HK1193799B - Facile synthesis of graphene, graphene derivatives and abrasive nanoparticles and their various uses, including as tribologically-beneficial lubricant additives - Google Patents

Description

The facile synthesis of graphene, graphene derivatives, and abrasive nanoparticles and their various uses, including as tribologically beneficial lubricant additives

Related application references

This application claims the benefit of U.S. Provisional Patent Application No. 61/596,936, filed on February 9, 2012, entitled “Tribologically Beneficial Carbonaceous Materials and Nano-Abrasive Lubricant Molecules from Intentional In-Situ Pyrolysis of Sacrificial Cyclic Carbon Constituents”; and U.S. Provisional Patent Application No. 61/596,936, filed on December 23, 2011, entitled “Graphene and Graphene Derivatives Synthesis by Dehydration or Pyrolysis of Carbonaceous Materials, Vapor Exfoliation or PAH Formation, and Subsequent Hydrophobic Self-Assembly.” and U.S. Provisional Patent Application No. 61/579,993, filed on December 9, 2011, entitled “Synthesis of Graphene, Graphene Derivatives, Carbon-Encapsulated Metallic Nanoparticles, and Nano-Steel, and the Use of Sequestered Carbonaceous Wastes and Greenhouse Gases in Such Synthesis Methods”; and U.S. Provisional Patent Application No. 61/568,957, filed on October 12, 2011, entitled “Combustion Synthesis of Graphene Oxide and Graphene”. and Graphene Oxide Synthesis; and U.S. Provisional Patent Application No. 61/541,637, filed on September 30, 2011, entitled “Lubricating Additives, Polishing Compositions, Nanoparticles, and Tribological Coatings, and Uses Thereof, and Methods of Nanoparticle, Graphene, and Graphene Oxide Synthesis.” and Methods of Polishing Surfaces; and and U.S. Provisional Patent Application No. 61/452,781 of the Company's parent company, Inc.; the disclosures of which are hereby incorporated by reference in their entirety.

Background of the Invention

Technical Field

The present invention relates to methods for the ex situ synthesis of graphene, graphene oxide, reduced graphene oxide, and other graphene derivative structures that are scalable to industrial scale, as well as nanoparticles and their use in such ex situ syntheses, including but not limited to composite materials, composite material preparation and coatings, tribology, nanotechnology, surface finishing, machining and machining tools, bores, drilling, tunneling, ballistics, anti-ballistic technology, thermal insulation, heat absorption, lubricant additives, lubricant compositions, coatings, lubrication methods, hard surface polishing methods, and methods for cutting, drilling, hardening, protecting, and fabricating steel and other hard surfaces. The present invention further relates to the use of abrasive nanoparticles in lubricant compositions for polishing, hardening, protecting, and extending the life of moving and stationary parts in equipment and systems, including but not limited to engines, turbochargers, turbines, magnetic tracks, raceways, wheels, bearings, gear systems, and other physical and mechanical systems that utilize interacting hard surfaces through machining, wherein the abrasive nanoparticles are formed in situ from the lubricant composition or (in some cases) formed ex situ from the lubricant composition and then added to the lubricant prior to use.

Related technical description

Synthesis of graphene and graphene derivatives

Due to its observed and theoretical physical properties (including its large specific surface area, high intrinsic mobility, high Young's modulus (~1.0 TPa), high thermal conductivity (~5000 Wm-1K-1), high optical transmittance (~97.7%), low gas permeability, and high electron transport capability), single-layer graphene has been the subject of considerable investigation, research, and discussion in recent years. For example, see Geim et al., "The Rise of Graphene", Natural Materials, Vol. 6, pp. 183-191, and Zhu et al., "Graphene and Graphene Oxide: Synthesis, Properties, and Applications", Advanced Materials, Vol. 22, pp. 3906-3924, 2010. Oxide: Synthesis, Properties, and Applications”, Advanced Materials, Vol. 22, pp. 3906-3924, 2010). Based on these properties, graphene has been considered for a variety of applications, such as photocatalysis, energy storage, solar cells, transparent electrodes, semiconductors, high-strength/low-weight composites, protective coatings, and electric field emission. However, large-scale and economical production methods remain elusive.

Pure graphene is a planar, multi-ringed, single-atomic layer of pure carbon in a honeycomb lattice of ^sp2- hybridized carbon rings. Graphene is theoretically a single pure layer of graphite, although the term "graphene" is traditionally used for materials with several stacked atomic layers of graphite, or for materials with slightly defective graphite layers that still have properties similar to pure graphene. Graphene is relatively hydrophobic and is traditionally formed by exfoliation of graphite (which can be accomplished using supercritical carbon dioxide or by micromechanical exfoliation) or by epitaxial growth on silicon carbide or certain metal substrates. Graphene can also be formed by passing ethanol droplets through an argon plasma in an atmospheric-pressure microwave plasma reactor. For details, see Dato et al., “Substrate-free Gas-phase Synthesis of Graphene Sheets”, Nano Letters, Vol. 8, pp. 2012-2016, 2008.

There have also been reports of graphene nanotube synthesis using aerosol pyrolysis. For details, see Pinault et al., "Carbon nanotubes produced by aerosol pyrolysis: growth mechanisms and post-annealing effects," Diamond and Related Materials, Vol. 13, pp. 1266-1269, 2004. A 2.5-5 wt% solution of ferrocene in toluene or cyclohexylamine is dissolved with argon and pyrolyzed at 800-850°C. The early stages of carbon nanotube formation are observed. A layer of nanoparticles, believed to be composed of iron, first forms on a solid substrate. An ordered carpet of nanotubes grows from this layer of nanoparticles, with a single nanotube growing from each nanoparticle. High temperature annealing of the sample resulted in the elimination of iron from the nanotubes and in improved ordering of the nanotubes.

Several recent publications report the formation of graphene bonds under combustion conditions. In one example, very small amounts of nanoparticles of all four forms of carbon (i.e., diamond, graphite, fullerene, and amorphous) were found in a paraffin candle flame—see Su et al., “New insight into the soot nanoparticles in a candle flame,” Chemical Communications, Vol. 47, pp. 4700-4702, 2011. In another previous example, small amounts of nanoparticulate graphitic carbon were discovered during acid treatment of carbon black from a methane flame—see Tian et al., “Nanosized Carbon Particles from Natural Gas Soot”, Chem. Mater., Vol. 21, pp. 2803-2809, 2009. In another previous example, highly graphitized hollow nanotubes were discovered from an ethanol flame—see Pan et al., “Synthesis and growth mechanism of carbon nanotubes and nanofibers from ethanol flames”, Micron, Vol. 35, pp. 461-468, 2004. Similarly, carbon nanotubes have been synthesized using a CO/H2/He/C2H2 (carbon monoxide/hydrogen/helium/acetylene) gas mixture combusted in an acetylene flame in the presence of laser-ablated iron or nickel nanoparticle catalysts. For details, see Vander Wal et al., “Flame Synthesis of Carbon Nanotubes using Catalyst Particles Prepared by Laser Ablation”, American Chemical Society, Division of Fuel Chemistry, Vol. 49, pp. 879-880, 2004.

