbacks can be overcome by the use of polymeric acetate; ethanol, isopropanol, t-butyl alcohol; and ethylene materials, which can have cost, weight, processability, and glycol, and mixtures thereof. In some embodiments, the flexibility of design advantages over metals. However, most aliphatic compound is hexanes. In other embodiments, the polymer materials are not intrinsically electrically or ther aromatic compound is toluene or Xylene. The compositions mally conductive enough for many applications. Conductive may further comprise a filler. In some embodiments, the polymeric resin compositions can be made in Some cases by filler is treated clays, calcium carbonate powders, alumino adding fillers to polymers, but high loadings are often silicate fine powders, fine-particle-size silica aerogel-type required, which can be to the detriment of physical and other pigments, and ultrahigh-molecular-weight polymers such as properties of the materials, as well as lead to melt processing modified cellulosic polymers, natural polymers like carra difficulties when thermoset materials are used, among other geenan, and high-molecular-weight water-soluble polymers. possible drawbacks. The composition may further comprise a pigment. In some 0007 Coatings can also be used for countless other embodiments, the pigment is a fine particle ranging in size applications, including providing moisture resistance, cor from 0.01 to 100 um like carbon black, TiO, Zinc oxide, rosion resistance, UV radiation resistance, abrasion resis antimony oxide, iron oxide (inorganic) Zinc powder, alumi tance, thermal conductivity, impact resistance, stiffness, and num metal flake, or an organic dye selected from the dye many others. classes of diazo, phthalocyanine, or quinacridone com 0008. It would be desirable to obtain coatings that can be pounds, or another pigment known in the art. The compo used with a wide variety of substrates to provide useful sitions may further comprise a dispersant. In some embodi properties. ments, the dispersant is alkali polyphosphate, alkali poly acrylate, poly-ethylene glycol, linear alkylbenzene SUMMARY Sulfonate, or other dispersants know in the art 0009 Disclosed and claimed herein is coatings compris 0016. In yet another aspect, the present disclosure pro ing graphene and polymers (resins) and which may further vides methods of coating a Substrate comprising: applying a comprise fillers and pigments. Further disclosed and claimed composition described herein to the surface of the substrate herein is a method for coating a Substrate with a coating to form a coating on the surface of the substrate. The comprising graphene and polymers (resins) and fillers and Substrate may be made of metal or may be made of a pigments. polymer. The substrate may be made of fabric, textile, or 0010. In one aspect, the present disclosure provides com pulp. positions comprising: 0017. In some embodiments, the coating is from about 0011 (A) functionalized graphene; and 0.1 um to about 10 mm (millimeters) thick. The coating may 0012 (B) a binder, be from about 0.1 um to about 300 um thick. The coating US 2017/0037257 A1 Feb. 9, 2017

may be from about 5um to about 300 um thick. The coating selected from: an e-coating, a primer, a base coat, or a top may be from about 15 um to about 30 um thick. In some coat. The composition may be incorporated into one or more embodiments, the coating of the composition is applied on of the additional coatings. The composition may be formu top of another coating. In some embodiments, another lated as a suspension, a solution, a paste, a material in coating is applied on top of the coating of the composition. Substantially solid form, a free-flowing Solid, a Viscous 0018. In still another aspect, the present disclosure pro Solid, or a powder. The composition may be applied to the vides compositions comprising: Surface by painting, spin casting, Solution casting, printing, 0019 (A) functionalized graphene; and electrospray printing, cathodic deposition, brush painting, 0020 (B) a resin. dip coating, roll coating, or powder coating. 0021. In some embodiments, the composition is used as 0026. The composition may also exhibit decreased UV a coating. In some embodiments, the coating is applied to degradation compared to a composition without functional steel. The steel may be galvanized or rolled steel. In some ized graphene. The composition may also exhibit decreased embodiments, the Steel has been grit blasted. The coating is corrosion compared to a composition without functionalized a coating may be on a metal Substrate, an automobile, a ship, graphene. The composition may also exhibit decreased a concrete surface, a marine structure, or a construction fowling compared to a composition without functionalized Structure. graphene. The composition may also exhibit increased 0022. In some embodiments, the functionalized graphene hydrophobicity compared to a composition without func contains at least one chemical group selected from: amine, tionalized graphene. The composition may further exhibit cyano, carboxylic acid, hydroxyl, isocyanate, aldehyde, improved adhesion compared to a composition without epoxide, urea, or anhydride. In some embodiments, the functionalized graphene. functionalized graphene contains at least one chemical 0027. In yet still another aspect, the present disclosure group which comprises a nitrogen containing group. provides compositions comprising: 0023. In some embodiments, the resin is a phenolic resin, 0028 (A) a functionalized graphene; and a polyester resin, a polyol resin, an epoxy resin, or an (0029 (B) a resin, isocyanate resin. The resin may be an epoxy resin. The 0030 wherein the functionalized graphene is reacted epoxy resin may be bisphenol A diglycidyl ether (DGEBA), with the resin to form a polymeric resin consisting essen bisphenol F epoxy resin, novolac epoxy resin, aliphatic tially of functionalized graphene and resin repeating units epoxy resin, or glycidylamine epoxy resin, or other epoxy and the resultant polymeric resin is used as a coating. In resins known in the art. In other embodiments, the resin is some embodiments, the functionalized graphene comprises an isocyanate resin. The resin may be methylene diphenyl one or more chemical groups selected from: amine, cyano, diisocyanate (MDI), toluene diisocyanate (TDI), hexameth carboxylic acid, hydroxyl, isocyanate, aldehyde, epoxide, ylene diisocyanate (HDI), or isophorone diisocyanate urea, alkene, aralkene, or anhydride. (IPDI), diamine bisphenols, or other isocyanate resins 0031. The resin may be an epoxy, isocyanate, polyol, known in the art. In other embodiments, the resin is a polyol polyester, or phenolic resin. The functionalized graphene resin. The polyol resin may be hydroxy-terminated aliphatic may comprise one or more amine, carboxylic acid, hydroxy, polyol, hydroxyl-terminated polybutadienes, hydroxy-ter or urea groups when the resin is an isocyanate resin. The minated block co-polymeric diol or other polyol resins functionalized graphene may comprise one or more amine, known in the art. In other embodiments, the resin is a anhydride, carboxylic acid, or hydroxyl groups when the polyester resin. The polyester resin may be polyglycolic resin is an epoxy resin. The functionalized graphene may acid, polylactic acid, polycaprolactone, polyhydroxyalkano comprise one or more isocyanate groups when the resin is a ate, polyhydroxybutyrate, polyethylene adipate, polybuty polyol resin. The functionalized graphene may comprise