WO2016070068A1

WO2016070068A1 - Resistive heating coatings containing graphene carbon particles and use of such coatings for low energy curing

Info

Publication number: WO2016070068A1
Application number: PCT/US2015/058349
Authority: WO
Inventors: Stephen B. Istivan; Eldon L. Decker; Noel R. Vanier; John M. Furar; Cheng-Hung Hung
Original assignee: PPG Industries Ohio Inc
Current assignee: PPG Industries Ohio Inc
Priority date: 2014-10-31
Filing date: 2015-10-30
Publication date: 2016-05-06
Anticipated expiration: 2017-04-30
Also published as: TW201630464A; TWI590702B

Abstract

Resistive heating assemblies comprising a substrate, a conductive coating comprising graphenic carbon particles applied to at least a portion of the substrate, and a source of electrical current connected to the conductive coating are disclosed. Conductive coatings comprising graphenic carbon particles having a thickness of less than 100 microns and an electrical conductivity of greater than 10,000 S/m are also disclosed. The conductive coatings may be used to thermally cure adjacent polymeric layer(s).

Description

RESISTIVE HEATING COATINGS CONTAINING GRAPHENE CARBON PARTICLES AND USE OF SUCH COATINGS FOR LOW ENERGY CURING

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from U.S. Patent Application Serial No. 14/529,786 filed October 31, 2014, which is incorporated herein by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to resistive heating coatings containing grapheme carbon particles and the use of such coatings for low energy curing.

BACKGROUND OF THE INVENTION

[0003] Heated panels have many potential uses in various industries such as architecture, consumer products, automotive and aircraft industries and the like.

SUMMARY OF THE INVENTION

[0004] An aspect of the invention provides a resistive heating assembly comprising: a substrate, a conductive coating comprising grapheme carbon particles applied to at least a portion of the substrate, and a source of electrical current connected to the conductive coating.

[0005] Another aspect of the invention provides a conductive coating comprising grapheme carbon particles having a thickness of less than 100 microns and an electrical conductivity of greater than 10,000 S/m.

[0006] A further aspect of the invention provides a method of curing a layer of curable material comprising applying electrical current to a conductive coating adjacent to the layer of curable material, wherein the conductive coating comprises grapheme carbon particles and has a thickness of less than 100 microns and an electrical conductivity of greater than 10,000 S/m.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Fig. 1 is a partially schematic sectional isometric view of a resistive heating coating applied on a substrate in accordance with an embodiment of the present invention. [0008] Figs. 2-8 are schematic side sectional views of resistive heating coatings applied on substrates with additional coatings that may be cured by the resistive heating coatings in accordance with embodiments of the present invention.

[0009] Fig. 9 is a partially schematic top view of a test panel for measuring heating rates of various coatings.

[0010] Fig. 10 is a graph of temperature versus time for two resistively heated coatings.

[0011] Fig. 11 is a partially schematic top view of a test panel for measuring heating rates of various coatings.

[0012] Fig. 12 is a graph of temperature versus time for three resistively heated coatings.

[0013] Fig. 13 is a graph of temperature versus time for coating layers that were cured through the use of a resistive heating coating.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

[0014] In accordance with embodiments of the present invention, grapheme carbon particles are used in coatings to provide increased electrical conductivity and the ability to serve as resistive heating coatings. Such coatings may be relatively thin while exhibiting desirable resistive heating properties.

[0015] The resistive heating coatings of the present invention have many potential applications, such as architectural coatings, industrial coatings, automotive seat warmers, clothing and the like. In architectural applications, the coatings may be applied to walls, ceilings, floors, and the like to provide heating for commercial and residential buildings. In industrial applications, the resistive heating coatings may be applied to aircraft for deicing, ice-prevention, shape controlling or other purposes, automotive vehicle panels, mirrors or other components for deicing or anti-fogging purposes. Other applications include the use of the resistive heating coatings to cure adjacent layers of materials such as coatings.

[0016] As used herein, the terms "electrically conductive coating" and "conductive coating", when referring to a coating containing grapheme carbon particles, means that the coating has an electrical conductivity of at least 0.001 S/m. For example, the coating may have a conductivity of at least 0.01, or at least 10 S/m. When the electrically conductive coating is used in a resistive heating assembly in accordance with embodiments of the invention, the conductivity may typically be from 10,000 to 50,000 S/m, or higher. In certain embodiments, the conductivity may be at least 12,000 S/m or at least 20,000 S/m. For example, the conductivity may be at least 30,000 S/m, or at least 40,000 S/m, or at least 50,000 S/m or higher, or at least 60,000 S/m or higher.

[0017] In accordance with certain embodiments, the coatings do not exhibit significant electrical conductivity absent the addition of grapheme carbon particles. For example, a cured or dried polymeric resin may have a conductivity that is not measureable, while cured or dried polymeric resins of the present invention including grapheme carbon particles may exhibit conductivities as noted above.

[0018] As used herein, the term "coating" means any type of film having a measurable thickness when applied to a substrate. In certain embodiments, the coating may include a film-forming resin, may be free of a film- forming resin, or may be provided in the form of an ink.

[0019] As used herein, the term "resistive heating coating" means a conductive coating which is heated by means of applying a voltage to the coating. This is also known as Joule heating or ohmic heating, where the electrical power dissipated in the coating is equal to I²R where I is the current flow in the coating due to the applied voltage, and R is electrical resistance of the coating. Such resistive heating coatings may be applied to various different types of rigid or flexible substrates such as metal, glass, plastic, ceramic, composite, fabric and the like.

Voltage may be selectively applied to such coatings by any suitable means, such as by electrically conductive contacts, wires or printed strips located on opposite edges of the coating that create an electric potential causing current to flow through the coating from one electrical contact to the other, e.g., in the plane of the coating.

[0020] As used herein when referring to the use of the resistive heating coatings to cure adjacent polymeric coating layers or articles, the term "cure" includes partial or total curing of the adjacent layer(s) or article(s) to toughen or harden the polymer material by cross-linking of polymer chains. The term "cure" includes cross- linking and any preliminary drying, dehydrating, etc. steps carried out at elevated temperatures prior to or during cross-linking of the polymer chains. [0021] Fig. 1 schematically illustrates a conductive coating or resistive heating coating 10 applied on a substrate 12 in accordance with an embodiment of the present invention. The conductive coating 10 may be applied directly on the substrate, or may be applied on the substrate with an intervening layer(s) (not shown). Electrical contacts 14 are provided on opposite edges of the coating 10. A conventional applied voltage (not shown) maybe connected to the electrical contacts 14 to generate a flow of electric current I through the coating 10. The coating 10 has a thickness T. In certain embodiments, the coating 10 has a typical thickness T of from 0.1 to 100 microns, for example, from 1 to 50 microns or from 5 to 25 microns. The coatings may be relatively thin while providing desirable resistive heating characteristics due to the electrical conductivity properties provided by the grapheme carbon particles. In certain embodiments, the thin coatings are sufficiently flexible such that they do not suffer damage when applied to flexible substrates.

[0022] Figs. 2-8 schematically illustrate the use of resistive heating coatings containing grapheme carbon particles to cure adjacent layers of materials in accordance with embodiments of the present invention. The terms "adjacent" and "adjacent to" mean that the various layers are close to each other, e.g., in direct contact with each other or near each other if intervening layer(s) are present. In each of the embodiments of Figs. 2-8, a resistive heating coating 10 is applied on a substrate 20, which may be any suitable type of material including electrically conductive, semi-conductive or insulating substrates. For example, the substrate may comprise metal, glass, plastic or any other substrate upon which curable layer(s) may be applied. Multiple substrates may be used in certain embodiments. The resistive heating coating 10 is arranged such that it is in thermal communication with various curable layers as more fully described below, e.g., the resistive heating coating is structured and arranged such that it transfers heat to the adjacent curable layers.

[0023] In the assembly 25 shown in Fig. 2, the resistive heating coating 10 is applied directly onto the substrate 20, and a curable layer 22 is applied directly on the resistive heating coating 10.

[0024] In the assembly 35 shown in Fig. 3, the resistive heating coating 10 is applied on a curable layer 22, which is applied on the substrate 20. [0025] In the assembly 45 shown in Fig. 4, the resistive heating coating 10 is applied on the substrate 20, a first curable layer 23 is applied on the resistive heating coating 10, and a second curable layer 24 is applied on the first curable layer 23.

[0026] In the assembly 55 shown in Fig. 5, a first curable layer 23 is applied on the substrate 20, the resistive heating coating 10 is applied on the first curable layer 23, and a second curable layer 24 is applied on the resistive heating coating 10.

[0027] In the assembly 65 shown in Fig. 6, a first curable layer 23 is applied on the substrate 20, a second curable layer 24 is applied on the first curable layer 23, and the resistive heating coating 10 is applied on the second curable layer 24.

[0028] In the assembly 75 shown in Fig. 7, an electrically insulating layer 26 is applied on the substrate 20. The resistive heating coating 10 is applied on the electrically insulating layer 26. A first curable layer 23 is applied on the resistive heating coating 10, and a second curable layer 24 is applied on the first curable layer 23.

[0029] In the assembly 85 shown in Fig. 8, the resistive heating coating 10 is applied on one side of the substrate 20, and a curable layer 22 is applied on the other side of the substrate 20.