Polycyclic aromatic hydrocarbons (PAHs) constitute part of the atmospheric "soot" contained in residual particulate matter from incomplete combustion, pyrolysis, or other low-oxygen thermal degradation of hydrocarbons. Because these PAHs are generally considered undesirable byproducts of incomplete combustion, much research has focused on how to minimize or completely eliminate the formation of "soot" during combustion, as seen, for example, in Coppalle et al., "Experimental and Theoretical Studies on Soot Formation in an Ethylene Jet Flame," Combustion Science and Technology, Vol. 93, pp. 375-386, 1993.

PAHs have a fully planar structure of fused aromatic carbon rings, with hydrogen atoms bonded to surrounding carbon atoms of the backbone. PAHs can be viewed as microscopic and nanoscale structures of graphene.

Graphene derivatives include structures with graphitic bonds that are partially incorporated with heteroatoms, such as oxygen or other structural defects in the carbon lattice. As described herein, graphene derivatives also include structures such as nanotubes, nanobuds, fullerenes, nanopeapods, intercalated fullerenes, nanoonions, graphene oxide, irregular carbon, and other non-graphene forms of graphitic carbon that may include structural or chemical defects.

Graphene oxide (GO) is an impure, oxidized form of graphene that includes hydroxyl and epoxy groups bonded to various carbon atoms in the lattice framework. The structural properties of GO have been extensively studied, as described in Mkhoyal et al., "Atomic and Electronic Structure of Graphene Oxide," Nano Letters, Vol. 9, pp. 1058-1063, 2009. However, the precise chemical structure of GO remains a subject of debate and is subject to considerable uncertainty, at least with respect to the frequency and location of hydroxyl and epoxy groups observed in the various samples studied.

Graphene oxide (GO) is also known to include carboxylic acid groups believed to be located at the edges of the carbon sheet. These various groups allow for further chemical functionalization of graphene oxide. Recently, it has been reported that the conversion of carboxyl groups to hydroxyl groups in a graphene derivative produces a substance called "graphenol." There have been reports of converting this "graphenol" to graphene via pyrolysis, however, these methods involve the use of toxic chemicals (such as hydrazine) - see U.S. Patent Application Publication No. 2011/0201739, entitled "Method and System for Producing Graphene and Graphenol," published by Beall on August 18, 2011.

Unlike graphene, graphene oxide (GO) is traditionally formed from exfoliated graphite oxide or by oxidation of the graphene itself. Graphene oxide flakes can be purposefully formed under a wide range of oxidation levels (with measured oxygen to carbon ratios up to approximately 1:2). Because graphene oxide has unique physical and chemical properties that differ from those of graphene, its structural variability has made it unattractive for many experimental studies. In contrast to graphene, graphene oxide is not only hydrophilic but also a highly rigid and strong electrical insulator—for details, see Dreyer et al., “The chemistry of graphene oxide”, Chemical Society Reviews, Vol. 39, pp. 228-240, 2010.

Graphene oxide (GO) was originally prepared by treating graphite with potassium chlorate and fuming nitric acid (Brodie, "On the Atomic Weight of Graphite", Proceedings of the Royal Society of London, Vol. 10, p. 249, 1859). A somewhat more efficient process uses sulfuric acid, sodium nitrate, and potassium permanganate to convert graphite to graphene oxide (Hummers et al., "Preparation of Graphitic Oxide", Journal of the American Chemical Society, Vol. 80, p. 1339, 1958). Recently, a more efficient method using sulfuric acid, phosphoric acid, and potassium permanganate has been reported. For details, see Marcano et al., “Improved Synthesis of Graphene Oxide,” ASC Nano, Vol. 4, pp. 4806-4814, 2010.

Colloidally dispersed graphene oxide (GO) in water can be chemically reduced to graphene using hydrazine hydrate. Other chemical reducing agents for GO include hydroquinone, gaseous hydrogen, and strongly alkaline solutions. Thermal exfoliation and reduction of GO occur when heated to 1050°C under hot extrusion conditions, eliminating the generated byproduct carbon dioxide gas. Finally, electrochemical reduction of GO can be achieved by placing electrodes at opposite ends of the GO film on a non-conductive substrate and then applying an electric current to the GO film.

While the complete reduction of graphene oxide to graphene has not been reported in the literature to date, graphene oxide has been reduced by a number of different processes, resulting in so-called "reduced graphene oxide" (rGO) with measured oxygen to carbon ratios as low as approximately 1:24.

Notably, reduced graphene oxide (rGO) has been observed to exhibit many chemical, physical, and electrical properties that are more similar to those of both graphene and graphene oxide.

Graphene and its various derivatives are currently the subject of much investigation and extensive research, in part due to their many potential uses, including but not limited to lubricants, molecular-level coatings for composite reinforcement, thermal insulation, ballistic transistors, integrated circuits, and reinforced fibers and cables.

Using chelated waste carbon in graphene production

Various forms of waste carbon sequestration are known in the art, including, but not limited to, converting carbonaceous waste into something like "biochar" or converting carbon dioxide into synthetic methanol—for example, see Hogan et al., "Biochar: Concept to Sequester Carbon," Encyclopedia of Earth, National Council for Science and the Environment, Washington, D.C., 2011; and Jiang et al., "Turning carbon dioxide into fuel," Philosophical Transactions of the Royal Society A, vol. 368, pp. 3343-3364, 2010. A, Vol. 368, pp. 3343-3364, 2010), but there has been no report on the beneficial use of such sequestered or captured carbon waste as a carbonaceous feedstock or enhancer in the synthesis of graphene.

Implantable medical prosthetic devices

A key factor in the success of implantable medical prostheses, both in terms of longevity and infection prevention, is the consistency of the tribological surface. Roughness on the surface of medical implanted metal components provides a location for microorganisms to linger. In the case of metal components in the vascular or circulatory system, these roughnesses also create a dangerous location for platelet aggregation, which can lead to heart attacks or strokes. Nanopolishing such implantable medical prostheses to near-atomic-level perfect smoothness would significantly improve their safety and efficacy.

Nanomedicine, oncology, and medical imaging

Improving the targeting of radiation or chemotherapy drugs to cancer sites and the ability to provide contrast in medical images are areas of active research in the medical field. Magnetic nanoparticles have been used as a tumor contrast agent in magnetic resonance imaging (MRI), for example, see Tiefenauer et al., "In vivo evaluation of magnetite nanoparticles for use as a tumor contrast agent in MRI", Magnetic Resonance Imaging, Vol. 14, No. 4, pp. 391-402, 1996. There has been fairly recent investigation and research into the use of “functionalized” “buckyballs” as a means of delivering targeted drug therapies to tumors in the body—an example of which is described in Yoon et al., “Targeted medication delivery using magnetic nanostructures”, Journal of Physics: Condensed Matter, Vol. 19, 9 pages, 2007.