one lene Succinate, poly(3-hydroxybutyrate-co-3-hydroxyvaler or more alkene, aralkene, or anhydride groups when the ate), polyethylene terephthalate, polybutylene terephthalate, resin is a polyester resin. The functionalized graphene may polytrimethylene terephthalate, polyethylene naphthalate, or comprise one or more aldehyde groups when the resin is a Vectran. In other embodiments, the resin is a phenolic resin. phenolic resin. In some embodiments, the resin comprises a In some embodiments, the resin comprises a cross-linked cross-linked resin of formaldehyde and phenol or a substi resin of formaldehyde and phenol or a substituted phenol. tuted phenol. The fluoropolymer resin may be partially fluorinated or 0032. The composition may also comprise a filler or a perfluorinated resins known in the art. pigment. In some embodiments, the composition further 0024. In other embodiments, the composition further comprises adding an accelerator. The accelerator may be a comprises a filler or a pigment. In some embodiments, the metal catalyst, a basic catalyst, an acid catalyst, an azide composition further comprises adding an accelerator. The compound, or a peroxide. The metal catalyst may be dibutyl accelerator may be a metal catalyst, a basic catalyst, an acid tin dilaurate or Zinc octoate. In some embodiments, the basic catalyst, an azide compound, or a peroxide. The metal catalyst is a tertiary amine. In some embodiments, the acid catalyst may be dibutyl tin dilaurate or zinc octoate. The catalyst is a carboxylic acid, phenol, oxalic acid, hydrochlo basic catalyst may be a tertiary amine. The acid catalyst may ric acid, or Sulfonic acid. The peroxide may be a ketone be a carboxylic acid, phenol, oxalic acid, hydrochloric acid, peroxide, a diacyl peroxide, a dialkyl peroxide, a peroxyes or Sulfonic acid. The peroxide may be a ketone peroxide, a ter, a peroxyketal, a peroxydicarbonate, or a peroxymono diacyl peroxide, a dialkyl peroxide, a peroxyester, a per carbonate. oxyketal, a peroxydicarbonate, or a peroxymonocarbonate. 0033. In some embodiments, the coating is from about 5 0025. In some embodiments, the coating is from about 5 um to about 300 um thick. The coating may be from about um to about 300 um thick. The coating may be from about 15 um to about 30 um thick. In some embodiments, the 15 um to about 30 um thick. In some embodiments, the Surface further comprises one or more additional coatings Surface further comprises one or more additional coatings selected from: an e-coating, a primer, a base coat, or a top US 2017/0037257 A1 Feb. 9, 2017 coat. The composition may be incorporated into one or more ing, corrosion protection and UV durability. In some of the additional coatings. The composition may be formu embodiments, the coating is used on the Surface of concrete lated as a Suspension, a solution, a paste, a material in Structures. Substantially solid form, a free-flowing Solid, a Viscous 0041. In some embodiments, the coating has a thickness Solid, or a powder. The composition may be applied to the of at least about 5 microns. In other embodiments, the Surface by painting, spin casting, Solution casting, printing, thickness is from 15-30 microns. In some embodiments, the electrospray printing, cathodic deposition, brush painting, coating has a thickness of 300 microns or less. In some dip coating, roll coating, or powder coating. embodiments, the coating is includes in the e-coat, primer, 0034. The composition may also exhibit decreased UV base, and top (clear) coatings to prevent corrosion. In some degradation compared to a composition without functional embodiments, the coating exhibits improved UV-absorption ized graphene. The composition may also exhibit decreased properties. In some embodiments, the coating exhibits corrosion compared to a composition without functionalized improved corrosion-resistant properties. In some embodi graphene. The composition may also exhibit decreased ments, the coating exhibits improved hydrophobicity and fowling compared to a composition without functionalized anti-fouling. In some embodiments, the coating exhibits graphene. The composition may also exhibit increased improved adhesion. In some embodiments, the composition hydrophobicity compared to a composition without func comprises functionalized graphene sheets and a resin. The tionalized graphene. The composition may further exhibit composition may further comprise a pigment or a filler. In improved adhesion compared to a composition without other embodiments, the composition further comprises an functionalized graphene. accelerator. In some embodiments, the accelerator is a 0035. In some aspects, the present disclosure provides peroxide or an amine or acid catalyst. articles wherein the article is coated with a composition 0042. In some embodiments, the graphene is functional described herein. In some embodiments, the article is a ized with OH, Amine, -COOH, -NHCONH, when the metal Substrate, a car, a ship, a marine instrument, a marine resin is isocyanate. In some embodiments, the isocyanate structure, construction equipment, or a construction tool. In resin is methylene diphenyl diisocyanate (MDI), toluene some embodiments, the article is made of steel. The steel diisocyanate (TDI), hexamethylene diisocyanate (HDI) or may be rolled steel or galvanized rolled steel. isophorone diisocyanate (IPDI). In some embodiments, the 0036. In some aspects, the present disclosure provides graphene is functionalized with amine, anhydride, hydroxy coatings comprising functionalized graphene and at least (OH), or —COOH, when the resin is epoxy. In some one binder (possibly including filler and pigment). The embodiments, the epoxy resin can be bisphenol Adiglycidyl binder may be a polymeric binder. The coating may further ether (DGEBA), bisphenol F epoxy resin, novolac epoxy comprise one or more carriers, fillers, pigments, or disper resin, aliphatic epoxy resin or glycidylamine epoxy resin. In sants, electrically conductive polymer. In some embodi Some embodiments, the graphene is functionalized with ments, the coating comprises at least one carbonaceous isocyanate when the resin is polyol. The graphene may be material other than the functionalized graphene sheets. In functionalized with styrene or anhydride (maleic or phthalic) Some embodiments, the graphene is single sheet graphene or when the resin is unsaturated polyester resin. In other double or 3-4 sheet graphene or combination thereof. In embodiments, the graphene is functionalized with aldehyde some embodiments, the size of the graphene is 0.05-10 when the resin is phenolic resin. microns. The coating may be 0.05-5 microns. The coating 0043. In some embodiments, the composition is a sus may also be 0.01-2 microns pension, Solution, paste, materials in Substantially solid form 0037. In still another aspect, the present disclosure pro containing little or no liquids, free-flowing, viscous, Solid, or vides methods for coating a substrate having a Surface, powder. In some embodiments, the composition may be comprising the step of applying a coating comprising func applied to a Substrate using any suitable method, including, tionalized graphene sheets and at least one binder to the but not limited to, painting, spin casting, solution casting, Surface. The Substrate may also comprise a polymeric mate printing (including inkjet printing), electrospray printing, rial. In some embodiments, the Substrate is a metal. In other cathodic deposition or painting, brush painting, dip coating, embodiments, the substrate is a fabric, textile, or pulp roll coating, or powder coating. product. 