[0030] In each of the embodiments shown in Figs. 2-8, the curable layers 22, 23 and 24 may have any suitable thicknesses. For example, when the curable layers 22, 23 and 24 are provided in the form of coatings, they may typically have thicknesses of from 1 to 100 microns, for example, from 5 to 75 microns, or from 10 to 50 microns.

[0031] In accordance with embodiments of the invention, the resistive heating coating 10 may be co-extensive with the substrate 12, 20 upon which it is applied, e.g., the resistive heating coating 10 may comprise a continuous sheet covering the entire surface area of the substrate 12, 20. Alternatively, the resisting heating coating 10 may be provided in any suitable type of pattern or configuration on the substrate 12, 20. For example, a patterned resistive heating coating 10 may be provided in the form of parallel lines, concentric circular or spiral lines, grids, circuitous lines and the like. The patterned resistive heating coating 10 may be provided in a single loop or multiple loops in parallel or series connections. Any suitable type of electrical connection maybe made to the resistive heating coating 10 such as conductive wires, bus bars and the like.

[0032] The composition of the resistive heating coating 10 can comprise any of a variety of thermoplastic and/or thermosetting compositions known in the art. For example, the coating compositions can comprise film- forming resins selected from epoxy resins, acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, bisphenol A based epoxy polymers, polysiloxane polymers, styrenes, ethylenes, butylenes, copolymers thereof, and mixtures thereof. Generally, these polymers can be any polymers of these types made by any method known to those skilled in the art. Such polymers may be solvent borne, water soluble or water dispersible, emulsifiable, or of limited water solubility. Furthermore, the polymers may be provided in sol gel systems, may be provided in core-shell polymer systems, or may be provided in powder form. In certain embodiments, the polymers are dispersions in a continuous phase comprising water and/or organic solvent, for example emulsion polymers or non-aqueous dispersions.

[0033] Thermosetting or curable coating compositions typically comprise film forming polymers or resins having functional groups that are reactive with either themselves or a crosslinking agent. The functional groups on the film- forming resin may be selected from any of a variety of reactive functional groups including, for example, carboxylic acid groups, amine groups, epoxide groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups and tris-alkylcarbamoyltriazine) mercaptan groups, styrenic groups, anhydride groups, acetoacetate acrylates, uretidione and combinations thereof.

[0034] Thermosetting coating compositions typically comprise a crosslinking agent that may be selected from, for example, aminoplasts, polyisocyanates including blocked isocyanates, polyepoxides, beta-hydroxyalkylamides, polyacids, anhydrides, organometallic acid-functional materials, polyamines, polyamides, and mixtures of any of the foregoing. Suitable polyisocyanates include multifunctional isocyanates. Examples of multifunctional polyisocyanates include aliphatic diisocyanates like hexamethylene diisocyanate and isophorone diisocyanate, and aromatic diisocyanates like toluene diisocyanate and 4,4'-diphenylmethane diisocyanate. The polyisocyanates can be blocked or unblocked. Examples of other suitable polyisocyanates include isocyanurate trimers, allophanates, and uretdiones of diisocyanates. Examples of commercially available polyisocyanates include DESMODUR N3390, which is sold by Bayer Corporation, and TOLONATE HDT90, which is sold by Rhodia Inc.

Suitable aminoplasts include condensates of amines and or amides with aldehyde. For example, the condensate of melamine with formaldehyde is a suitable aminoplast. Suitable aminoplasts are well known in the art. A suitable aminoplast is disclosed, for example, in U.S. Pat. No. 6,316,119 at column 5, lines 45-55, incorporated by reference herein. In certain embodiments, the resin can be self-crosslinking. Self- crosslinking means that the resin contains functional groups that are capable of reacting with themselves, such as alkoxysilane groups, or that the reaction product contains functional groups that are coreactive, for example hydroxyl groups and blocked isocyanate groups.

[0035] In certain embodiments, the grapheme carbon particles of the resistive heating layer 10 may be dispersed within a matrix material such as film-forming resins as described above, a dispersant or a mixture of dispersants in amounts of from 0.1 to 95 weight percent based on the total solids of the material. For example, the grapheme carbon particles may comprise from 1 to 90 weight percent, or from 5 to 85 weight percent of the material. In certain embodiments, the amount of grapheme carbon particles contained in the materials may be relatively large, such as from 40 or 50 weight percent up to 90 or 95 weight percent. For example, the grapheme carbon particles may comprise from 60 to 85 weight percent, or from 70 to 80 weight percent. In certain embodiments, conductivity properties of ink or coating may be significantly increased with relatively minor additions of the grapheme carbon particles, for example, less than 50 weight percent, or less than 30 weight percent. In certain embodiments, the coatings or other materials have sufficiently high electrical conductivities at relatively low loadings of the grapheme carbon particles. For example, the above-noted electrical conductivities may be achieved at grapheme carbon particle loadings of less than 20 or 15 weight percent. In certain embodiments, the particle loadings may be less than 10 or 8 weight percent, or less than 6 or 5 weight percent. For example, for coatings comprising film-forming polymers or resins that by themselves are non-conductive, the dispersion of from 3 to 5 weight percent of grapheme carbon particles may provide an electrical conductivity of at least 0.1 S/m, e.g., or at least 10 S/m. [0036] In addition to the resin and grapheme carbon particle components, the coatings or other materials in accordance with certain embodiments of the present invention may include additional components conventionally added to coating or ink compositions, such as cross-linkers, pigments, tints, flow aids, defoamers, dispersants, solvents, UV absorbers, catalysts and surface active agents. In certain embodiments, the coatings may be colored, while in other embodiments the coatings may be clear.

[0037] In the embodiments shown in Figs. 2-8, each of the curable layers 22, 23 and 24 may comprise materials such as any of a variety of thermoplastic and/or thermosetting compositions known in the art. For example, the coating compositions can comprise film-forming resins selected from epoxy resins, acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, bisphenol A based epoxy polymers, polysiloxane polymers, styrenes, ethylenes, butylenes, copolymers thereof, and mixtures thereof. Generally, these polymers can be any polymers of these types made by any method known to those skilled in the art. Such polymers may be solvent borne, water soluble or water dispersible, emulsifiable, or of limited water solubility. Furthermore, the polymers may be provided in sol gel systems, may be provided in core-shell polymer systems, or may be provided in powder form. In certain embodiments, the polymers are dispersions in a continuous phase comprising water and/or organic solvent, for example emulsion polymers or non-aqueous dispersions.

[0038] Thermosetting or curable coating compositions typically comprise film forming polymers or resins having functional groups that are reactive with either themselves or a crosslinking agent. The functional groups on the film- forming resin may be selected from any of a variety of reactive functional groups including, for example, carboxylic acid groups, amine groups, epoxide groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups and tris-alkylcarbamoyltriazine) mercaptan groups, styrenic groups, anhydride groups, acetoacetate acrylates, uretidione and combinations thereof.

[0039] Thermosetting coating compositions typically comprise a crosslinking agent that may be selected from, for example, aminoplasts, polyisocyanates including blocked isocyanates, polyepoxides, beta-hydroxyalkylamides, polyacids, anhydrides, organometallic acid-functional materials, polyamines, polyamides, and mixtures of any of the foregoing. Suitable polyisocyanates include multifunctional isocyanates. Examples of multifunctional polyisocyanates include aliphatic diisocyanates like hexamethylene diisocyanate and isophorone diisocyanate, and aromatic diisocyanates like toluene diisocyanate and 4,4'-diphenylmethane diisocyanate. The polyisocyanates can be blocked or unblocked. Examples of other suitable polyisocyanates include isocyanurate trimers, allophanates, and uretdiones of diisocyanates. Examples of commercially available polyisocyanates include DESMODUR 3390, which is sold by Bayer Corporation, and TOLONATE HDT90, which is sold by Rhodia Inc.

[0040] In accordance with embodiments of the invention, an electrical voltage applied to the resistive heating coating 10 may be controlled in order to produce desired curing parameters including curing temperatures and curing times. For example, curing temperatures may typically range from above ambient temperature to 500°C, for example, from 25 to 350°C, or from 80 to 140°C, depending upon the particular material of each coating layer 22, 23 and 24. Curing times may typically range from 2 seconds to 2 hours, for example, from 5 to 60 minutes, or from 20 to 35 minutes for certain types of coatings.

[0041] In embodiments where the assembly includes an electrically insulating layer, such as the insulating layer 26 shown in Fig. 7, such insulating layers may comprise a primary resin vehicle, auxiliary resins, grind resins, crosslinking agents, organic and inorganic colorants, and additives. For example, the material of the insulating layer 26 may comprise resins comprised of polyurea, polyurethane, polyester, polyol, acrylic, polyepoxide, ketohydrazide and/or carbamate. Crosslinking agents may include mixtures of aminoplasts, polyisocyanates, epoxides, polyacids and anhydrides. Colorants may be added to the insulating layer 26 including pigments such as aluminum, mica, titanium dioxide, iron oxide, chromium oxide, lead chromate, carbon black and the like. Additives such as associative thickeners, surface tension modifiers, UV absorbers, hindered amine light stabilizers, defoamers and others used commonly by those familiar in the art may be included in the insulating layer 26. The thickness of the insulating layer 26 may be selected as desired, for example, from 0.001 to 30 mm, or from 0.01 to 0.1 mm. The use of an insulating layer 26 as shown in the embodiment of Fig. 7 may be useful in various different types of applications, including embodiments in which the substrate 20 is electrically conductive and it is desired to electrically insulate the resistive heating coating 10 from the conductive substrate.