Steel production

The pits and roughness on the steel surface provide a surface for destructive oxidation in the form of iron oxide (also known as rust). Reducing or eliminating these pits and roughness will increase the service life of such steel structures.

Reaction environment of graphene and graphene oxide

In some embodiments of the present invention, graphene and graphene oxide structures are used in various solvents to act as reaction envelopes, creating a nanoenvironment that allows reactions to occur that are thermodynamically similar or unfavorably similar to how enzymes work in biological systems. These graphene reaction envelopes (GREs) and graphene oxide reaction envelopes (GOREs) allow chemical reactions and atomic recombination (such as the reorganization of atoms into crystals) to occur that would not normally occur outside the reaction envelope. The graphene reaction envelope or graphene oxide reaction envelope acts as a "micro- or nanoreaction container," and portions of the envelope can then be trimmed into a nanoabrasive or other nanoparticle to become part of the reaction product. In one embodiment, the envelope acts as a nanoblast furnace for the production of iron into steel.

Steel can take many different forms, including but not limited to ferrite, austenite, pearlite, martensite, bainite, ledeburite, cementite, beta iron, hexavalent iron, and any combination thereof, depending on its manufacturing conditions. The nanosteel formed in the graphene reaction envelope or graphene oxide reaction envelope of the present invention can be ferrite, austenite, pearlite, martensite, bainite, ledeburite, cementite, beta iron, hexavalent iron, and any combination thereof.

Nanosteel, nanorobotics, and nanomachine manufacturing

The synthesis of nanocrystalline metal alloys is well known in the art, as described in Alavi et al., "Alkaline-earth Metal Carbonate, Hydroxide and Oxide Nano-crystals Synthesis Methods, Size and Morphologies Considerations," pp. 237-262 in Nanocrystals, ed. by Matsuda, InTech, Rijeka, Croatia, 2011. However, there are no reports on the synthesis of steel-reinforced nanoparticles, nano-onions, or methods for producing pure nanosteel crystals and nanometal sheets.

Nanorobotics generally refers to the science of nanotechnological engineering and the fabrication of mechanical devices from nanoscale components ranging in size from 0.1 to 10 μm (micrometers). Other common names for these theoretical devices are nanobots, nanooids, nanites, and nanomites. Future developments in this field are hypothesized to allow the construction of miniature teleoperated surgical instruments and nanoscale electronic devices. Simple and inexpensive nanofabrication methods for tiny steel crystals or ingots are likely to significantly advance this science.

Concrete pouring and asphalt paving technology

Concrete and asphalt concrete are two common composite materials used in construction. Concrete is a composite material consisting minimally of a cementitious base material, fine sand and gravel, coarse sand and gravel, and water. Asphalt concrete is generally a composite material consisting minimally of asphalt, a highly viscous, sticky, black, tar-like substance found in certain petroleum and natural sediments, and coarse sand and gravel. Over the years, a wide variety of admixtures and additives have been developed to enhance the strength of these materials.

The most common of these concrete "additives" fall into two general categories: water-reducing superplasticizers (also known as "superplasticizers") and synthetic reinforcing fibers used in the production of fiber-reinforced concrete (FRC). The superplasticizers, including the latest generation of polycarboxylate ether-based superplasticizers (PCEs) and polypropylene glycol (PPG) derivative admixtures, function to reduce the amount of water required to form the composite. Superplasticizers also improve the rheology (flow characteristics) of concrete pastes, thereby improving workability before concrete curing—for details, see Palacios et al., “Effect of superplasticizer and shrinkage-reducing admixtures on alkali-activated slag pastes and mortars,” Cement and Concrete Research, Vol. 35, pp. 1358-1367, 2004; and Aitcin et al., “Superplasticizers: How they Work and Why the Occasionally Don’t Work,” Concrete International, Vol. 16, pp. 45-52, 1994. Don’t”, Concrete International, Vol. 16, pp. 45-52, 1994).

In fiber-reinforced concrete (FRC), the purpose of the synthetic fibers (typically polypropylene fibers) is to increase the strength of the matrix and improve the plasticity of the concrete. The reinforcing fibers in concrete are intended to bridge microcracks in the concrete, allowing the concrete to maintain its ability to support its load without failing by completely separating along the cracks (for details, see Soroushian et al., "Mechanical Properties of Concrete Materials Reinforced with Polyproplene or Polyethelene Fibers," Materials Journal, Vol. 89, pp. 535-540, 1992).

In fact, none of the "additives" showed a dramatic increase in the strength of the concrete or asphalt concrete products or systems. It is believed that graphene and certain graphene derivatives can replace current state-of-the-art methods as reinforcing "additives" for concrete and asphalt.

Military and Ballistic Science

According to Columbia University (New York, NY, USA), graphene has been identified as the strongest material on Earth. Columbia researchers attribute graphene's extraordinary strength to its covalent carbon-carbon bond framework. The graphene samples tested were defect-free single-layer graphene. These tests revealed that a single sheet of graphene possesses an intrinsic strength of 42 ^Nm⁻¹ .

Modern anti-ballistic science seeks to develop thinner and thinner materials that can provide protection from ballistic projectiles and shrapnel. To this end, new methods of molecular reinforcement of polymer matrix composites (PMCs) are constantly being researched. The current state-of-the-art technology uses several types of high-performance ballistic yarns and fibers, including S-glass fibers, aramid fibers (e.g., 29, 49, 129, KM2), highly oriented ultra-high molecular weight polyethylene (e.g., polybenzoxazole (PBO) and polyphenylene pyridinium diimidazole (PIPD), etc.

Typical properties of these fibers are low density and high tensile strength, with correspondingly high energy absorption capabilities. In the case of polymer matrix composite (PMC) ballistic panels, the force-distributing deformation capabilities of the fibers are severely constrained by the surrounding resin of the composite, leading to failure under conditions of fracture and delamination of the resin matrix upon impact from projectiles. Graphene and its derivatives incorporated into textile composite ballistic panels would not suffer from the limitations of typical PMC resin matrices.

Graphene and its derivatives present unique anti-ballistic opportunities and materials. They possess high elastic modulus and tensile strength, with Young's modulus reaching up to 1000 GPa and tensile strength ranging from 13 to 53 GPa. Compared to traditional anti-ballistic fibers and composites, the potential of graphene and its derivatives far exceeds current state-of-the-art approaches.

Nanocomp Technologies Inc., a company working with the U.S. Army's Natick Soldier Center, is pursuing the development of a new generation of lightweight ballistic armor based on carbon nanotube technology. In April 2009, the company reportedly demonstrated that a 5mm thick carbon nanotube composite armor panel could withstand a 9mm diameter bullet. Further advances in the synthesis of graphene and graphene derivatives that can be scaled to industrial levels will undoubtedly bring this technology closer to commercialization.