0044. In some embodiments, the accelerator is added in 0038. In still yet another aspect, the present disclosure the presence of heat. In other embodiments, the accelerator provides articles coated with a coating comprising function is added in the absence of heat. alized graphene sheets having at least one binder. 0045. In some embodiments, the accelerator is metal 0039. In still another aspect, the present disclosure pro catalyst Such as dibutyl tin dilaurate or Zinc octoate. In some vides graphene-based coatings wherein the coating is used embodiments, the accelerator is acid catalyst Such as a for corrosion protection on a steel surface. The steel surface tertiary amine, a carboxylic acid or a phenol. In some may be a roll steel Surface or a galvanized roll steel Surface. embodiments, the accelerator is a peroxide Such as a ketone The steel surface may be a grit blasted roll steel surface. In peroxide, a diacyl peroxide, a dialkyl peroxide, a peroxyes Some embodiments, the coating is used on automobile ters, a peroxyketal, a peroxydicarbonate or a peroxymono surfaces for corrosion protection, UV durability and ease of carbonate. In some embodiments, the accelerator is Oxalic cleaning. In other embodiments, the coating is used on the acid, hydrochloric acid or Sulfonate acid. Surface of ships. In some embodiments, the thickness of the composition on 0040. In some embodiments, the coating provides anti a surface of a substrate is 1-100 microns. In some embodi fouling, corrosion protection and UV durability to the coated ments, the thickness is 20-60 microns (1-2 mils). Surface. In some embodiments, the coating is used on the 0046 Embodiments of the disclosure are also directed to Surface of construction and marine structures for anti-foul a method for coating a Substrate having a surface, compris US 2017/0037257 A1 Feb. 9, 2017

ing the step of applying a coating comprising functionalized 0055 FIG. 2 plots the function of the coating loss based graphene sheets and at least one binder (resin) to the Surface. upon the graphene content in a salt water solution. 0047. An embodiment of the disclosure is directed to an 0056 FIG.3 plots the function of the coating loss based article coated with a coating comprising functionalized upon the graphene content in high humidity. graphene sheets having at least one binder. Other embodi 0057 FIG. 4 plots the change in corrosion from a salt ments of the disclosure include the functionalized graphene water Solution based upon the amount of graphene in the based coating wherein the coating is used for corrosion coating after about 1100 hours. protection on a steel Surface; the graphene-based coating, 0.058 FIG. 5 plots the change in corrosion from a salt wherein the coating is used on automobile Surfaces for water Solution based upon the amount of graphene in the corrosion protection, UV durability and ease of cleaning; the coating after about 1500 hours. graphene-based coating, wherein the coating is used on the 0059 FIG. 6 plots the change in contact angle based Surface of ships, wherein the coating provides anti-fouling, upon the amount of graphene in an artistic gloss varnish. corrosion protection and UV durability to the coated surface; 0060 FIG. 7 plots the change in contact angle based the graphene-based coating wherein the coating is used on upon the amount of graphene in an dammar Varnish. the Surface of construction and marine structures for anti 0061 FIG. 8 plots the change in contact angle based fouling, corrosion protection and UV durability; the gra upon the amount of graphene in an acrylic varnish. phene-based coating wherein the coating is used on the 0062 FIG. 9 plots the change in UV absorbance based Surface of concrete structures. upon graphene concentration in a gloss varnish. 0.048 Embodiments of the disclosure are further directed 0063 FIG. 10 plots the change in UV absorbance based to the graphene-based coating wherein the coating has a upon graphene concentration in a dammar Varnish. thickness of at least about 5 microns, or more preferably at 0064 FIG. 11 plots the change in UV absorbance based least about 30-60 microns. Certain embodiments of the upon graphene concentration in a acrylic varnish. disclosure are directed to the graphene-based coating 0065 FIG. 12—shows a representative diagram of a wherein the coating has a thickness of 300 microns or less. simple graphene enchanced base coat on a marine concrete Further embodiments of the disclosure are directed to a base structure or metal substrate. graphene-based coating wherein the coating is includes in 0.066 FIG. 13—shows a representative diagram of a the primer (or e-coat), base, and top coatings to prevent simple graphene enchanced base coat on a metal Substrate corrosion, fouling, and UV deterioration. with an additional UV protection graphene top coat. 0049. The use of the word “a” or “an, when used in 0067 FIG. 14—shows a representative diagram of an conjunction with the term "comprising in the claims and/or enhanced graphene based coating for automotive vehicles. the specification may mean "one.” but it is also consistent The graphene enhanced coatings can include the primer, with the meaning of “one or more.” “at least one.” and “one base, and top coatings to prevent corrosion. or more than one.” DESCRIPTION OF EXEMPLARY 0050. Throughout this application, the term “about is EMBODIMENTS used to indicate that a value includes the inherent variation of error for the device, the method being employed to 0068. As used herein, the term “coating refers to a determine the value, or the variation that exists among the coating in a form that is suitable for application to a substrate study Subjects. In some aspects, the term “about may be as well as the material after it is applied to the substrate, used to represent a difference of plus or minus 5%. while it is being applied to the substrate, and both before and 0051. It is contemplated that any method or composition after any post-application treatments (such as evaporation, described herein can be implemented with respect to any cross-linking, curing, and the like). The components of the other method or composition described herein. coating compositions may vary during these stages. 0052. Other objects, features and advantages of the pres 0069. The coatings comprise functionalized graphene ent disclosure will become apparent from the following and polymer binders and may optionally comprise additional detailed description. It should be understood, however, that components, such as at least one carrier like filler, pigment, the detailed description and the specific examples, while catalyst, or accelerator other than a binder. indicating specific embodiments of the disclosure, are given 0070. Some non-limiting examples of types of binders by way of illustration only, since various changes and include polymeric binders. Polymeric binders (resins) can be modifications within the spirit and scope of the disclosure thermoplastics or thermosets or modified natural alkyl resins will become apparent to those skilled in the art from this and may be elastomers or fluoropolymers. Binders may also detailed description. Note that simply because a particular comprise monomers that can be polymerized before, during, compound is ascribed to one particular generic formula or after the application of the coating to the Substrate. doesn’t mean that it cannot also belong to