[0042] As used herein, the term "grapheme carbon particles" means carbon particles having structures comprising one or more layers of one-atom-thick planar sheets of sp²-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The average number of stacked layers may be less than 100, for example, less than 50. In certain embodiments, the average number of stacked layers is 30 or less, such as 20 or less, 10 or less, or, in some cases, 5 or less. The grapheme carbon particles may be substantially flat, however, at least a portion of the planar sheets may be substantially curved, curled, creased or buckled. The particles typically do not have a spheroidal or equiaxed morphology.

[0043] In certain embodiments, the grapheme carbon particles have a thickness, measured in a direction perpendicular to the carbon atom layers, of no more than 10 nanometers, no more than 5 nanometers, or, in certain embodiments, no more than 4 or 3 or 2 or 1 nanometers, such as no more than 3.6 nanometers. In certain embodiments, the grapheme carbon particles may be from 1 atom layer up to 3, 6, 9, 12, 20 or 30 atom layers thick, or more. In certain embodiments, the grapheme carbon particles have a width and length, measured in a direction parallel to the carbon atoms layers, of at least 50 nanometers, such as more than 100 nanometers, in some cases more than 100 nanometers up to 500 nanometers, or more than 100 nanometers up to 200 nanometers. The grapheme carbon particles may be provided in the form of ultrathin flakes, platelets or sheets having relatively high aspect ratios (aspect ratio being defined as the ratio of the longest dimension of a particle to the shortest dimension of the particle) of greater than 3: 1, such as greater than 10: 1. [0044] In certain embodiments, the grapheme carbon particles have relatively low oxygen content. For example, the grapheme carbon particles may, even when having a thickness of no more than 5 or no more than 2 nanometers, have an oxygen content of no more than 2 atomic weight percent, such as no more than 1.5 or 1 atomic weight percent, or no more than 0.6 atomic weight, such as about 0.5 atomic weight percent. The oxygen content of the grapheme carbon particles can be determined using X-ray Photoelectron Spectroscopy, such as is described in D. R. Dreyer et al, Chem. Soc. Rev. 39, 228-240 (2010).

[0045] In certain embodiments, the grapheme carbon particles have a B.E.T. specific surface area of at least 50 square meters per gram, such as 70 to 1000 square meters per gram, or, in some cases, 200 to 1000 square meters per grams or 200 to 400 square meters per gram. As used herein, the term "B.E.T. specific surface area" refers to a specific surface area determined by nitrogen adsorption according to the ASTMD 3663-78 standard based on the Brunauer-Emmett-Teller method described in the periodical "The Journal of the American Chemical Society", 60, 309 (1938).

[0046] In certain embodiments, the grapheme carbon particles have a Raman spectroscopy 2D/G peak ratio of at least 1 :1, for example, at least 1.2:1 or 1.3: 1. As used herein, the term "2D/G peak ratio" refers to the ratio of the intensity of the 2D peak at 2692 cm^"1 to the intensity of the G peak at 1,580 cm^"1.

[0047] In certain embodiments, the grapheme carbon particles have a relatively low bulk density. For example, the grapheme carbon particles are characterized by having a bulk density (tap density) of less than 0.2 g/cm³, such as no more than 0.1 g cm³. For the purposes of the present invention, the bulk density of the grapheme carbon particles is determined by placing 0.4 grams of the grapheme carbon particles in a glass measuring cylinder having a readable scale. The cylinder is raised approximately one-inch and tapped 100 times, by striking the base of the cylinder onto a hard surface, to allow the grapheme carbon particles to settle within the cylinder. The volume of the particles is then measured, and the bulk density is calculated by dividing 0.4 grams by the measured volume, wherein the bulk density is expressed in terms of g/cm³.

[0048] In certain embodiments, the grapheme carbon particles have a compressed density and a percent densification that is less than the compressed density and percent densification of graphite powder and certain types of substantially flat grapheme carbon particles such as those formed from exfoliated graphite. Lower compressed density and lower percent densification are each currently believed to contribute to better dispersion and/or rheological properties than grapheme carbon particles exhibiting higher compressed density and higher percent densification. In certain embodiments, the compressed density of the grapheme carbon particles is 0.9 or less, such as less than 0.8, less than 0.7, such as from 0.6 to 0.7. In certain embodiments, the percent densification of the grapheme carbon particles is less than 40%, such as less than 30%, such as from 25 to 30%.

[0049] For purposes of the present invention, the compressed density of grapheme carbon particles is calculated from a measured thickness of a given mass of the particles after compression. Specifically, the measured thickness is determined by subjecting 0.1 grams of the grapheme carbon particles to cold press under 15,000 pound of force in a 1.3 centimeter die for 45 minutes, wherein the contact pressure is 500 MPa. The compressed density of the grapheme carbon particles is then calculated from this measured thickness according to the following equation:

Compressed Density (g/cm³) = 0.1 grams

n*(1.3cm/2)²*(measured thickness in cm)

[0050] The percent densification of the grapheme carbon particles is then determined as the ratio of the calculated compressed density of the grapheme carbon particles, as determined above, to 2.2 g/cm³, which is the density of graphite.

[0051] In certain embodiments, the grapheme carbon particles have a measured bulk liquid conductivity of at least 100 microSiemens, such as at least 120 microSiemens, such as at least 140 microSiemens immediately after mixing and at later points in time, such as at 10 minutes, or 20 minutes, or 30 minutes, or 40 minutes. For the purposes of the present invention, the bulk liquid conductivity of the grapheme carbon particles is determined as follows. First, a sample comprising a 0.5% solution of grapheme carbon particles in butyl cellosolve is sonicated for 30 minutes with a bath sonicator. Immediately following sonication, the sample is placed in a standard calibrated electrolytic conductivity cell ( =l). A Fisher Scientific AB 30 conductivity meter is introduced to the sample to measure the conductivity of the sample. The conductivity is plotted over the course of about 40 minutes.

[0052] In accordance with certain embodiments, percolation, defined as long range interconnectivity, occurs between the conductive grapheme carbon particles. Such percolation may reduce the resistivity of the coating compositions. The conductive grapheme particles may occupy a minimum volume within the coating such that the particles form a continuous, or nearly continuous, network. In such a case, the aspect ratios of the grapheme carbon particles may affect the minimum volume required for percolation.

[0053] In certain embodiments, at least a portion of the grapheme carbon particles to be dispersed in the resistive heating coating compositions of the present invention are may be made by thermal processes. In accordance with embodiments of the invention, thermally produced grapheme carbon particles are made from carbon- containing precursor materials that are heated to high temperatures in a thermal zone such as a plasma. As more fully described below, the carbon-containing precursor materials are heated to a sufficiently high temperature, e.g., above 3,500°C, to produce grapheme carbon particles having characteristics as described above. The carbon- containing precursor, such as a hydrocarbon provided in gaseous or liquid form, is heated in the thermal zone to produce the grapheme carbon particles in the thermal zone or downstream therefrom. For example, thermally produced grapheme carbon particles may be made by the systems and methods disclosed in U.S. Patent Nos. 8,486,363 and 8,486,364.

[0054] In certain embodiments, the thermally produced grapheme carbon particles may be made by using the apparatus and method described in U.S. Patent No. 8,486,363 at [0022] to [0048] in which (i) one or more hydrocarbon precursor materials capable of forming a two-carbon fragment species (such as n-propanol, ethane, ethylene, acetylene, vinyl chloride, 1 ,2-dichloroethane, allyl alcohol, propionaldehyde, and/or vinyl bromide) is introduced into a thermal zone (such as a plasma), and (ii) the hydrocarbon is heated in the thermal zone to form the grapheme carbon particles. In other embodiments, the thermally produced grapheme carbon particles may be made by using the apparatus and method described in U.S. Patent No. 8,486,364 at [0015] to [0042] in which (i) a methane precursor material (such as a material comprising at least 50 percent methane, or, in some cases, gaseous or liquid methane of at least 95 or 99 percent purity or higher) is introduced into a thermal zone (such as a plasma), and (ii) the methane precursor is heated in the thermal zone to form the grapheme carbon particles. Such methods can produce grapheme carbon particles having at least some, in some cases all, of the characteristics described above.

[0055] During production of the grapheme carbon particles by the thermal production methods described above, a carbon-containing precursor is provided as a feed material that may be contacted with an inert carrier gas. The carbon-containing precursor material may be heated in a thermal zone, for example, by a plasma system. In certain embodiments, the precursor material is heated to a temperature of at least 3,500°C, for example, from a temperature of greater than 3,500°C or 4,000°C up to 10,000°C or 20,000°C. Although the thermal zone may be generated by a plasma system, it is to be understood that any other suitable heating system may be used to create the thermal zone, such as various types of furnaces including electrically heated tube furnaces and the like.