Lubrication of mechanical systems

All mechanical systems involve friction between interacting components. Such interactions can be as simple as a ball bearing sliding along a raceway, a piston ring moving relative to a cylinder liner, or the contact between a camshaft and its cam follower. In all of these examples, friction between the interacting surfaces is a factor to consider. Friction in any system is a cause of stress, fatigue, wear, heat, noise, vibration, and ultimately, failure. Another common enemy of these metal-containing mechanical systems is corrosion.

In most cases, engineering science seeks to reduce the inherent friction in physical and mechanical systems with interacting surfaces by machining and polishing the interacting surfaces to the highest possible smoothness. Currently, no friction surface is completely smooth (i.e., completely free of roughness). As required, the interacting components of physical and mechanical systems are machined and polished to the required tolerances to allow proper operating performance and reduce inherent friction. The significant friction reduction achieved by so-called "super polishing" of components to high tolerances ("average roughness" (R _a ) <50 nm) has so far meant longer production times and higher production costs. In general, modern machining science has been forced to trade economic efficiency for machining precision.

Furthermore, all internal combustion engines (including naturally aspirated and turbocharged kerosene and diesel engines), turbines, and other geared systems require lubrication to operate properly. Since the dawn of engine and gear lubrication, numerous attempts have been made in the field to provide optimal lubrication for these machines. Initial attempts at lubrication (such as olive oil and certain carbolic soaps) have been replaced by more sophisticated hydrocarbon-based lubricants, many of which contain even more sophisticated additive packages, each attempting to address the various inherent problems inherent in the lubrication of these systems.

The current state-of-the-art in lubrication of metal-containing mechanical systems (such as internal combustion engines) uses elastohydrodynamic lubrication (EHL) technology, which "addresses" the problem of asperities on the interacting metal surfaces of a mechanical system by using incompressible fluids and protective coatings to prevent direct metal-to-metal contact. None of these methods affects the so-called _Ra ("average roughness") value of the interacting metal component surfaces, nor does it mitigate the friction-generating effects of the asperities themselves.

To maintain and protect metallic friction surfaces and systems including metallic friction surfaces, a variety of lubricant additives are used for various purposes, such as dispersants, corrosion inhibitors, tackifiers, rubber expanders, pour point depressants, foam inhibitors, antiwear agents, and antioxidants. Some lubricant additives that have been developed to reduce friction include the following: tri-o-cresol phosphate (TOCP or TCP), popular in aviation lubricants but known to slowly attack elastomeric gaskets and seals; cycloparaffin detergents known to combine with the products of incomplete combustion to form hydrochloric acid; zinc dialkyl dithiophosphates (ZDDPs), which are problematic for vehicles equipped with catalytic converters; chlorinated paraffins, which are globally classified as very harmful to aquatic life; suspended solids such as polytetrafluoroethylene (PTFE), which many consider unsuitable for lubrication; graphite powder, which many consider unsuitable for use in systems using bearings; molybdenum, a metal reported to reduce fuel economy; tungsten disulfide nano-onions, a temporary shielding solution; buckminsterfullerenes, another expensive and temporary solution; and nanodiamonds suspended in graphite to prevent the typical aggregation of abrasive particles (the use of this additive has caused complaints from those who oppose the use of graphite in systems with bearings). Lubricant additives also often contain phosphates and sulfides, which can produce harmful gases when they decompose.

Carbonaceous deposits within mechanical systems are almost universally considered undesirable, and many modern lubricants are specifically designed and formulated to inhibit and/or prevent any carbonaceous deposit formation. Conventional elastohydrodynamic lubrication knowledge dictates that internal combustion engine lubricants must be formulated to be as physically and chemically stable as possible to resist (rather than promote) thermal degradation of the base lubricant and its additives due to incomplete combustion and pyrolysis; this is because such thermal destruction of conventional lubricants produces harmful carbonaceous deposits (e.g., sludge) that tend to clog valves, coat piston rings, and generally reduce the engine's operating efficiency and life expectancy. Dispersants are commonly used in lubricants to prevent sediment aggregation. For example, see Won et al., “Effect of Temperature on Carbon-Black Agglomeration in Hydrocarbon Liquid with Adsorbed Dispersant,” Langmuir, Vol. 21, pp. 924-932, 2005; Tomlinson et al., “Adsorption Properties of Succinimide Dispersants on Carbonaceous Substrates,” Carbon, Vol. 38, pp. 13-28, 2000. Substrates”, Carbon, Vol. 38, pp. 13-28, 2000); Wang, “Synthesis and Characterization of Ethylene Carbonate Modified Polyisobutylene Succinimide Dispersants”, University of Waterloo Masters Thesis, 2010. Blow-by soot from engines due to incomplete combustion has been shown to be highly abrasive and capable of damaging metal parts—for example, see Jao et al., “Soot Characterization and Diesel Engine Wear,” Lubrication Science, Vol. 16, pp. 111-126, 2004; Ryason et al., “Polishing Wear by Soot,” Wear, Vol. 137, pp. 15-24, 1990; Yamaguichi et al., “Soot Wear in Diesel Engines,” Journal of Engineering Tribology, Vol. 220, pp. 463-469, 2006. Wear in Diesel Engines”, Journal of Engineering Tribology, Vol. 220, pp. 463-469, 2006; and Gautam et al., “Effect of Diesel Soot Contaminated Oil on Engine Wear—Investigation of Novel Oil Formulations”, Tribology International, Vol. 32, pp. 687-699, 1999. “Ashless” engine lubricants are another example of products that support the concept that lubricant formulations must be kept as free as possible of carbon particles and all harmful carbonaceous engine deposits. In the current elastohydrodynamic lubrication paradigm, thermal degradation and pyrolysis of lubricant additives that lead to the formation of carbonaceous soot and deposits are generally considered undesirable.

Current test standards for lubricants and their derivatives are further evidence of and support this lubrication philosophy. The "Noack Volatility Test" (ASTM D5800) measures the evaporation of a lubricant composition as a function of temperature, since lubricant compositions become more viscous as evaporation increases. The test involves placing a mass of engine oil in a "Noack" apparatus at a temperature of 250°C, with a constant flow of air passing through the sample for one hour. The mass of the sample is then measured to determine the mass loss due to the loss of volatile organic compounds (VOCs). An acceptable mass loss is no more than 13-15%. Lubricants must pass this test to be approved under the API CJ-4 engine lubricant standard (USA) or the ISLAC GF-4 engine lubricant standard (European Union).

Other industry evaporation tests for lubricants include ASTM D972 and ASTM D2595. ASTM D972 tests lubricant compositions at temperatures between 100°C and 150°C with a constant air flow rate (2 L/min) passing through the specimen. ASTM D2595 tests lubricant compositions at temperatures between 93°C and 316°C with a constant air flow rate (2 L/min) passing through the specimen.