another generic Polymeric binders may be cross-linked or otherwise cured formula. after the coating has been applied to the Substrate. Examples of polymeric binders include polyethers such as poly(eth BRIEF DESCRIPTION OF THE FIGURES ylene oxide)S (also known as poly(ethylene glycol)s, poly (propylene oxide)S (also known as poly(propylene glycol)S. 0053. The following drawings form part of the present and ethylene oxide?propylene oxide copolymers, cellulosic specification and are included to further demonstrate certain resins (such as ethyl cellulose, ethyl hydroxyethyl cellulose, aspects of the present disclosure. The disclosure may be carboxymethyl cellulose, cellulose acetate, cellulose acetate better understood by reference to one or more of these propionates, and cellulose acetate butyrates), and polyvinyl drawings in combination with the detailed description. butyral, polyvinyl alcohol and its derivatives, ethylene/vinyl 0054 FIG. 1 plots the change in the contact angle as a acetate polymers, acrylic polymers and copolymers, styrene? function of the graphene content. acrylic copolymers, styrene? maleic anhydride copolymers, US 2017/0037257 A1 Feb. 9, 2017 isobutylene/maleic anhydride copolymers, vinyl acetate/eth When isocyanate resin is used with a functionalized gra ylene copolymers, ethylene? acrylic acid copolymers, poly phene, the functionalized group can be hydroxyl, amine, olefins, polystyrenes, olefin and styrene copolymers, ure urea, and other functional groups known to react with thane resins, isocyante resins. epoxy resins, acrylic latex isocyanate resin in the art and the isocyanate resin can be polymers, polyester acrylate oligomers and polymers, poly methylene diphenyl diisocyanate (MDI), toluene diisocya ester diol diacrylate polymers, UV-curable resins, and poly nate (TDI), hexamethylene diisocyanate (HDI) or iso amide, including polyamide polymers and copolymers. phorone diisocyanate (IPDI) or other known isocyanate 0071. One method of obtaining graphene is from graphite resins. and/or graphite oxide (also known as graphitic acid or 0077. When epoxy resin is used, the functionalized group graphene oxide). Graphite may be treated with oxidizing and can be amine, anhydride or hydroxyl (OH) and the epoxy intercalating agents and exfoliated. Graphite may also be resin can be bisphenol A diglycidyl ether (DGEBA), bis treated with intercalating agents and electrochemically oxi phenol F epoxy resin, novolac epoxy resin, aliphatic epoxy dized and exfoliated. resin or glycidylamine epoxy resin, or other known epoxy 0072 Reduction of graphite oxide to graphene may be by resins. means of chemical reduction using hydrogen gas or other 0078. When polyol resin is used, the functionalized group reducing agents. Examples of useful chemical reducing can be isocyanate. When unsaturated polyester resin is used, agents include, but are not limited to, hydrazines (such as the functionalized group can be styrene or anhydride such as hydrazine, N1N-dimethylhydrazine, etc.), sodium borohy maleic or phthalic anhydride when phenolic resin is used, dride, hydroquinone, and the like. For example, a dispersion the functionalized group can be aldehyde. of exfoliated graphite oxide in a carrier (Such as water, 007.9 The ratio of total number of functional group from organic solvents, or a mixture of solvents) can be made using graphene in Part A to the total number of functional group any suitable method (such as ultrasonication and/or from resin in Part B is preferably 1-3 and most preferably mechanical grinding or milling) and reduced to graphene. close to 1 0073 Graphite oxide may be produced by any method 0080. The weight% of graphene in solids once Part A and known in the art, Such as by a process that involves oxidation Part B is mixed is in the range of 0.1-10%, preferably 1-5%. of graphite using one or more chemical oxidizing agents I0081. The size of graphene is 0.01-25 microns, prefer and, optionally, intercalating agents such as Sulfuric acid. ably, 0.1-10 microns, most preferably 0.05-0.50 microns. Examples of oxidizing agents include nitric acid, sodium Functionalized graphene can be a single layered graphene and potassium nitrates, perchlorates, hydrogen peroxide, sheet, double layered, triple layered or combination thereof, Sodium and potassium permanganates, phosphorus pentox and preferably single layered graphene. ide, bisulfites, and the like. Some potential oxidants include I0082 In certain embodiments, the coating is composed of KCIO: HNO, and KCIO, KMnO, and/or NaMnO: one Part: water-based latex paints; and solvent-based paints, KMnO, and NaNO; KSOs and POs and KMnO, interior and exterior, primer and sealer. KMnO and HNO; and HNO. One intercalation agent 0.083. 1) Water-based latex paints or primer: function includes sulfuric acid. Graphite may also be treated with alized graphene where X—OH, COOH or Ketone or intercalating agents and electrochemically oxidized. Graph —NH, weight % of graphene in solids in the paint is ite may also be treated with intercalating agents and elec in the range of 0.1-10%, preferably 1-5%. trochemically oxidized to be exfoliated to individual gra 0084. 2) Solvent-based paints, primer: functionalized phene oxide (GO) sheet or sheets by using Sonication or graphene where X=Ketone or none; Weight % of other methods. The GO products, reduces or as prepared are graphene in Solids in the paint is in the range of commercially available. Furthermore, graphene oxide can 0.1-10%, preferably 1-5%. be further functionalized with an amine, a hydroxyl, or 0085 3) Silicone sealant: functionalized graphene carboxylic acid as described in the literature. where X=Ketone or none; Weight % of graphene in 0074 The coatings may optionally contain electrically solids in the paint is in the range of 0.1-10%, preferably conductive components other than the functionalized gra 1-5%. phene Such as metals (including metal alloys), conductive I0086 4) Electro-deposition coating: Waterborne metal oxides, polymers, carbonaceous materials other than cathodic electrodeposition (CED) coating composi the high Surface area functionalized graphene sheets, and tions comprising resin Solids and optionally pigments, metal-coated materials. These components can take a variety fillers and conventional coating additives, wherein said of forms, including particles, powders, flakes, foils, needles, CED coating compositions comprise at least one gra etc phene compound in a quantity of 0.1 to 5 wt.% where 0075. The coatings may optionally contain fillers or pig X can be OH, COOH, NH, NCO, Epoxy when it was ments other than the functionalized graphene Such as silica, reacted with resin. fumed silica, alumina, calcium carbonate, Zeolite and clays 0.087 5) Powder coating: Powder coating resin is pre or TiO2 and other color pigments known in the art. The pared by a resin Synthesis followed by removing sol coatings may also optionally contain catalysts or accelerator vent thru spray drying. The functionalized graphene is including hardener other than the functionalized graphene to added during the resin synthesis. Weight% of graphene promote a fast curing of coatings as well as better cross in solids is in the range of 0.1-10%, preferably 1-5%. linking of thermoset coatings. X can be dependent of kind of resin. For instance, if the 0076. In certain embodiments of the disclosure, the coat resin is a urethane, X can be OH, COOH or - NH. ing is composed of two parts: Part A contains functionalized I0088. The current technology for ship base coats involves graphene sheets and Part B contains reactive resin or a resin grit blasting followed by application of zinc powder with with a catalyst or accelerator incorporated. An accelerator organosilane binders which is not only labor intensive but (amine or acid catalyst) can be therefore included in part A. hazardous to health. These coatings are required to be US 2017/0037257 A1 Feb. 9, 2017