[0056] The gaseous stream may be contacted with one or more quench streams that are injected into the plasma chamber through at least one quench stream injection port. The quench stream may cool the gaseous stream to facilitate the formation or control the particle size or morphology of the grapheme carbon particles. In certain embodiments of the invention, after contacting the gaseous product stream with the quench streams, the ultrafme particles may be passed through a converging member. After the grapheme carbon particles exit the plasma system, they may be collected. Any suitable means may be used to separate the grapheme carbon particles from the gas flow, such as, for example, a bag filter, cyclone separator or deposition on a substrate.

[0057] In certain embodiments, at least a portion of the grapheme carbon particles may be obtained from commercial sources, for example, from Angstron, XG Sciences and other commercial sources. In such embodiments, the commercially available grapheme carbon particles may comprise exfoliated graphite and have different characteristics in comparison with the thermally produced grapheme carbon particles, such as different size distributions, thicknesses, aspect ratios, structural morphologies, oxygen contents, and chemical functionalities at the basal planes/edges. [0058] In certain embodiments, the grapheme carbon particles are

functionalized. As used herein, "functionalized", when referring to grapheme carbon particles, means covalent bonding of any non-carbon atom or any organic group to the grapheme carbon particles. The grapheme carbon particles may be functionalized through the formation of covalent bonds between the carbon atoms of a particle and other chemical moieties such as carboxylic acid groups, sulfonic acid groups, hydroxyl groups, halogen atoms, nitro groups, amine groups, aliphatic hydrocarbon groups, phenyl groups and the like. For example, functionalization with carbonaceous materials may result in the formation of carboxylic acid groups on the grapheme carbon particles. The grapheme carbon particles may also be functionalized by other reactions such as Diels-Alder addition reactions, 1,3 -dipolar cycloaddition reactions, free radical addition reactions and diazonium addition reactions. In certain embodiments, the hydrocarbon and phenyl groups may be further functionalized. If the grapheme carbon particles already have some hydroxyl functionality, the functionality can be modified and extended by reacting these groups with, for example, an organic isocyanate.

[0059] In certain embodiments, a single type of grapheme carbon particles may be dispersed in the resistive heating coatings 10. In other embodiments, co- dispersions of different types of grapheme particles may be used. As used herein, the term "co-dispersed" means that different types of grapheme carbon particles are dispersed together in a medium such as a solvent containing a polymeric dispersant to form a substantially uniform dispersion of the grapheme carbon particles throughout the medium without substantial agglomeration of the particles. As used herein, the term "mixture" means that different types of grapheme carbon particles are dispersed separately in a medium, followed by mixing the separate dispersions together. The presence of agglomerations may be determined by standard methods such as visual analysis of TEM micrograph images. Agglomerations may also be detected by standard particle size measurement techniques, as well as measurements of electrical conductivity or measurements of optical characteristics of materials containing the grapheme carbon particles such as color, haze, jetness, reflectance and transmission properties. The different types of grapheme particles that are dispersed together may comprise particles having different particle size distributions, thicknesses, aspect ratios, structural morphologies, edge functionalities and/or oxygen contents. In certain embodiments, the grapheme carbon particles are made by different processes, such as thermal production methods, exfoliation methods, and the like, as more fully described below.

[0060] In certain embodiments, thermally produced grapheme carbon particles are combined with commercially available grapheme carbon particles to produce a bi- modal distribution, tri-modal distribution, etc. of grapheme carbon particles. The grapheme carbon particles contained in the compositions may have multi -modal particle size distributions, aspect ratio distributions, structural morphologies, edge functionality differences, oxygen content, and the like.

[0061] In an embodiment of the present invention in which both thermally produced grapheme carbon particles and commercially available grapheme carbon particles, e.g., from exfoliated graphite, are co-dispersed and added to a coating composition to produce a bi-modal grapheme particle size distribution, the relative amounts of the different types of grapheme carbon particles are controlled to produce desired conductivity properties of the coatings. For example, the thermally produced grapheme particles may comprise from 1 to 50 weight percent, and the commercially available grapheme carbon particles may comprise from 50 to 99 weight percent, based on the total weight of the grapheme carbon particles. In certain embodiments, the thermally produced grapheme carbon particles may comprise from 2 or 4 to 40 weight percent, or from 6 or 8 to 35 weight percent, or from 10 to 30 weight percent. When co-dispersions of the present invention having such relative amounts of thermally produced grapheme carbon particles and commercially available grapheme carbon particles are incorporated in coatings, inks, or other materials, such materials may exhibit significantly increased electrical conductivities in comparison with similar materials containing mixtures of such types of grapheme carbon particles at similar ratios. For example, the co-dispersions may increase electrical conductivity by at least 10 or 20 percent compared with the mixtures. In certain embodiments, the electrical conductivity may be increased by at least 50, 70 or 90 percent, or more.

[0062] In certain embodiments, the coating compositions or other materials produced with the present dispersions are substantially free of certain components such as polyalkyleneimines, graphite, or other components. For example, the term "substantially free of polyalkyleneimines" means that polyalkyleneimines are not purposefully added, or are present as impurities or in trace amounts, e.g., less than 1 weight percent or less than 0.1 weight percent. The term "substantially free of graphite" means that graphite is not purposefully added, or is present as an impurity or in trace amounts, e.g., less than 1 weight percent or less than 0.1 weight percent. In certain embodiments, graphite in minor amounts may be present in the materials, e.g., less than 5 weight percent or less than 1 weight percent of the material. If graphite is present, it is typically in an amount less than the grapheme carbon particles, e.g., less than 30 weight percent based on the combined weight of the graphite and grapheme carbon particles, for example, less than 20 or 10 weight percent.

[0063] In certain embodiments, the compositions of the present invention are prepared from a dispersion comprising: (a) grapheme carbon particles such as any of those described above; (b) a carrier that may be selected from water, at least one organic solvent, or combinations of water and at least one organic solvent; (c) at least one polymeric dispersant, such as the copolymer described generally below; and, optionally, (d) at least one resin as described above or other additives.

[0064] Certain compositions of the present invention comprise at least one polymeric dispersant. In certain embodiments, such a polymeric dispersant comprises a tri-block copolymer comprising: (i) a first segment comprising grapheme carbon affinic groups, such as hydrophobic aromatic groups; (ii) a second segment comprising polar groups, such as hydroxyl groups, amine groups, ether groups, and/or acid groups; and (iii) a third segment which is different from the first segment and the second segment, such as a segment that is substantially non-polar, i.e., substantially free of polar groups. As used herein, term "substantially free" when used with reference to the absence of groups in a polymeric segment, means that no more than 5% by weight of the monomer used to form the third segment comprises polar groups.

[0065] Suitable polymeric dispersants include acrylic copolymers produced from atom transfer radical polymerization. In certain embodiments, such copolymers have a weight average molecular weight of 1,000 to 20,000.

[0066] In certain embodiments, the polymeric pigment dispersant has a polymer chain structure represented by the following general formula (I),

wherein G is a residue of at least one radically polymerizable ethylenically unsaturated monomer; W and Y are residues of at least one radically polymerizable ethylenically unsaturated monomer with W and Y being different from one another; Y is optional; Φ is a hydrophobic residue of or derived from an initiator and is free of the radically transferable group; T is or is derived from the radically transferable group of the initiator; p, q and s represent average numbers of residues occurring in a block of residues; p, q and s are each individually selected such that the polymeric dispersant has a number average molecular weight of at least 250.

[0067] The polymeric dispersant may be described generally as having a head and tail structure, i.e., as having a polymeric head portion and a polymeric tail portion. The polymeric tail portion may have a hydrophilic portion and a hydrophobic portion, particularly at the terminus thereof. While not intending to be bound by any theory, it is believed that the polymeric head portion of the polymeric dispersant can be associated with the grapheme carbon particles, while the polymeric tail portion aids in dispersing the grapheme carbon particles and can be associated with other components of an ink or coating composition. As used herein, the terms "hydrophobic" and "hydrophilic" are relative to each other.

[0068] In certain embodiments, the polymeric dispersant is prepared by atom transfer radical polymerization (ATRP). The ATRP process can be described generally as comprising: polymerizing one or more radically polymerizable monomers in the presence of an initiation system; forming a polymer; and isolating the formed polymer. In certain embodiments, the initiation system comprises: a monomeric initiator having a single radically transferable atom or group; a transition metal compound, i.e., a catalyst, which participates in a reversible redox cycle with the initiator; and a ligand, which coordinates with the transition metal compound. The ATRP process is described in further detail in International Patent Publication No. WO 98/40415 and U.S. Pat. Nos. 5,807,937, 5,763,548 and 5,789,487.