The modern lubricant industry almost exclusively uses a linear or branched hydrocarbon based lubricant in elastohydrodynamic lubrication (EHL) lubricant compositions, along with small amounts of relatively expensive additives, including (in some cases) antioxidants such as certain hindered phenols, certain salicylates, and certain amines. For the most part, the prior art use of cyclic carbon-containing lubricant antioxidant additives has been limited to improving or protecting the base lubricant by inhibiting the base oxidation of the base lubricant from in-situ formed peroxides.

The above-described elastohydrodynamic lubrication (EHL) paradigm and the industry test standards described are based on the assumption that carbonaceous products of incomplete combustion or pyrolysis are generally harmful and undesirable within engines and mechanical systems. This means that the best results from using lubricants containing detergents, dispersants, and boundary films are achieved by keeping the lubricated interior of a mechanical system as clean, free of carbonaceous deposits, and free of wear as possible.

Production of fullerenes and their lubricating uses

Fullerenes, first discovered in 1985 and named after the late Buckminster Fuller, the architect of the Geodetic Dome, are a class of molecules whose outer shells are composed entirely of carbon rings. The basic spherical variety of fullerene is buckminsterfullerene, or simply "buckyball." Buckyballs can exhibit endohedral properties, trapping various atoms, ions, or composite materials within their hollow cores. Endohedral metallofullerenes containing metal ions are currently a topic of significant scientific inquiry and research.

Mathematically, a buckyball is a trivalent convex polyhedron composed of pentagonal and hexagonal carbon rings. Buckyballs obey the Euler polyhedron formula, since V – E + F = 2, where V, E, and F are the number of vertices, edges, and faces on the sphere's exterior, respectively. There are approximately 214,127,713 different species of non-isostructural fullerenes. Pure, ordinary buckyballs are commercially available in the chemical forms of C ₆₀ and C ₇₀ , but are quite expensive; typically, they cost between $900 and $1,000 per 100 mg.

Bucky-diamonds are nanoscale carbon composites consisting of a diamond core within a fullerene or fullerene-like shell. For example, see Barnard et al., "Coexistence of Bucky-diamond with nanodiamond and fullerene carbon phases," Physical Review B, Vol. 68, pp. 73406, 2003. This structure is believed to be an intermediate between the interconversion of nano-onions and nanodiamonds. Barnard et al. predicted that Bucky-diamonds are a metastable form of carbon that coexists with fullerenes in the form of nanodiamonds ranging in size from 500 to 1,850 atoms (1.4 to 2.2 nm in diameter).

Barnard et al., in "Substitutional Nitrogen in Nanodiamond and Bucky-Diamond Particles," Journal of Physical Chemistry B, Vol. 109, pp. 17107-17112, 2005, proposed the possibility of incorporating heteroatoms (such as nitrogen in this case) into the bucky-diamond structure. Recently, Yu et al. proposed a stable Si68C79 bucky-diamond structure based on computer molecular simulations in their article "Is There a Stable Bucky-diamond Structure for SiC Cluster," submitted to the Journal of Chemical Physics on August 24, 2011. In the stable state, the nanodiamond core and the fullerene-like shell are believed to be not chemically bonded to each other. Yu et al.'s simulations predict that upon heating this silicon carbide structure, _{the 35 -} atom core decomposes at a temperature lower than that of the 112-atom shell. The core then becomes incorporated into the shell, forming a larger, retained fullerene-like shell structure upon cooling.

Fullerenes represent a promising new technology in lubrication science. Numerous attempts have been made to use fullerenes as sealing lubricants, filling asperities on moving parts, and providing tribological films on moving parts. Unfortunately, large-scale, commercially viable methods for producing useful fullerenes have been elusive. Furthermore, the current state of tribology focuses on tribological films and coatings on moving parts. However, this old approach does not address the root cause of friction itself—the asperities on interacting metal parts.

The advent of nanotechnology and tribology has introduced several new lubrication methods using various nanoparticles. U.S. Patent Application Publication No. 2007/0292698, entitled "Trimetaspheres as Dry Lubricants, Wet Lubricants, Lubricant Additives, Lubricant Coatings, Corrosion-Resistant Coatings and Thermally-Conductive Materials," published by Gause on December 20, 2007, discloses the use of scandium-containing metallofullerene buckyballs as a suspended solid lubricant, replacing conventional carbon fullerenes, or "buckyballs," which rapidly decompose at high temperatures.

Externally isolated "single-nanobucky diamonds" (SNBDs) have been postulated for use as lubricant additives, however these molecules are inherently difficult to separate from undesirable aggregates, a necessary step in making them useful in lubrication and other applications—for example, see Ho, D. (ed.), Nanodiamonds : Applications in Biology and Nanoscale Medicine, Ch. 1, "Single-Nano Buckydiamond Particles, Synthesis Strategies, Characterization Methodologies and Emerging Applications", by Osawa, E., Springer Science+Business Media, LLC, New York, 2010.

NanoMaterials, Ltd. of Ness Ziona, Israel, has produced a series of lubricants containing tungsten disulfide nanopowders. These black tungsten sulfide onion structures are intended to fill surface roughness and exfoliation layers to act as a low-friction interaction shield between interacting metal engine parts.

NanoLube, Inc. of Lombard, Illinois, USA claims to produce non-abrasive carbon nanospheres under the DiamondLube ^™ trademark that are incorporated into lubricants to reduce friction. The DiamondLube ^™ product appears to be an expensive but common fullerene suspension in a light oil.

PlasmaChem GmbH of Berlin, Germany, markets an additive for engine lubricants under the trademark ® that contains diamond and graphite particles synthesized by detonation, claiming to polish internal engine components to a mirror-like finish. The graphite is presumably added to the suspension to reduce agglomeration of the nanoparticles.

Detonation nanodiamonds are typically formed by detonating an oxygen-deficient mixture of trinitrotoluene and cyclotrimethyltrinitramine. For example, see Mochalin et al., "The Properties and Applications of Nanodiamonds," Nature Nanotechnology, Vol. 7, pp. 11-23, 2012. Nanodiamonds produced by this method typically exist as 1-nm clusters of 5-nm (nanometer) diamond-shaped particles, each consisting of a diamond core with a layer of surface groups.

Other methods for forming nanodiamonds use non-detonation techniques, such as laser ablation of diamond microcrystals, high-energy ball milling, plasma-assisted chemical vapor deposition of carbides, autoclave synthesis, chlorination, ion irradiation of graphite, electron irradiation of carbon nano-onions, and ultrasonic cavitation. The non-detonation nanodiamonds obtained by these methods tend to cluster during synthesis, and considerable effort has been invested in developing methods to cleanly separate the agglomerated nanodiamond products.

The common element among most of these friction reduction solutions, and the current state of the art in the industry, is the use of elastohydrodynamic lubrication (EHL) technology. EHL uses various methods and materials to "treat" the problem of asperities on interacting metal surfaces in mechanical systems, rather than eliminating or "solving" the root cause of the problem—the asperities themselves. Those methods and materials that attempt to address asperity polishing and reduction do so by using externally supplied nanodiamond abrasives, which must be suspended in a material that prevents them from agglomerating into undesirable clusters. None of these methods and materials involve the in situ formation of beneficial carbonaceous tribological particles or non-abrasives from liquid precursors, a novel approach to addressing the current state of the art issue of undesirable particle agglomeration from externally supplied nanodiamond lubricant abrasives.