stripped and reapplied periodically which can be costly. In Examples of suitable carriers include, but are not limited to, addition, current anti-fouling paints contained either toxic water, distilled or hydrocarbons. copper oxide or silane base resin System having on-purpose 0104. The coatings may optionally comprise one or more peeling property to be fouling resistance. In contrast to it, additional additives. Such as dispersion aids (including Sur described herein the enhancement of hydrophobicity of top factants, emulsifiers, and wetting aids), adhesion promoters, coating may be used to increase the anti-fouling effects of thickening agents (including clays), defoamers and anti the top coating. To have adequate corrosion and fouling foamers, biocides, additional fillers, flow enhancers, stabi protection, currently available compositions coat thicker lizers, cross-linking and curing agents, and the like. In one coating (>300 microns) which requires deeper grit blasting embodiment of the present disclosure, the Surfactant is at to Sustain adhesion between Substrate and coating. Since the least one ethylene oxide/propylene oxide copolymer. claimed system does not use peeling to be anti-fouling and enhance corrosion protection of each layer, the thickness can 0105. The (graphene or) functionalized graphene is pres be reduced. The reduction of thickness will save a lot of ent in the coating in at least about 0.01-5.0 weight percent material and labor cost and reduce VOC release, and make based on the total weight of the coating. In one embodiment the claimed system become a humane friendly and environ of the disclosure, the functionalized graphene is preferably mentally friendly system. present in the coatings in at least about 0.01-2.0 weight percent, or more preferably in at least about 0.05 weight percent, or yet more preferably in at least about 0.1 weight Use of the Finishes (Two Parts or One Part) percent, or still more preferably in at least about 2.0 weight 0089 Purposes/benefits: Corrosion resistant, water resis percent, or even more preferably in at least about 1-2 weight tant, fouling resistant and UV durable coating. percent, where the weight percentages are based on the total 0090. Applications: equipment, automobiles, ships, weight of the coating Solids after it has been applied to a architectural buildings, bridges, civil and marine structures Substrate and Subjected to any post-application treatments 0091 Automotive: e-coat, primer, base coat and color (such drying, curing, cross-linking, etc.). However, as will coat and clear coat (1-2 mill thickness each) be appreciated by those skilled in the art, the amount of 0092 Body shop: primer, base coat and color coat and functionalized graphene present in the coatings can be clear coat (1-2 mill thickness each) selected based on the desired properties and the particular 0093 Ship & marine structure: primer and top coat. binders and other optional components chosen. Besides the benefits, the present formulation will reduce 0106. In one embodiment of the present disclosure, the degree of grit blasting (less surface roughness) and thinner coatings are electrically conductive. The coatings may be coating VS. current coating system: significant labor cost made using any Suitable method, including wet or dry savings and alleviate environmental problem of current methods and batch, semi-continuous, and continuous meth system. Current primer has Zinc dust in composition but our ods. The resulting blends may be further processed by graphene based finish can reduce the amount of its use or grinding using wet or dry grinding technologies or Sonica eliminate its use. tion. The technologies can be continuous or discontinuous. Examples include ball mills, attrition equipment, Sandmills, Methods of Application and horizontal and vertical wet grinding mills, bath Sonica 0094 Spray—cars, ships, structures tion or probe Sonication. Suitable materials for use as 0095 Flow roll steels grinding media include metals, carbon steel, stainless steel, 0096 Brush home ceramics, stabilized ceramic media (Such as yttrium stabi 0097 Roll home lized Zirconium oxide), PTFE, glass, tungsten carbide, and 0098 Electrodeposition (cathodic)—cars, roll steel the like. After blending and/or grinding steps, additional 0099 Powder coating cars, appliances components may be added to the coatings, including, but not 0100 Examples of metals used in the compositions limited to, thickeners, viscosity modifiers, and the like. The include, but are not limited to silver, copper, aluminum, coatings may also be diluted by the addition of more carrier. platinum, palladium, nickel, chromium, gold, bronze, and 0107 After they have been applied to a substrate, the the like. Examples of metal oxides include titanium oxide, coatings may be cured using any suitable technique, includ antimony tin oxide and indium tin oxide and color pigments, ing drying and oven-drying (in air or another inert or and materials such as fillers coated with metal oxides. Metal reactive atmosphere), UV curing, IR curing, microwave and metal-oxide coated materials include, but are not limited curing or drying, and the like. The coatings may be applied to metal coated carbon and graphite fibers, metal coated to a wide variety of Substrates, including, but not limited to, glass fibers, metal coated glass beads, metal coated ceramic metals; polymeric materials; fabrics (including cloths) and materials (such as beads), and the like. These materials can textiles; glasses and other minerals; ceramics; silicon Sur be coated with a variety of metals, including nickel. faces; wood; pulp-based materials such as paper, and card 0101 Examples of electrically conductive polymers board; silicon and other semiconductors; laminates; con include, but are not limited to, polyacetylene, polyethylene crete, bricks, and other building materials; and the like. The dioxythiophene, polyaniline, polypyrroles, and the like. Substrates may have been treated with other coatings or 0102) Examples of carbonaceous materials other than similar materials before the coatings of the present disclo graphene include, but are not limited to, carbon black, Sure are applied. graphite, carbon nanotubes, vapor-grown carbon nanofibers, 0108. The coatings may be in a variety of forms, includ carbon fibers, metal coated carbon fibers. ing, but not limited to, Suspensions, solutions, pastes, and 0103) The coatings may optionally comprise one or more materials in Substantially solid form like powders containing carriers in which some or all of the components are dis little or no liquids. They may be free-flowing, viscous, Solid, Solved, Suspended, or otherwise dispersed or carried. powdery, and the like. US 2017/0037257 A1 Feb. 9, 2017