[0069] Catalysts that may be used in the ATRP preparation of the polymeric dispersant include any transition metal compound that can participate in a redox cycle with the initiator and the growing polymer chain. It may be preferred that the transition metal compound not form direct carbon-metal bonds with the polymer chain. Transition metal catalysts useful in the present invention may be represented by the following general formula (II),

wherein M is the transition metal; n is the formal charge on the transition metal having a value of from 0 to 7; and X is a counterion or covalently bonded component. Examples of the transition metal M include, but are not limited to, Cu, Fe, Au, Ag, Hg, Pd, Pt, Co, Mn, Ru, Mo, Nb and Zn. Examples of X include, but are not limited to, halide, hydroxy, oxygen, Ci-C6-alkoxy, cyano, cyanato, thiocyanato and azido. In one specific example, the transition metal is Cu(I) and X is halide, for example, chloride. Accordingly, one specific class of transition metal catalysts is the copper halides, for example, Cu(I)Cl. In certain embodiments, the transition metal catalyst may contain a small amount, for example, 1 mole percent, of a redox conjugate, for example, Cu(II)C when Cu(I)Cl is used. Additional catalysts useful in preparing the polymeric dispersant are described in U.S. Pat. No. 5,807,937 at column 18, lines 29 through 56. Redox conjugates are described in further detail in U.S. Pat. No.

5,807,937 at column 11, line 1 through column 13, line 38.

[0070] Ligands that may be used in the ATRP preparation of the polymeric dispersant include, but are not limited to, compounds having one or more nitrogen, oxygen, phosphorus and/or sulfur atoms, which can coordinate to the transition metal catalyst compound, for example, through sigma and/or pi bonds. Classes of useful ligands include, but are not limited to, unsubstituted and substituted pyridines and bipyridines; porphyrins; cryptands; crown ethers; for example, 18-crown-6;

polyamines, for example, ethylenediamine; glycols, for example, alkylene glycols, such as ethylene glycol; carbon monoxide; and coordinating monomers, for example, styrene, acrylonitrile and hydroxyalkyl (meth)acrylates. As used herein, the term "(meth)acrylate" and similar terms refer to acrylates, methacrylates and mixtures of acrylates and methacrylates. One specific class of ligands are the substituted bipyridines, for example, 4,4'-dialkyl-bipyridyls. Additional ligands that may be used in preparing polymeric dispersant are described in U.S. Pat. No. 5,807,937 at column 18, line 57 through column 21, line 43.

[0071] Classes of monomeric initiators that may be used in the ATRP preparation of the polymeric dispersant include, but are not limited to, aliphatic compounds, cycloaliphatic compounds, aromatic compounds, polycyclic aromatic compounds, heterocyclic compounds, sulfonyl compounds, sulfenyl compounds, esters of carboxylic acids, nitrites, ketones, phosphonates and mixtures thereof, each having a radically transferable group, and preferably a single radically transferable group. The radically transferable group of the monomenc initiator may be selected from, for example, cyano, cyanato, thiocyanato, azido and halide groups. The monomeric initiator may also be substituted with functional groups, for example, oxyranyl groups, such as glycidyl groups. Additional useful initiators are described in U.S. Pat. No. 5,807,937 at column 17, line 4 through column 18, line 28.

[0072] In certain embodiments, the monomeric initiator is selected from 1 - halo-2,3-epoxypropane, p-toluenesulfonyl halide, p-toluenesulfenyl halide, C6-C20- alkyl ester of alpha-halo-C2-C6-carboxylic acid, halomethylbenzene, (1- haloethyl)benzene, halomethylnaphthalene, halomethylanthracene and mixtures thereof. Examples of C₂-C6-alkyl ester of alpha-halo-C2-C6-carboxylic acids include, hexyl alpha-bromopropionate, 2-ethylhexyl alpha-bromopropionate, 2-ethylhexyl alpha-bromohexionate and icosanyl alpha-bromopropionate. As used herein, the term "monomeric initiator" is meant to be distinguishable from polymeric initiators, such as polyethers, polyurethanes, polyesters and acrylic polymers having radically transferable groups.

[0073] In the ATRP preparation, the polymeric dispersant and the amounts and relative proportions of monomeric initiator, transition metal compound and ligand may be those for which ATRP is most effectively performed. The amount of initiator used can vary widely and is typically present in the reaction medium in a

concentration of from 10^"4 moles/liter (M) to 3 M, for example, from 10^~3 M to 10^"1 M. As the molecular weight of the polymeric dispersant can be directly related to the relative concentrations of initiator and monomer(s), the molar ratio of initiator to monomer is an important factor in polymer preparation. The molar ratio of initiator to monomer is typically within the range of 10^"4: 1 to 0.5 : 1 , for example, 10^"3 : 1 to 5 x 10^" ²: 1.

[0074] In preparing the polymeric dispersant by ATRP methods, the molar ratio of transition metal compound to initiator is typically in the range of 10^"4:1 to 10 : 1 , for example, 0.1 :1 to 5 : 1. The molar ratio of ligand to transition metal compound is typically within the range of 0.1 : 1 to 100 : 1 , for example, 0.2 : 1 to 10 : 1. [0075] The polymeric dispersant may be prepared in the absence of solvent, i.e., by means of a bulk polymerization process. Often, the polymeric dispersant is prepared in the presence of a solvent, typically water and/or an organic solvent.

Classes of useful organic solvents include, but are not limited to, esters of carboxylic acids, ethers, cyclic ethers, C5-C10 alkanes, C5-C8 cycloalkanes, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amides, nitrites, sulfoxides, sulfones and mixtures thereof. Supercritical solvents, such as CO2, C1-C4 alkanes and

fluorocarbons, may also be employed. One class of solvents is the aromatic hydrocarbon solvents, such as xylene, toluene, and mixed aromatic solvents such as those commercially available from Exxon Chemical America under the trademark SOLVESSO. Additional solvents are described in further detail in U.S. Pat. No. 5,807,937, at column 21, line 44 through column 22, line 54.

[0076] The ATRP preparation of the polymeric dispersant is typically conducted at a reaction temperature within the range of 25°C to 140°C, for example, from 50°C to 100°C, and a pressure within the range of 1 to 100 atmospheres, usually at ambient pressure.

[0077] The ATRP transition metal catalyst and its associated ligand are typically separated or removed from the polymeric dispersant prior to its use in the polymeric dispersants of the present invention. Removal of the ATRP catalyst may be achieved using known methods, including, for example, adding a catalyst binding agent to the mixture of the polymeric dispersant, solvent and catalyst, followed by filtering. Examples of suitable catalyst binding agents include, for example, alumina, silica, clay or a combination thereof. A mixture of the polymeric dispersant, solvent and ATRP catalyst may be passed through a bed of catalyst binding agent.

Alternatively, the ATRP catalyst may be oxidized in situ, the oxidized residue of the catalyst being retained in the polymeric dispersant.

[0078] With reference to general formula (I), G may be a residue of at least one radically polymerizable ethylenically unsaturated monomer, such as a monomer selected from an oxirane functional monomer reacted with a carboxylic acid which may be an aromatic carboxylic acid or polycyclic aromatic carboxylic acid.

[0079] The oxirane functional monomer or its residue that is reacted with a carboxylic acid may be selected from, for example, glycidyl (meth)acrylate, 3,4- epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, allyl glycidyl ether and mixtures thereof. Examples of carboxylic acids that may be reacted with the oxirane functional monomer or its residue include, but are not limited to, napthoic acid, hydroxy napthoic acids, para-nitrobenzoic acid and mixtures thereof.

[0080] With continued reference to general formula (I), in certain

embodiments, W and Y may each independently be residues of, include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isobornyl

(meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isocane (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, butyl (meth)acrylate, methoxy poly(ethylene glycol) mono(meth)acrylate, poly(ethylene glycol) mono(meth)acrylate, methoxy

poly(propylene glycol) mono (meth)acrylate, poly(propylene glycol) mono

(meth)acrylate, methoxy copoly(ethylene glycol/propylene glycol) mono

(meth)acrylate, copoly(ethylene glycol/propylene glycol) mono (meth)acrylate.

[0081] In general formula (I), in certain embodiments, W and Y may each independently be residues of monomers having more than one (meth)acryloyl group, such as (meth)acrylic anhydride, diethyleneglycol bis(meth)acrylate, 1 ,4 -butanediol diacrylate, 1,6-hexanediol diacrylate, 4,4'-isopropylidenediphenol bis(meth)acrylate (Bisphenol A di(meth)acrylate), alkoxylated 4,4'-isopropylidenediphenol

bis(meth)acrylate, trimethylolpropane tris(meth)acrylate, alkoxylated

trimethylolpropane tris(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and copoly(ethylene glycol/propylene glycol) di(meth)acrylate.

[0082] The numerals p, q and s represent the average total number of G, W and Y residues, respectively, occurring per block or segment of G residues (G-block or G-segment), W residues (W-block or W-segment) and Y residues (Y-block G or Y- segment), respectively. When containing more than one type or species of monomer residue, the W- and Y-blocks may each have at least one of random block (e.g., di- block and tri-block), alternating, and gradient architectures. Gradient architecture refers to a sequence of different monomer residues that change gradually in a systematic and predictable manner along the polymer backbone. For purposes of illustration, a W-block containing 6 residues of butyl methacrylate (B MA) and 6 residues of hydroxy propyl methacrylate (HPMA), for which q is 12, may have di- block, tetra-block, alternating and gradient architectures as described in U.S. Pat. No. 6,642,301, col. 10, lines 5-25. In certain embodiments, the G-block may include about 5-15 residues of glycidyl(meth)acrylate) reacted with an aromatic carboxylic acid (such as 3-hydroxy-2-napthoic acid), the W-block may be a random block of about 20-30 BMA and HPMA residues and the Y-block may be a uniform block of about 5-15 butyl acrylate (BA) residues.