Summary of the Invention

The present invention relates to the facile synthesis of graphene, graphene derivatives, and nanoparticles and their use as tribologically beneficial lubricant additives. The products of the methods of the present invention have numerous uses in a variety of fields, including but not limited to tribology, nanotechnology, machining and machining tools, lubrication, metalworking, drilling, mining, paint manufacturing, corrosion protection coating manufacturing, rock tunneling, grooving, mold making, optical lens manufacturing, military engineering, gemstone cutting and polishing, aerospace engineering, automotive engineering, high-speed rail, maritime engineering, medicine, nuclear medicine, medical imaging and diagnostics, trucking, crane and heavy equipment manufacturing, farm equipment manufacturing, motorcycle manufacturing, motor manufacturing, cable and wire manufacturing, sanding, nuclear power generation, solar power generation, wind power generation, conventional power generation, hydroelectric power generation, electronics, integrated circuit technology, battery technology, polishing compound manufacturing, steel manufacturing, metal polishing, and chemical hardening of metal surfaces.

The present invention further relates to lubricant compositions comprising a lubricant and at least one additive, the at least one additive being selected to function as a sacrificial carbon source that contributes to the in situ formation of tribologically useful graphitic carbon structures under localized pyrolysis conditions of normal operation. Furthermore, the present invention discloses methods for the ex situ synthesis of graphitic carbon, graphitic oxidized carbon, reduced graphitic oxidized carbon, and other graphitic carbon derivative structures, as well as abrasive nanoparticles. Methods for isolating the ex situ synthesis products are further disclosed using a "power furnace" apparatus.

Furthermore, the present invention is particularly useful because it relates to lubricant compositions and methods for polishing, hardening, and lubricating moving parts in engines, turbochargers, turbines, magnetic tracks, raceways, wheels, bearings, shafts, transmissions, gear systems, and other physical and mechanical systems that utilize machined interacting hard surfaces. In one embodiment, the methods and lubricant compositions provide frictionless perfection in metal interacting surfaces.

In one embodiment, the lubricant composition of the present invention enables the engine, supercharger, or turbine to produce more useful power and torque than when lubricated with conventional lubricants due to the reduced friction achieved through the lubricating and polishing effects of the lubricant composition and method. Efficiency indicators such as engine power and torque have been observed to increase over a period of days, weeks, or even months after the lubricant composition is initially introduced into the engine. In some embodiments, the benefits of the methods and lubricant compositions disclosed herein include nanoparticles or nanoflakes that form a friction boundary layer on the surface of the lubricated moving part, where such nanoparticles or nanoflakes act to actively eliminate oxidation from the metal surface, coat the metal surface, and beneficially use the oxidized molecules in their designated task of reducing friction.

In medicine, nuclear medicine, medical imaging, and diagnostics, the present invention produces highly inert, safe, and infinitesimal carriers for delivering radioisotopes, other metal ions, or other ion-bound therapeutic agents to various locations within the body for therapeutic purposes or to enhance the resolution of magnetic or other diagnostic imaging. Furthermore, these magnetic or paramagnetic spheroids can be used to eradicate tumors and cancer cells in an artificially induced strong magnetic field (such as magnetic resonance imaging) to cause the spheroids to rotate or oscillate vigorously, thereby generating sufficient heat to thermally eliminate target cells or tissues from within.

In one embodiment, the present invention comprises an economical method for forming graphitic carbon from a carbonaceous material carbon source by dehydration reaction or reflux pyrolysis. The method can be scaled up to industrial production scale. The carbon source is preferably a sugar or other structure containing 6 carbon rings, although other carbonaceous materials can be subjected to reflux pyrolysis, oxidation/reduction, incomplete combustion or acid dehydration to form the graphitic carbon reactant starting material. In one embodiment, the graphitic carbon is subjected to reflux with a liquid solvent and then the graphene/graphene oxide (GO) is emitted in the form of nano-scale or "nanoscale" structures suspended in a steam/vapor. In one embodiment, a graphitic carbon source can be subjected to a physical attack of a high pressure liquid or steam to produce mechanically exfoliated graphene flakes without the need for pyrolysis, dehydration or oxidation steps. The graphene/graphene oxide flakes obtained by the above method can be propagated in the vapor and collected by directly depositing onto a solid substrate in physical contact with the emitted vapor, or by applying the particle-containing vapor to an aqueous solution or liquid that promotes the "hydrophobic self-assembly" of the flakes into larger graphene/graphene oxide flakes.

In one embodiment, the reaction environment is controlled to limit the amount of ambient oxygen (O ₂ ) in the reaction chamber, preventing complete combustion of the reactants during heating. In one embodiment, the reaction is carried out in the presence of an added solvent. In one embodiment, the generated graphene oxide (GO) is converted to reduced graphene oxide (rGO) or graphene flakes suspended in a heated or unheated liquid collection medium. The reduced graphene oxide or graphene flakes obtained by the above method can be used to produce a wide range of useful products, including but not limited to protective coatings, low-weight/high-strength graphene-reinforced composites, yarns, and fibers.

In one embodiment, a carbonaceous starting material undergoes a dehydration reaction or pyrolysis to form graphitic carbon. In one embodiment, the carbonaceous source comprises graphite. The graphitic carbon is subjected to reflux in the presence of a solvent, causing graphene/graphene oxide exfoliation or reflux-synthesized polycyclic aromatic hydrocarbons (PAHs) to be emitted in a generated vapor upon heating. The graphene/graphene oxide exfoliation or polycyclic aromatic hydrocarbons (PAHs) are collected by deposition onto a solid substrate in physical contact with the emitted vapor, or by applying the vapor to a pool of aqueous solution for hydrophobic self-assembly of graphene/graphene oxide. The process is scalable to industrial scale. In some embodiments, the generated graphene oxide is converted into reduced graphene oxide flakes suspended in a heated or unheated liquid medium.

In one embodiment, the present invention relates to the production of abrasive nanoparticles for use as a polishing agent. According to this embodiment, the abrasive nanoparticles can be generated by adding a metal oxide or nanodiamonds to the reaction mixture.

In one embodiment, the obtained graphene flakes can be used to produce a variety of useful products, including but not limited to low weight/high strength graphene reinforced composite materials.

In one embodiment, the addition of a suitable additive to a conventional lubricant promotes the in-situ formation of tribologically useful graphite-containing carbon nanoparticles or microparticles in tribologically effective amounts. In one embodiment, the additive comprises a chemical structure having at least one carbon ring. In one embodiment, the nanoparticles are abrasive nanoparticles that act as a nanopolishing agent that nanopolishes the friction surface to a high smoothness by reducing or eliminating roughness, thereby reducing friction between the worn surfaces. In one embodiment, the additive added to the lubricant comprises a form of graphite carbon that is formed ex-situ before the additive is added to the lubricant to form a lubricant composition.