0109 The coatings may be applied to a substrate using minimal number of carbon atoms for that particular group. any Suitable method, including, but not limited to, painting, By way of an example, aryl groups must comprise a minimal spin casting, Solution casting, printing (including inkjet number of 5 carbon atoms. Also, as used herein, the term printing), electrospray printing or painting, dip coating, micron is used interchangeably with Lum. In some aspects, cathodic deposition, powder coating, and other methods the chemical terms when used in the context of functional known in the art. The coatings can be applied in multiple ized graphene comprise a chemical group attached to one or layers. When applied to a Substrate, the coatings can have a more carbon atoms of the graphene layer. The term “amine' variety of forms. They can be present as a film or lines, is the group —NR wherein each R is either hydrogen, an patterns, and other shapes. The coatings may be covered aliphatic group, or an aromatic group. The term “alkene' or with additional material. Such as overcoatings, varnishes, “aralkene' is a carbon group which comprises at least one polymers, fabrics, and the like. non-aromatic carbon carbon double bond. The term "alde 0110. When applied to a substrate, the coatings can have hyde' represents the group —C(O)H. The term "carboxylic a variety of thicknesses. In one embodiment of the disclo acid represents the group —C(O)CR, wherein R is hydro Sure, when applied to a Substrate the coating can preferably gen, an aliphatic group, or an aromatic group. The term have a thickness of at least about 5 microns, or more “cyano represents the group —C=N. The term "isocya preferably at least about 15 microns. In various embodi nate' represents the group, —N=C=O. The term ments of the disclosure, the coatings can have a thickness of “hydroxyl represents the group, —OH. The term “urea’ about 5 microns to 2 mm, about 15 microns to 1 mm, about represents the group - NHC(NH)NH2. The term “epoxide 5 microns to about 30 microns, about 5 microns to about 90 represents a divalent group which is attached to two carbon microns, about 5 microns to about 300 microns, about 5 atoms of the graphene and forms a three membered ring with microns to about 1 mm, about 15 microns to about 90 an oxygen atom and two carbon atoms of the graphene or microns, about 15 microns to about 300 microns, about 15 one carbon atom from the graphene and another carbon microns to about 1 mm. atom. The term “aldehyde' represents the divalent group, 0111. The coatings can be applied to the same substrate in —C(O)CC(O)—, wherein the group is joined to two differ varying thicknesses at different points and can be used to ent carbon atoms of the graphene backbone. build up three-dimensional structures on the substrate. 0116. The terms “comprise,” “have” and “include” are 0112 Some of the purposes and benefits of the coatings open-ended linking verbs. Any forms or tenses of one or is corrosion resistance, water resistance, fouling resistance more of these verbs, such as “comprises.” “comprising.” and UV durable coating. Applications for the coating include “has,” “having,” “includes” and “including.” are also open equipment, auto, ship, architectural building, bridges, civil ended. For example, any method that “comprises.” “has or and marine structures. In automotive applications, the coat “includes one or more steps is not limited to possessing ing can be used as an e-coat, primer, base coat and color coat only those one or more steps and also covers other unlisted and clear coat (1-2 mill thickness each). In ship and marine steps. structures, the coating can be used as a primer and top coat. 0117. The term “effective, as that term is used in the The amount of functionalized graphene in each coating can specification and/or claims, means adequate to accomplish a also vary. desired, expected, or intended result. 0113 Besides the benefits, the coating reduces the degree 0118. The above definitions supersede any conflicting of grit blasting (less Surface roughness) and thinner coating definition in any reference that is incorporated by reference vs. current coating system. Additionally, significant labor herein. The fact that certain terms are defined, however, cost savings are realized along with alleviation of the should not be considered as indicative that any term that is environmental problem of current system. Current primer undefined is indefinite. Rather, all terms used are believed to has Zinc dust in composition but the graphene based finish describe the disclosure in terms such that one of ordinary can reduce the amount of its use or eliminate its use. skill can appreciate the scope and practice the present 0114. The coatings can also be used for the passivation of disclosure. Surfaces, such as metal (e.g. steel, aluminum, etc.) Surfaces, including exterior structures Such as bridges and buildings. EXAMPLES Examples of other uses of the coatings of the disclosure include: UV radiation resistant coatings, abrasion resistant 0119 The following examples are included to demon (lubricant) coatings, coatings having permeation resistance strate preferred embodiments of the disclosure. It should be to liquids (such as hydrocarbon, alcohols, water, and the appreciated by those of skill in the art that the techniques like) and ions and/or gases, electrically conductive coatings, disclosed in the examples which follow represent techniques static dissipative coatings, and impact resistant coatings. discovered by the inventor to function well in the practice of They can be used to make fabrics having electrical conduc the disclosure, and thus can be considered to constitute tivity. The coatings can be used in Solar cell applications; preferred modes for its practice. However, those of skill in signage, flat panel displays; flexible displays, including the art should, in light of the present disclosure, appreciate light-emitting diode, organic light-emitting diode, and poly that many changes can be made in the specific embodiments mer light-emitting diode displays; backplanes and front which are disclosed and still obtain a like or similar result planes for displays; and lighting, including electrolumines without departing from the spirit and scope of the disclosure. cent and OLED lighting. Example 1 DEFINITIONS Sample Preparation 0115. When used herein, carbon based groups comprise from 1 to 18 carbons or in other embodiments, from 1 to 12 0120 A 2"x2" steel substrate was washed and dried with carbons. The range of carbon atoms is limited by the Soap, Xylene, and isopropanol. The Surface was roughed US 2017/0037257 A1 Feb. 9, 2017

with Sandpaper and rewashed with isopropanol and dried. A square grid (-2x2 cm) was etched in the center of the coated graphene composition was dispersed in DPX 172 at 1%. 2% sample on 1 side of the sample exposing the metal Surface and 4% by final weight using bath Sonication. The graphene under the coating. The sample was then exposed to a high mixed DPX 172 was then mixed with DPX 171 (DPX 172 humidity conditions and Scotch tape was applied across the & 171 are 2K epoxy coating from PPG). The cleaned steel grid Surface ensuring good contact. The Scotch tape was then pieces were then dipped in mixed DPX 171/DPX 172/ removed quickly and the remaining amount of coating on graphene solution and air dried vertically for a total of three the grid was recorded coating cycles. 0.133 Results. 0121 Contact Angle Measurement. 0122 Contact angle was measured by first placing the 0.134 FIG. 3 also shows the same trend for 3.5% NaCl coated steel samples horizontally flat with the addition of a Solution conditions. drop of DI water on the surface of the flat edge. A digital image was from the edge and water droplet angle was TABLE (1) measured. Raw Data for FIG. 4 - ASTM G111 - 97 (2013 (0123 Results. 