[0083] The order in which monomer residues occur along the polymer backbone of the polymeric dispersant is typically determined by the order in which the corresponding monomers are fed into the vessel in which the controlled radical polymerization is conducted. For example, the monomers that are incorporated as residues in the G-block of the polymeric dispersant are generally fed into the reaction vessel prior to those monomers that are incorporated as residues in the W-block, followed by the residues of the Y-block.

[0084] During formation of the W- and Y-blocks, if more than one monomer is fed into the reaction vessel at a time, the relative reactivities of the monomers typically determines the order in which they are incorporated into the living polymer chain. Gradient sequences of monomer residues within the W- and Y-blocks can be prepared by controlled radical polymerization, and, in particular, by ATRP methods by (a) varying the ratio of monomers fed to the reaction medium during the course of the polymerization, (b) using a monomer feed containing monomers having different rates of polymerization, or (c) a combination of (a) and (b). Copolymers containing gradient architecture are described in further detail in U.S. Pat. No. 5,807,937, at column 29, line 29 through column 31, line 35.

[0085] In certain embodiments, subscripts q and s each have a value of at least 1, such as at least 5 for general formula (I). Also, subscript s often has a value of less than 300, such as less than 100, or less than 50 (for example 20 or less) for general formula (I). The values of subscripts q and s may range between any combination of these values, inclusive of the recited values, for example, s may be a number from 1 to 100. Subscript p may have a value of at least 1, such as at least 5. Subscript p also often has a value of less than 300, such as less than 100 or less than 50 (e.g., 20 or less). The value of subscript p may range between any combination of these values, inclusive of the recited values, for example, p may be a number up to 50. The polymeric dispersant often has a number average molecular weight (Mn) of from 250 to 40,000, for example, from 1000 to 30,000 or from 2000 to 20,000, as determined by gel permeation chromatography using polystyrene standards.

[0086] Symbol Φ of general formula (I) is, or is derived from, the residue of the initiator used in the preparation of the polymeric dispersant by controlled radical polymerization, and is free of the radically transferable group of the initiator. For example, when the polymeric dispersant is initiated in the presence of toluene sulfonyl chloride, the symbol Φ, more specifically Φ- is the residue,

The symbol Φ may also represent a derivative of the residue of the initiator.

[0087] In general formula (I), T is or is derived from the radically transferable group of the ATRP initiator. The residue of the radically transferable group may be (a) left on the polymeric dispersant, (b) removed or (c) chemically converted to another moiety. The radically transferable group may be removed by substitution with a nucleophilic compound, for example, an alkali metal alkoxylate. When the residue of the radically transferable group is, for example, a cyano group (— CN), it can be converted to an amide group or carboxylic acid group by methods known in the art.

[0088] The polymeric dispersant is typically present in the grapheme carbon particle dispersion described above in an amount of at least 0.1 percent by weight, such as at least 0.5 percent by weight, or, in some cases, at least 1 percent by weight, based on the total weight of the grapheme carbon particle dispersion. The polymeric dispersant may typically be present in the grapheme carbon particle dispersion in an amount of less than 75 percent by weight, or less than 50 percent by weight, based on the total weight of the grapheme carbon particle dispersion. In certain embodiments, the polymeric dispersant may be present in the grapheme carbon particle dispersion in an amount of less than 30 percent by weight, or less than 15 percent by weight, based on the total weight of the grapheme carbon particle dispersion.

[0089] The grapheme carbon particle dispersion often also comprises at least water and/or at least one organic solvent. Classes of organic solvents that may be present include, but are not limited to, xylene, toluene, alcohols, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butyl alcohol, tert-butyl alcohol, iso-butyl alcohol, furfuryl alcohol and tetrahydrofurfuryl alcohol; ketones or ketoalcohols, for example, acetone, methyl ethyl ketone, and diacetone alcohol;

ethers, for example, dimethyl ether and methyl ethyl ether; cyclic ethers, for example, tetrahydrofuran and dioxane; esters, for example, ethyl acetate, ethyl lactate, ethylene carbonate and propylene carbonate; polyhydric alcohols, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, 2-methyl-2,4-pentanediol and 1,2,6-hexantriol; hydroxy functional ethers of alkylene glycols, for example, butyl 2-hydroxyethyl ether, hexyl 2-hydroxyethyl ether, methyl 2-hydroxypropyl ether and phenyl 2-hydroxypropyl ether; nitrogen containing cyclic compounds, for example, pyrrolidone, N-methyl-2- pyrrolidone and l,3-dimethyl-2-imidazolidinone; and sulfur containing compounds such as thioglycol, dimethyl sulfoxide and tetramethylene sulfone. When the solvent comprises water, it can be used alone or in combination with organic solvents such as propylene glycol monometheylether, ethanol and the like.

[0090] The grapheme carbon particle dispersion may be prepared by the use of conventional mixing techniques such as energy intensive mixing or grinding means, such as ball mills or media mills (e.g., sand mills), attritor mills, 3 -roll mills, rotor/stator mixers, high speed mixers, sonicators, and the like.

[0091] The grapheme carbon particles may be mixed with film-forming resins as described above and other components of the compositions. For example, for two- part coating systems, the grapheme carbon particles may be dispersed into part A and/or part B. In certain embodiments, the grapheme carbon particles are dispersed into part A by various mixing techniques such as sonication, high speed mixing, media milling and the like. In certain embodiments, the grapheme carbon particles may be mixed into the coating compositions using high-energy and/or high-shear techniques such as sonication, 3 -roll milling, ball milling, attritor milling, rotor/stator mixers, and the like.

[0092] Figs. 9 and 11 schematically illustrate resistive heating assemblies in the form of test panels in accordance with embodiments of the present invention. In Fig. 9, the resistive heating test panel includes a resistive heating coating 110 applied on a glass substrate 112. Electrically conductive wires 114 are connected at opposite ends of the resistive heating coating 110 by adhesive 116. In Fig. 11, the resistive heating test panel includes a resistive heating coating 210 applied on a metal substrate 212. Electrically conductive wires 214 are connected at opposite ends of the resistive heating coating 210 by adhesive 216.

[0093] The following examples are intended to illustrate various aspects of the invention, and are not intended to limit the scope of the invention.

Example 1

[0094] The compositions summarized in Table 1 were dispersed by adding 70g of the following composition into 8 oz. glass jars with 220g of SEP Ermil 1.0- 1.25mm milling media. All of the compositions were formulated comprising 60.95 g of n-methyl-2-pyrrolidone, 7.0 g total of grapheme carbon particles, and 2.05 g of solvent-born block copolymer dispersant (which comprises 43 weight % n-butyl acetate and 57 weight % block copolymer as disclosed in US 2008/0188610). The samples in the jars were shaken for 4 hours using a Lau disperser (Model DAS 200, Lau, GmbH). After shaking, the dispersions were diluted with additional n-methyl-2- pyrrolidone before filtering off the milling media. The P/B (pigment to binder ratio) in each composition is 6.

Table 1

Dispersions

[0095] In Table 1, the designation M-25 stands for xGnP-M-25 exfoliated grapheme carbon particles commercially available from XG Sciences. The designation TGC stands for thermally produced grapheme carbon particles produced in accordance with the method disclosed in U.S. Patent No. 8,486,364 having a measured BET surface area of 280 m²/g. The %TS (% total solids) of each dispersion after dilution and filtering off the milling media is shown. Sample A contains only the TGC grapheme carbon particles, while Samples B and C contain only the M-25 grapheme carbon particles. Samples D, E, F, G, H, I and J contain both types of grapheme carbon particles co-dispersed together. The weight % of each type of grapheme carbon particle relative to the total grapheme carbon particle content in each composition is shown.

Example 2

[0096] Sample A from Table 1 containing only TGC grapheme carbon particles was mixed with Sample B from Table 1 containing only M-25 grapheme carbon particles in different ratios, as listed below in Table 2. Each mixture was made by adding the appropriate amount of each sample together into a glass jar and vigorously stirring with a stir blade until thoroughly mixed. The P/B for each resulting composition is 6.

Table 2

Mixtures

Example 3

[0097] Samples C through J from Table 1 and Samples 1 through 13 from Table 2 were applied as 1 -2 mm wide lines in a serpentine circuit pattern to a 2 x 3 inch glass slide (Fisherbrand, Plain, Precleaned) using a dispensing jet (PICO valve, MV-100, Nordson, EFD) and a desktop robot (2504N, Janome) and then dried in an oven at 212 °F for 30 minutes. The electrical conductivity was determined by first measuring the resistance of the serpentine circuit vs. the length of the circuit line. Then, the cross-sectional area of the serpentine lines was measured using a stylus profilometer (Dektak). Using the measured values for the cross sectional area (A) and the resistance (R) for a given length (L) of the circuit, the resistivity (p) was calculated using the equation p = RA/L. Then the conductivity (σ) was calculated by taking the reciprocal of the resistivity, σ = 1/p. Conductivity results are shown in Table 3 in units of Siemen per meter.