In one embodiment, the additive added to the lubricant comprises an iron composite molecule. In one embodiment, the additive comprises nanoparticles of a carbonaceous particulate material. In one embodiment, the additive dissolves in the lubricant to form the lubricant composition. In one embodiment, the additive readily mixes with the lubricant to form the lubricant composition. In one embodiment, a carbonaceous precursor molecule in the form of one or more sugar or sugar-like amphiphiles is used to provide a sugar or sugar-like component in the lubricant composition that is less likely to coagulate or clog internal components of the system. In one embodiment, a cyclic carbon-containing precursor is added to a lubricant that already contains such a precursor in the form of a currently commercially available solution. The synthetic graphitic carbon does not improve the inherent physical lubrication properties of the conventional base lubricant, but rather conducts and absorbs heat, forms a friction coating on internal components, and converts into a nanoabrasive that promotes nanopolishing of metal surfaces of the lubricated system, thereby reducing friction.

In one embodiment, further friction reduction and efficiency improvements are achieved by using a conventional lubricant with a lower viscosity than other conventional lubricants. The effective removal of asperities through nanopolishing eliminates the need for viscous formulations that typically tend to adhere to asperities under high shear forces. The smoothness of the wear surfaces also allows an engine to operate with thinner films of lubrication between its two wear surfaces (due to the use of a lower viscosity fluid) without damaging the metal parts. The lower viscosity base fluid provides less resistance to moving parts, thereby improving the lubrication system and the mechanical system it lubricates.

In one embodiment, the method delivers and provides a friction-reducing film or coating to internal mechanical system components via the circulating lubricant composition while simultaneously utilizing naturally occurring engine combustion products to form a film or coating. In other embodiments, the method delivers and provides a friction-reducing film or coating via the circulating lubricant alone.

In one embodiment, the lubricant composition improves the performance of an engine, turbocharger, turbine, gear, or other component or system. In one embodiment, the lubricant composition provides tribologically anti-friction films and coatings for automotive and aerospace lubricant compositions and applications, including lubrication of gears, bearings, or journal systems. In some embodiments, the lubricant composition reduces friction between friction surfaces by micropolishing the friction surfaces to a lower roughness over time while lubricating the system during operation.

In one embodiment, the lubricant composition combines with naturally occurring combustion products and chemical reaction byproducts to provide tribologically anti-friction films and coatings for friction surfaces of automotive and aerospace mechanical parts. In one embodiment, the additives in the lubricant composition combine with each other through chemical reactions to provide tribologically anti-friction films and coatings for friction surfaces of automotive and aerospace mechanical parts.

In one embodiment, the present invention includes a method for synthesizing graphene, the synthesis method comprising refluxing a reaction mixture comprising at least one solvent and at least one carbonaceous material (the carbonaceous material promoting the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions where complete combustion of the carbonaceous material is inhibited); collecting vapor generated by the refluxing of the reaction mixture; directing the vapor to a substrate, whereupon graphene is deposited on a surface of the substrate; and recovering the graphene from the surface of the substrate.

In one embodiment, the present invention includes a method for producing graphene oxide, the method comprising: refluxing a reaction mixture comprising at least one solvent, at least one oxidant, and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; collecting vapor generated by the refluxing of the reaction mixture; directing the vapor toward a substrate, whereupon graphene oxide is deposited on a surface of the substrate; and recovering the graphene oxide from the surface of the substrate.

A lubricant composition comprises a base lubricant and at least one carbonaceous additive, wherein the carbonaceous additive forms a tribologically effective amount of at least one graphite-containing carbon structure under partial pyrolysis conditions.

In one embodiment, the present invention includes a lubricant composition comprising a base lubricant and graphene, wherein the graphene has been formed prior to being combined with the base lubricant.

In one embodiment, the present invention includes a lubricant composition comprising a base lubricant and one or more buckybond diamonds, wherein at least some of the buckybond diamonds comprise iron or an iron-containing molecule.

In one embodiment, the present invention comprises a method for lubricating a mechanical system comprising at least one internal friction surface having asperities, the method comprising operating the mechanical system with a lubricant composition comprising a nanopolishing agent to remove the asperities from the internal friction surface, wherein the lubricant composition comprises at least one carbonaceous additive formed in situ in the system under localized pyrolysis conditions and at least one nanopolishing agent.

In one embodiment, the present invention includes a friction coating comprising graphene oxide.

In one embodiment, the present invention includes a lubricant composition comprising a base lubricant and at least one carbonaceous additive that forms a tribologically effective amount of graphene oxide under localized pyrolysis conditions.

In one embodiment, the present invention includes a lubricant composition comprising a base lubricant and at least one carbonaceous additive that forms a tribologically effective amount of reduced graphene oxide under localized pyrolysis conditions.

In one embodiment, the present invention includes a method for synthesizing a plurality of surface graphitized abrasive nanoparticles, the method comprising: refluxing a reaction mixture comprising at least one solvent, at least one metal oxide, and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) to form at least one surface graphitized abrasive nanoparticle; and collecting the surface graphitized abrasive nanoparticles from the reaction mixture.

In one embodiment, the present invention includes methods of using graphene in drug delivery agents, medical imaging contrast agents, metal prosthetic devices, polishing agents and metal prosthetic devices and steel devices polished by the polishing agents, cleaning agent formulations, and macroscopic solid-state materials including surface-graphitized abrasive nanoparticles.

In one embodiment, the present invention includes a nanoparticle comprising a core comprising at least one metal atom and a surface graphitized shell surrounding the core. In one embodiment, the surface graphitized shell comprises a fullerene carbon shell.

In one embodiment, the present invention comprises a micronized particle agglomerate comprising at least one nanoparticle, wherein the nanoparticle comprises a core comprising at least one metal atom and a surface graphitized shell surrounding the core, and at least one graphitic carbon structure associated with the nanoparticle. In one embodiment, the surface graphitized shell comprises a fullerene carbon shell, and the graphitic structure comprises graphene and/or its derivatives.

In one embodiment, the present invention comprises a lubricant composition comprising a base lubricant and a tribologically effective amount of a plurality of nanoparticles, wherein the plurality of nanoparticles comprises a core comprising at least one metal atom and a surface graphitized shell surrounding the core. In one embodiment, the surface graphitized shell comprises a fullerene carbon shell.

In one embodiment, the present invention comprises an additive formulation for addition to a base lubricant, the additive formulation comprising a base solvent and an effective amount of at least one carbonaceous additive, wherein the carbonaceous additive forms a tribologically effective amount of at least one graphitic carbon structure when partial pyrolysis occurs.