0.124 FIG. 1 indicates as the graphene content in the Coating Type coating increases, so does the hydrophobic nature and thus contact angle. This indicates increase presence of the gra O% 2% 4% phene composition in the coating has an increasing hydro Corrosion Rate 19.8661 mpy 12.5012 mpy .5421 mpy phobic effect on the coating's Surface. Note: micron per year (mpy) Example 2 Test period: 1123 hours in 3.5% NaCl solution at room temperature Sample Preparation 0.125 2"x2" steel substrate were washed and dried with Example 4 Soap, Xylene, and isopropanol. The Surface was roughed with sandpaper and rewashed with isopropanol and dried. Sample Preparation Graphene was dispersed in DPX 172 at 1%, 2% and 4% by final weight using bath sonication. The graphene mixed 0.135 2"x2" steel substrate were washed and dried with DPX 172 was then mixed with DPX 171. The cleaned Steel Soap, Xylene, and isopropanol. The Surface was roughed pieces were then dipped in mixed DPX 171/DPX 172/ with Sandpaper and rewashed with isopropanol and dried. graphene solution and air dried vertically for a total of three The graphene composition was dispersed in DPX 172 at 1%, coating cycles. 2% and 4% by final weight using bath sonication. The 0126 Adhesion Test. graphene mixed DPX 172 was then mixed with DPX 171. 0127. Coating adhesion was test using ASTM D 3359 The cleaned steel pieces were then dipped in mixed DPX standard test for measuring adhesion by tape test. A 5 by 5 171/DPX 172/graphene solution and air dried vertically for square grid (-2x2 cm) was etched in the center of the coated a total of three coating cycles. sample on 1 side of the sample exposing the metal Surface under the coating. The sample was then exposed to a 3.5% 0.136 Corrosion Test. NaCl solution and Scotch tape was applied across the grid 0.137 Corrosion rate was tested by first weighting and Surface ensuring good contact. The Scotch tape was then measuring of Surface area of the coated Steel samples. Each removed quickly and the remaining amount of coating on sample was then placed in a 3.5% NaCl solution. With the grid was recorded constant replacement of 3.5% NaCl solution and a minimal 0128 Results. time of 5 weeks, each sample was then removed from the 0129 FIG. 2 indicates most solution behave similarly in solution, washed with DI water and acetone, and dried. Rust 3.5% NaCl water. In the case of the 4% graphene content, was then removed by washing with 4M HCl and samples without wishing to be bound by any theory, the graphene were washed with water again and dried in a 100° C. oven. might have a delamination effect. Samples were washed and dried in a similar manner with HCl until sample weight is stabilized. Corrosion rate was Example 3 measured using the formula: Sample Preparation 0130 2"x2" steel substrate were washed and dried with Soap, Xylene, and isopropanol. The Surface was roughed with sandpaper and rewashed with isopropanol and dried. The graphene composition was dispersed in DPX 172 at 1%, where density of the metal is 7.9 g/cm. 2% and 4% by final weight using bath sonication. The graphene mixed DPX 172 was then mixed with DPX 171. 0.138 Results. The cleaned steel pieces were then dipped in mixed DPX 0.139 Table 1 and FIG. 4 indicates increased amount of 171/DPX 172/graphene solution and air dried vertically for Graphene used in the coating significantly lowers the cor a total of three coating cycles. rosion rate; as we predicted, in fact the hydrophobic property 0131) Adhesion Test. of graphene Successfully resists the moisture and acts as a 0132) Coating adhesion was test using ASTM D 3359 high surface corrosion barrier therefor the reduction of standard test for measuring adhesion by tape test. A 5 by 5 corrosion rate. US 2017/0037257 A1 Feb. 9, 2017

TABLE (2) Sonication. Commercial artistic gloss varnish was mixed with the graphene/toluene dispersion. Cleaned quartz slides Raw Data for FIG. 5 - ASTM G111 - 97 (2013 were then dip coated in the graphene/top coat dispersion and Coating Type air dried for a total of 3 cycles. 0146 Contact Angle Measurement. O% 2% 4% 0147 Contact angle was measured by first placing the coated quartz samples horizontally flat with the addition of Corrosion Rate 32.560 mpy 18.921 mpy NA a drop of DI water on the surface of the flat edge. A digital Note: image was from the edge and water droplet angle was micron per year (mpy) measured. Test period: 1459 hours in 3.5% NaCl solution at room temperature 0148 Results. 0149 Table 3 and FIG. 6 contact angle measurements vs Example 5 graphene content for artistic gloss varnish. With increased graphene content, hydrophobicity of the coating is Sample Preparation increased. 0140 2"x2" steel substrate were washed and dried with Soap, Xylene, and isopropanol. The Surface was roughed TABLE (4) with sandpaper and rewashed with isopropanol and dried. Raw Data for FIG. 7 The graphene composition was dispersed in DPX 172 at 1%, 2% and 4% by final weight using bath sonication. The Graphene content (% wt graphene mixed DPX 172 was then mixed with DPX 171. O% 196 2% The cleaned steel pieces were then dipped in mixed DPX 171/DPX 172/graphene solution and air dried vertically for Contact Angle 75 - 14.18 79 - 2.08 81 - 4:16 a total of three coating cycles. 0141 Corrosion Test. 0142 Corrosion rate was tested by first weighting and Example 7 measuring of Surface area of the coated Steel samples. Each sample was then placed in a 3.5% NaCl solution. With Sample Preparation constant replacement of 3.5% NaCl solution and a minimal 0150. Quartz slides were first cleaned by washing with DI time of 5 weeks, each sample was then removed from the water and 1M HCl and dried. The graphene composition was solution, washed with DI water and acetone, and dried. Rust dispersed in toluene at 1% and 2% (by weight) by bath was then removed by washing with 4M HCl and samples Sonication. Commercial Dammar Varnish was mixed with were washed with water again and dried in a 100° C. oven. the graphene/toluene dispersion. Cleaned quartz slides were Samples were washed and dried in a similar manner with then dip coated in the graphene/top coat dispersion and air HCl until sample weight is stabilized. Corrosion rate was dried for a total of 3 cycles. measured using the formula: 0151 Contact Angle Measurement. 0152 Contact angle was measured by first placing the coated quartz samples horizontally flat with the addition of a drop of DI water on the surface of the flat edge. A digital image was from the edge and water droplet angle was measured. where density of the metal is 7.9 g/cm. 0153. Results. 0143 Results. 0154 Table 4 and FIG. 7 contact angle measurements vs 0144 Table 2 and FIG. 5 is an extended study of the graphene content for Dammar Varnish. With increased gra corrosion rate and the increased graphene content on the phene content, hydrophobicity of the coating is increased. coating continues to increase corrosion protection TABLE (5) TABLE (3) Raw Data for FIG. 8 Raw Data for FIG. 6 Graphene content (% wt Graphene content (% wt O% 190 296 O% 190 296 Contact Angle 106 6.OO 114 + 4.16 118 6.24 Contact Angle 99 2.65 109 2.89 121 - 3.61