Table 3

Electrical Conductivity

[0098] In Table 3, %TGC designates the weight % of thermally produced grapheme carbon particles of the total grapheme carbon particle content of the composition. M-25 designates the dispersion of just xGnP-M-25 (from Sample C). M designates the mixture of dispersions with two different grapheme carbon particle types (Samples 1 through 13). C designates the co-dispersions of two types of grapheme carbon particles (Samples D through J). The conductivity results listed in Table 3 are shown graphically in Fig. 1, which plots electrical conductivity versus %TGC for both the co-dispersions and the mixtures of the grapheme carbon particles.

Example 4

[0099] A co-dispersion is made by adding 70 g of the following composition into an 8 oz. glass jar with 350 g of Zirconox 1.0-1.2 mm media: 87.02 weight % n- methyl-2-pyrrolidone, 1.00 weight % n-butyl acetate, 7.70 weight % xGnP-M-25 exfoliated grapheme carbon particles, 2.57 weight % thermally-produced grapheme carbon particles produced in accordance with the method disclosed in U.S. Patent No. 8,486,364 having a measured BET surface area of 280 m²/g, and 1.71 weight % of dispersant solids, where the dispersant solids arise from a 50/50 mixture of two types of solvent-born block copolymer dispersants (both of which are block copolymers as disclosed in US 2008/0188610), in which the chemical composition of the dispersants is similar, but the molecular weight of the two dispersants is different; specifically, one has a molecular weight of 9,700 g/mol, and the other has a molecular weight of 4,850 g/mol. The jar and milling media were shaken for 4 hours using a Lau disperser (Model DAS 200, Lau, GmbH). After shaking, the co-dispersion was diluted with additional n-methyl-2-pyrrolidone before filtering off the milling media. The P/B (pigment to binder ratio) of this composition is 6. The conductivity of this composition was measured to be 27,893 S/m.

Example 5

[00100] The compositions summarized in Table 4 were dispersed by adding 21.88 g of the following composition into 2.5 oz. glass jars with 109 g of milling media (Zirconox 1.0-1.2 mm). All of the compositions were formulated comprising 19.34 g of n-methyl-2-pyrrolidone, 2.19 g total of carbon particles, and 0.18 g of a solvent-born block copolymer dispersant comprising 39.89 weight % n- butyl acetate and 60.11 weight % block copolymer as disclosed in US2008/0188610 with a molecular weight of 9,700 g/mol, and 0.17 g of a solvent-born block copolymer dispersant comprising 33.73 weight % n-butyl acetate and 66.27 weight % block copolymer as disclosed in US 2008/0188610 with a molecular weight of 4,850 g/mol. The samples in the jars were shaken for 4 hours using a Lau disperser (Model DAS 200, Lau, GmbH). Extra n-methyl-2-pyrrolidone (from 0 g up to 6.25g) was added after milling to enable easier filtration of the product from the milling media. The milling media were then filtered off from the dispersions. The final % total solids were then measured. The P/B (pigment to binder ratio) in each composition is 10.

[00101] Each of these compositions (Samples , L and M) were applied as 1 -2 mm wide lines in a serpentine circuit pattern to a 2 x 3 inch glass slide

(Fisherbrand, Plain, Precleaned) using a dispensing jet (PICO valve, MV-100, Nordson, EFD) and a desktop robot (2504N, Janome) and then dried in an oven at 212°F for 30 minutes. The electrical conductivity for each composition was determined by first measuring the resistance of the dried circuit lines vs. the length of the circuit lines using a digital multi-meter (DVM890, Velleman). Then, the cross- sectional areas of the circuit lines were measured using a stylus profilometer (Dektak). For each composition, using the measured values for the cross sectional area (A) and the resistance (R) for a given length (L) of the circuit lines, the resistivity (p) was calculated using the equation p = RA/L. Then the conductivity (σ) was calculated by taking the reciprocal of the resistivity, σ = 1/p.

Table 4

Dispersions

[00102] In Table 4, the designation Functionalized M-25 stands for xGnP-M-25 exfoliated grapheme carbon particles commercially available from XG Sciences, which has been functionalized by refluxing 10 g of M25 in 500 ml of nitric acid (ACS Reagent, 70 %) at 120°C for 2 hrs, filtering and washing well with distilled water. The oxygen content is increased from less than 1 % to greater than 4% by this process as measured by XPS. The designation TGC stands for thermally produced grapheme carbon particles produced in accordance with the method disclosed in U.S. Patent No. 8,486,364 having a measured BET surface area of 280 m²/g. The Graphite is C-nergy SFG6 L Graphite AL-010, from Timcal. The %TS (% total solids) of each dispersion after dilution and filtering off the milling media is shown. Sample K contains both types of grapheme carbon particles (M25 and TGC) co-dispersed together. Sample L contains only functionalized M25graphenic carbon particles. Sample M contains no grapheme carbon particles, and contains a single type of carbon particle, namely, graphite.

Example 6

[00103] Sample C was applied onto a cleaned glass panel (4 x 8 inches) using a multiple clearance square applicator (2 inch square frame, Cat. No. 5361 , from Byk Additives & Instruments) at 1 mil wet film thickness. The panel with the applied coating was baked in an oven for 30 minutes at 212°F. Wire Glue™ (conductive glue from Idolon Technologies) was used to glue copper wire electrodes at the ends of the coating to thereby produce a test panel similar to that shown in Fig. 9. The glue dried for 24 hours. The thickness of the coating was measured with an optical profilometer (Veeco Wyko NT3300 run in VSI mode) to be 2.2 μηι. The resistance between the electrodes was measured to be 183 ohms using a digital multi -meter (DVM890, Velleman). In a resistive heating experiment, an electrical potential of 60 V was applied to the to the copper wire electrodes using a Xantrex HPD 60-5 power supply, and the temperature of the glass plate was then measured between the electrodes using a Fluke 62 Max I thermometer. The temperature at the center of the glass plate rose from 73°F to 138°F in 12.3 minutes, as graphically shown in Fig. 10.

Example 7

[00104] Sample G was diluted with n-methyl-2-pyrrolidone to a total solids value of 5.2%. The diluted sample was then applied onto a cleaned glass panel (4 x 8 inches) using a multiple clearance square applicator (2 inch square frame, Cat. No. 5361, from Byk Additives & Instruments) at 2 mil wet film thickness. The panel with the applied coating was baked in an oven for 30 minutes at 212°F. Wire Glue™ (conductive glue from Idolon Technologies) was used to glue copper wire electrodes at the ends of the coating to thereby produce a test panel similar to that shown in Fig. 9. The glue dried for 24 hours. The resistance between the electrodes was measured to be 54.3 ohms using a digital multi-meter (DVM890, Velleman). In a resistive heating experiment, an electrical potential of 60 V was applied to the to the copper wire electrodes using a Xantrex HPD 60-5 power supply, and the temperature of the glass plate was then measured between the electrodes using a Fluke 62 Max IR thermometer. The temperature at the center of the glass plate rose from 78° F to 230° F in 2.2 minutes, as graphically shown in Fig. 10.

Example 8

[00105] Sample K, L and M were applied onto 4 x 12 inch, primed, metal panels (ACT Test Panels, 04X12X032, Item No. 54476, C710C59, ED6060C, HP78) using a multiple clearance square applicator (2 inch square frame, Cat. No. 5361, from Byk Additives & Instruments) at 8 mil wet film thickness. The panels with the applied coatings dried for 3 days and were then baked in an oven for 30 minutes at 212°F. Wire Glue™ (conductive glue from Idolon Technologies) was used to glue copper wire electrodes at the ends of the coating to thereby produce test panels similar to that shown in Fig. 11. The glue dried for 24 hours. Table 5 shows dry film thickness (DFT) measurements, resistance measurements, and the results of resistive heating experiments with these panels. The thickness of the coating on each panels was measured with an optical profilometer (Veeco Wyko NT3300 run in VSI mode). The resistance between the electrodes was measured using a digital multi-meter (DVM890, Velleman). In the resistive heating experiments, an electrical potential of only 6 V was applied to the to the copper wire electrodes using a Hewlett Packard E3610A DC power supply, and the temperature of the metal panel between the electrodes was then measured using a Fluke 62 Max IR thermometer. The temperature is plotted vs. time in Fig. 12.

Table 5

Resistive Heating Panels

[00106] Table 5 and Fig. 12 show the advantage of the grapheme carbon particle coatings (panels with Samples K and L) compared to the graphite coatings (panel with Sample M). In particular, the panel with Sample K shows exceptional heating (27.9 °F temperature increase) with only 6 V of applied voltage and from only a 13.6 μιη thick film.