Example 8 Example 6 Sample Preparation Sample Preparation 0155 Quartz slides were first cleaned by washing with DI 0145 Quartz slides were first cleaned by washing with DI water and 1M HCl and dried. The graphene composition was water and 1M HCl and dried. The graphene composition was dispersed in water at 1% and 2% (by weight) by bath dispersed in toluene at 1% and 2% (by weight) by bath Sonication. Commercial acrylic varnish was mixed with the US 2017/0037257 A1 Feb. 9, 2017 graphene/toluene dispersion. Cleaned quartz slides were graphene/toluene dispersion. Cleaned quartz slides were then dip coated in the graphene/top coat dispersion and air then dip coated in the graphene/top coat dispersion and air dried for a total of 3 cycles. dried for a total of 3 cycles. 0156 Contact Angle Measurement. (0171 UV Measurements. 0157 Contact angle was measured by first placing the 0172 UV absorption was measured by placing the quartz coated quartz samples horizontally flat with the addition of slide in a UV-Vis spectrophotometer and reading from 400 a drop of DI water on the surface of the flat edge. A digital to 200 nm with a blank quartz slide as control. image was from the edge and water droplet angle was (0173 Results. measured. 0.174 FIG. 11 shows an increase the UV absorption when 0158 Results. graphene is mixed with acrylic varnish. FIG. 12 is a repre 0159 Table 5 and FIG. 8 contact angle measurements vs sentative diagram of a simple graphene enhanced base coat graphene content for acrylic varnish. With increased gra on a marine concrete base structure or metal substrate. FIG. phene content, hydrophobicity of the coating is increased. 13 is a representative diagram of a simple graphene enhanced base coat on a metal Substrate with an additional Example 9 UV protection graphene top coat. FIG. 14 is a representative diagram of an enhanced graphene based coating for auto Sample Preparation motive vehicles. The graphene enhanced coatings can include the primer, base, and top coatings to prevent corro 0160 Quartz slides were first cleaned by washing with DI S1O. water and 1M HCl and dried. The graphene composition was 0.175 All of the compositions and methods disclosed and dispersed in toluene at 2% and 7% (by weight) by bath claimed herein can be made and executed without undue Sonication. Commercial gloss varnish was mixed with the experimentation in light of the present disclosure. While the graphene/toluene dispersion. Cleaned quartz slides were disclosure may have focused on several embodiments or then dip coated in the graphene/top coat dispersion and air may have been described in terms of preferred embodi dried for a total of 3 cycles. ments, it will be apparent to those of skill in the art that (0161 UV Measurements. variations and modifications may be applied to the compo 0162 UV absorption was measured by placing the quartz sitions and methods without departing from the spirit, scope, slide in a UV-Vis spectrophotometer and reading from 400 and concept of the disclosure. All variations and modifica to 200 nm with a blank quartz slide as control. tions apparent to those skilled in the art are deemed to be (0163 Results. within the spirit, scope, and concept of the disclosure as 0164 FIG. 9 shows an increase the UV absorption when defined by the appended claims. increase concentration of graphene, when graphene is mixed 1. A composition comprising: into gloss varnish. The gloss varnish contains UV protectant and a great improvement is not seen with low graphene (A) functionalized graphene; and content. However when graphene content is increased to 7% (B) a binder; then a great improvement in UV absorbance is observed. wherein the composition is used as a coating. 2. The composition of claim 1, wherein the binder is a Example 10 polymeric binder. 3.-5. (canceled) Sample Preparation 6. The composition of claim 1, wherein the coating comprises from about 0.5-20 wt % of functionalized gra 0.165 Quartz slides were first cleaned by washing with DI phene. water and 1M HCl and dried. The graphene composition was 7. The composition of claim 1, wherein the functionalized dispersed in toluene at 1% and 2% (by weight) by bath graphene comprises one or more functional groups selected Sonication. Commercial gloss varnish was mixed with the from: amino, cyano, hydroxyl, carboxylic acid, isocyanate, graphene/toluene dispersion. Cleaned quartz slides were aldehyde, epoxide, urea, alkene, aralkene, or anhydride. then dip coated in the graphene/top coat dispersion and air 8. The composition of claim 1 further comprising a dried for a total of 3 cycles. carrier, a filler, a pigment, or a dispersant. (0166 UV Measurements. 9.-10. (canceled) 0167 UV absorption was measured by placing the quartz 11. A composition comprising: slide in a UV-Vis spectrophotometer and reading from 400 (A) functionalized graphene; and to 200 nm with a blank quartz slide as control. (B) a resin. (0168 Results. 12. The composition of claim 11, wherein the composition (0169 FIG. 10 shows an increase the UV absorption when is used as a coating. graphene is mixed with the dammar Varnish. 13. (canceled) Example 11 14. The composition of claim 11, wherein the coating is a coating on a steel Substrate, an automobile, a ship, a Sample Preparation concrete surface, a marine structure, or a construction struc ture. 0170 Quartz slides were first cleaned by washing with DI 15. The composition of claim 11, wherein the function water and 1M HCl and dried. The graphene composition was alized graphene contains at least one chemical group dispersed in water at 1% and 2% (by weight) by bath selected from: amine, cyano, carboxylic acid, hydroxyl, Sonication. Commercial gloss varnish was mixed with the isocyanate, aldehyde, epoxide, urea, or anhydride. US 2017/0037257 A1 Feb. 9, 2017

16. The composition of claim 15, wherein the function 27. The composition of claim 25, wherein the resin is an alized graphene contains at least one chemical group which epoxy, isocyanate, polyol, polyester, or phenolic resin. comprises a nitrogen containing group. 28. The composition of claim 25, wherein the function 17. The composition of claim 11, wherein the resin is a alized graphene comprises phenolic resin, a polyester resin, a polyol resin, an epoxy (1) one or more amine, carboxylic acid, hydroxy, or urea resin, or an isocyanate resin. groups when the resin is an isocyanate resin; 18. (canceled) (2) one or more amine, anhydride, carboxylic acid, or 19. The composition of claim 11, wherein the composition hydroxyl groups when the resin is an epoxy resin; further comprises a filler, a pigment, or an accelerator. (3) one or more isocyanate groups when the resin is a 20.-21. (canceled) polyol resin; 22. The composition of claim 11, wherein the coating is (4) one or more alkene, aralkene, or anhydride groups from about 5um to about 300 um thick. when the resin is a polyester resin; 23.-24. (canceled) (5) one or more aldehyde groups when the resin is a 25. A composition comprising: phenolic resin. (A) a functionalized graphene; and 29. (canceled) (B) a resin, 30. The composition of claim 25, wherein the composi wherein the functionalized graphene is reacted with the tion further comprises a filler, a pigment, or an accelerator. resin to form a polymeric resin consisting essentially of 31. (canceled) functionalized graphene and resin repeating units and 32. The composition of claim 30, wherein the accelerator the resultant polymeric resin is used as a coating. is a metal catalyst, a basic catalyst, an acid catalyst, an azide 26. The composition of claim 25, wherein the function compound, or a peroxide. alized graphene comprises one or more chemical groups 33. The composition of claim 25, wherein the coating is selected from: amine, cyano, carboxylic acid, hydroxyl, from about 5um to about 300 um thick. isocyanate, aldehyde, epoxide, urea, alkene, aralkene, or 34-35. (canceled) anhydride.