Example 9

[00107] A co-dispersion was made by adding into a 2.5 oz. jar, 109 g of

Zirconox 1.0-1.2 mm milling media, and the following ingredients: 0.18 g of a solvent-born block copolymer dispersant comprising 39.89 weight % n-butyl acetate and 60.11 weight % block copolymer as disclosed in US 2008/0188610 with a molecular weight of 9700 g mol, and 0.17 g of a solvent-born block copolymer dispersant comprising 33.73 weight % n-butyl acetate and 66.27 weight % block copolymer as disclosed in US 2008/0188610 with a molecular weight of 4850 g/mol, 19.34 g of n-methyl-2-pyrrolidone, 1.64 g of xGnP-M-25 exfoliated grapheme carbon particles commercially available from XG Sciences, which had been functionalized by refiuxing 10 g of the exfoliated grapheme carbon particles in 500 ml of nitric acid (ACS Reagent, 70 %) at 120°C for 2 hrs, and filtering and washing well with distilled water, and 0.55 g of thermally produced grapheme carbon particles produced in accordance with the method disclosed in U.S. Patent No. 8,486,364 having a measured BET surface area of 280 m2/g, and which had been functionalized by adding 25 g of the thermally produced grapheme carbon particles to 3.75 g of sulfanilic acid in 225 g of DI water at 80°C with stirring, then adding gradually 1.50 g of sodium nitrite in 6 g of DI water and rinsing it in with a further 6 g of water. The reaction was cooled after gas evolution ceased and the grapheme carbon particles were filtered, washed with 10% sulfuric acid and then with water before drying at 80°C for 2 hrs. The jar was shaken for 4 hours using a Lau disperser (Model DAS 200, Lau, GmbH). After shaking, the co-dispersion was diluted with additional n-methyl-2- pyrrolidone before filtering off the milling media. The P/B (pigment to binder ratio) of this composition was 10. The final weight % of total solids was 8.75%. This sample was applied as 1 -2 mm wide lines in a serpentine circuit pattern to a 2 x 3 inch glass slide (Fisherbrand, Plain, Precleaned) using a dispensing jet (PICO valve, MV- 100, Nordson, EFD) and a desktop robot (2504N, Janome) and then dried in an oven at 212 °F for 30 minutes. The electrical conductivity the sample was determined by first measuring the resistance of the dried circuit lines vs. the length of the circuit lines using a digital multi-meter (DVM890, Velleman). Then, the cross-sectional areas of the circuit lines were measured using a stylus profilometer (Dektak). Using the measured values for the cross sectional area (A) and the resistance (R) for a given length (L) of the circuit lines, the resistivity (p) was calculated using the equation p = RA/L. Then the conductivity (σ) was calculated by taking the reciprocal of the resistivity, σ = 1/p. The conductivity of this composition was measured to be 64,400 S/m.

Example 10

[00108] The co-dispersion described in Example 9 was diluted to 7.4 weight % total solids using n-methyl-2-pyrrolidone and was applied onto 4 x 12 inch, primed, metal panels (ACT Test Panels, 04X12X032, Item No. 54476, C710C59, ED6060C, HP78) using a multiple clearance square applicator (3 inch square frame, Cat. No. 5353, from Byk Additives & Instruments) at 5 mil wet film thickness. The panels with the applied coatings dried for 3 days and were then baked in an oven for 30 minutes at 212°F. Wire Glue™ (conductive glue from Idolon Technologies) was used to glue copper wire electrodes at the ends of the applied co-dispersion. The glue dried for 24 hours. A silver automotive basecoat composition was prepared according to Example 10 described in US 8,846,156 B2, composed in part of a polyester latex, polyurethane-acrylic latex, inorganic pigments, solvent and additives. The electrodes glued to the applied co-dispersion were masked with aluminum foil and the silver basecoat was spray applied over top of the applied co-dispersion. Spray application was performed using a Compuspray Automatic Test Panel Machine (Spraymation, Inc.) equipped with a 9 AR spraygun (Binks, Inc.) at 60 PSI using a 10 inch fan pattern, 2 inch index distance, 6 inch initial index position up from bottom, and 10 strokes per coat. Basecoat was spray applied in an environment controlled to 70-75° F. (21-24° C.) and 55-65% relative humidity at a film thickness of 11-13μηι. Dry film thickness measurements were made using a Feritscope FMP30 (Fischer, Windsor CT). The basecoat was applied in two coats, without a flash between coats, and then flashed at ambient temperature for 5 minutes and then dehydrated for 10 minutes at 176° F. (80° C.) by applying an electrical current through the conductive coating. Voltage was applied as described in Example 8, ramping from 30V to 55V over 5.5 minutes and held for an additional 4.5 minutes, achieving a peak temperature of 80° C. Fig. 13 illustrates the temperatures achieved during this partial curing dehydration process and the voltages applied. TKAPO1000, a 2K clear coat composition commercially available from PPG Industries, Inc., was then applied over the coated panel in two coats without a flash between coats. The clear coated panels were allowed to flash for 10 minutes at ambient conditions and baked for 30 minutes at 266° F. (130° C.) by applying electrical current through the conductive coating.

Voltage was applied as described in Example 8, holding at 63kV for 30 minutes and achieving a peak temperature of 130° C. The clear coat had a dry film thickness of approximately 1.8 mils (45 microns). Fig. 13 also illustrates the temperatures achieved during this fully curing process at the applied voltage.

Example 11

[00109] A conventional oven cured control was produced to compare to

Example 10 by spray application of the basecoat directly to the same type of 4x12, primed, metal panels used for Example 10. No conductive coating was applied, but the same basecoat and clearcoat were applied as were applied in Example 10. All application conditions, film builds, flash times and cure temperatures were the same as those used for Example 10, but dehydration and cure of the sample was

accomplished conventionally via an oven. [00110] For purposes of this detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[00111 ] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[00112] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[00113] In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in this application, the use of "or" means "and/or" unless specifically stated otherwise, even though "and/or" may be explicitly used in certain instances.

[00114] It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the following claims unless the claims, by their language, expressly state otherwise. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof.

Claims

WE CLAIM:

1. A resistive heating assembly comprising:

a substrate;

a conductive coating comprising grapheme carbon particles applied to at least a portion of the substrate; and

a source of electrical current connected to the conductive coating.

2. The resistive heating assembly of Claim 1 , wherein the conductive coating has an electrical conductivity of greater than 10,000 S/m.

3. The resistive heating assembly of Claim 2, wherein the conductive coating has a thickness of less than 100 microns.

4. The resistive heating assembly of Claim 1 , wherein the grapheme carbon particles comprise thermally produced grapheme carbon particles.

5. The resistive heating assembly of Claim 4, wherein the thermally produced grapheme carbon particles have a BET specific surface area of at least 70 square meters per gram.

6. The resistive heating assembly of Claim 1 , wherein the grapheme carbon particles are functionalized.

7. The resistive heating assembly of Claim 1 , further comprising at least one curable layer adjacent to the conductive coating, wherein the at least one curable layer may be cured by heat generated from the conductive coating when the electrical current is applied to the conductive coating.

8. The resistive heating assembly of Claim 7, wherein the conductive coating is located between the substrate and the at least one curable layer.

9. The resistive heating assembly of Claim 7, further comprising an insulating layer between the substrate and the conductive coating.

10. The resistive heating assembly of Claim 7, wherein the assembly comprises two of the curable layers and the conductive coating is located adjacent to the substrate under the two curable coatings.

11. The resistive heating assembly of Claim 7, wherein the at least one curable layer comprises a thermoplastic or thermosetting film-forming resin.

12. The resistive heating assembly of Claim 7, wherein the at least one curable layer has a thickness of less than 50 microns.

13. A conductive coating comprising grapheme carbon particles having a thickness of less than 100 microns and an electrical conductivity of greater than 10,000 S/m.

14. The conductive coating of Claim 13, wherein the grapheme carbon particles comprise thermally produced grapheme carbon particles.

15. The conductive coating of Claim 14, wherein the thermally produced grapheme carbon particles are produced in a thermal zone having a temperature of greater than 3,500°C and have an average aspect ratio of greater than 3:1.

16. The conductive coating of Claim 14, wherein the thermally produced grapheme carbon particles have a BET specific surface area of at least 70 square meters per gram.

17. The conductive coating of Claim 13, wherein the grapheme carbon particles comprise at least two types of grapheme carbon particles.

18. The conductive coating of Claim 17, wherein one of the types of grapheme carbon particles comprises thermally produced grapheme carbon particles.

19. The conductive coating of Claim 18, wherein the thermally produced grapheme carbon particles comprise from 4 to 40 weight percent of the total amount of the grapheme carbon particles.

20. The conductive coating of Claim 13, further comprising at least one film-forming resin.

21. The conductive coating of Claim 20, wherein the at least one film forming resin comprises epoxy resins, acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, bisphenol A based epoxy polymers, polysiloxane polymers, styrenes, ethylenes, butylenes, copolymers thereof, or combinations thereof.

22. The conductive coating of Claim 20, wherein the grapheme carbon particles comprise from 40 to 95 weight percent of the conductive coating.

23. The conductive coating of Claim 20, wherein the grapheme carbon particles comprise from 50 to 90 weight percent of the conductive coating.

24. The conductive coating of Claim 13, wherein the electrical conductivity is greater than 20,000 S/m.

25. The conductive coating of Claim 13, wherein the electrical conductivity is greater than 30,000 S/m.

26. The conductive coating of Claim 13, wherein the coating is deposited from a co-dispersion comprising:

a solvent;

at least one polymeric dispersant; and

at least two types of grapheme carbon particles co-dispersed in the solvent and the polymeric dispersant.

27. A method of curing a layer of curable material comprising applying electrical current to a conductive coating adjacent to the layer of curable material, wherein the conductive coating comprises grapheme carbon particles and has a thickness of less than 100 microns and an electrical conductivity of greater than 10,000 S/m.

28. The method of Claim 27, wherein the conductive coating is heated to a temperature of from greater than 25°C to 350°C for a time of from 2 seconds to 2 hours.