In one embodiment, the present invention comprises a coating applied to a surface of a material, the coating comprising at least one nanoparticle, the nanoparticle comprising a core comprising at least one metal atom and a surface graphitized shell surrounding the core. In one embodiment, the surface graphitized shell comprises a fullerene carbon shell.

In one embodiment, the present invention comprises a composite material comprising a matrix material and at least one nanoparticle dispersed in the matrix material, wherein the nanoparticle comprises a core comprising at least one metal atom and a surface graphitized shell surrounding the core. In one embodiment, the surface graphitized shell comprises a fullerene carbon shell.

In one embodiment, the present invention includes a composite material comprising a material coated with a solution comprising graphene, wherein the solution comprising graphene is formed by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and applying the reaction mixture to a surface of a composite material.

In one embodiment, the present invention comprises a composite material comprising fibers coated with a solution comprising graphene, wherein the solution comprising graphene is formed by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and applying the reaction mixture to a surface of the fibers comprising a composite material.

In one embodiment, the present invention comprises a composite material comprising a fiber web coated with a solution comprising graphene, wherein the solution comprising graphene is formed by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and applying the reaction mixture to a surface of the fiber web comprising a composite material.

In one embodiment, the present invention includes a concrete mix mixed with a solution comprising graphene and its derivatives, wherein the solution comprising graphene and its derivatives is prepared by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and mixing the reaction mixture with the concrete mix.

In one embodiment, the present invention includes an asphalt mixture mixed with a solution comprising graphene and its derivatives, wherein the solution comprising graphene and its derivatives is made by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound, wherein the at least one compound promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent the complete combustion of the carbon source into carbon dioxide or carbon monoxide; and mixing the reaction mixture with the asphalt mixture.

In one embodiment, the present invention includes a glass fiber coated with a solution comprising graphene and its derivatives, wherein the solution comprising graphene and its derivatives is formed by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and applying the reaction mixture to a surface of the glass fiber.

In one embodiment, the present invention includes a plastic coated with a solution comprising graphene and its derivatives, wherein the solution comprising graphene and its derivatives is formed by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and applying the reaction mixture to a surface of the plastic.

In one embodiment, the present invention includes a polymer mixture configured for preparing a plastic for mixing with a solution comprising graphene and its derivatives, wherein the solution comprising graphene and its derivatives is prepared by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and mixing the reaction mixture with the polymer mixture configured for preparing a plastic.

In one embodiment, the present invention includes graphite coated with a solution comprising graphene and its derivatives, wherein the solution comprising graphene and its derivatives is prepared by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and coating the graphite with the reaction mixture.

In one embodiment, the present invention includes a wire or cable coated with a solution comprising graphene and its derivatives, wherein the solution comprising graphene and its derivatives is made by a process comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions that prevent complete combustion of the carbon source to carbon dioxide or carbon monoxide; and coating the wire or cable with the reaction mixture.

In one embodiment, the present invention includes a method for synthesizing nanosteel, the method comprising: refluxing a reaction mixture comprising at least one solvent, at least one metal oxide, and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) to form at least one surface-graphitized abrasive nanoparticle; collecting a vapor generated by the refluxing of the reaction mixture containing the surface-graphitized abrasive nanoparticles; and subjecting the collected vapor to an annealing treatment.

In one embodiment, the present invention includes a method for collecting graphene, the method comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs); and collecting a vapor generated by the refluxing of the reaction mixture.

In one embodiment, the present invention includes a method for collecting graphene derivatives, the method comprising: refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs); and collecting a vapor generated by the refluxing of the reaction mixture.

In one embodiment, the present invention includes a collection assembly configured to collect the vapor generated by reflux of a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs).

In one embodiment, the present invention comprises a hydrophobic self-assembly configured to self-assemble graphene and its derivatives from the vapor generated by refluxing a reaction mixture comprising at least one solvent and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs).

In one embodiment, the present invention includes a method for hydrophobic self-assembled graphene, the method comprising: refluxing a reaction mixture, the reaction mixture comprising at least one solvent and at least one carbonaceous material, the at least one carbonaceous material promoting the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions where complete combustion of the at least one carbonaceous material is inhibited; collecting vapor generated by the reflux of the reaction mixture; directing the vapor to a water matrix, whereupon graphene is deposited on a surface of the water matrix; and recovering the graphene from the surface of the water matrix.

In one embodiment, the present invention includes a method for producing graphene, the method comprising: refluxing a reaction mixture, the reaction mixture comprising at least one solvent and at least one carbonaceous material, the at least one carbonaceous material promoting the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions where complete combustion of the at least one carbonaceous material is inhibited; collecting vapor generated by the refluxing of the reaction mixture; directing the vapor to a substrate, whereupon graphene is deposited on a surface of the substrate; and recovering the graphene from the surface of the substrate.

In one embodiment, the present invention comprises a method of lubricating a mechanical system, the method comprising: operating the mechanical system with a lubricant composition comprising an effective amount of at least one carbon-containing additive, the at least one carbon-containing additive promoting the in situ chemical formation of a tribologically effective amount of at least one tribologically useful graphitic carbon structure during operation of the mechanical system.

In one embodiment, the present invention comprises a method of improving the efficiency of an engine, the method comprising: operating the engine with a lubricant composition comprising an effective amount of at least one carbonaceous additive, the at least one carbonaceous additive promoting the in situ chemical formation of a tribologically effective amount of at least one tribologically useful graphitic carbon structure during operation of the engine.

In one embodiment, the present invention comprises a method of reducing negative horsepower of an engine, the method comprising: operating the engine with a lubricant composition comprising an effective amount of at least one carbon-containing additive, the at least one carbon-containing additive promoting the in situ chemical formation of a tribologically effective amount of at least one tribologically useful graphitic carbon structure during operation of the engine.

In one embodiment, the present invention comprises a method of reducing torque in an engine, the method comprising: operating the engine with a lubricant composition comprising an effective amount of at least one carbon-containing additive, the at least one carbon-containing additive promoting the in situ chemical formation of a tribologically effective amount of at least one tribologically useful graphitic carbon structure during operation of the engine.

In one embodiment, the present invention comprises a method of producing a friction resin, film, coating, or lacquer, the method comprising: refluxing a reaction mixture comprising at least one solvent and at least one carbonaceous material, the at least one carbonaceous material promoting the formation of polycyclic aromatic hydrocarbons (PAHs) under conditions in which complete combustion of the at least one carbonaceous material is inhibited; and mixing the reaction mixture with the resin, film, coating, or lacquer before applying the resin, film, coating, or lacquer or before setting the resin, film, coating, or lacquer.

In one embodiment, the present invention includes a power furnace configured for the production of surface graphitized abrasive nanoparticles, the production comprising: refluxing a reaction mixture comprising at least one solvent, at least one metal oxide, and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons (PAHs) to form at least one surface graphitized abrasive nanoparticle; collecting a vapor generated by the refluxing of the reaction mixture containing the surface graphitized abrasive nanoparticles, and then subjecting the collected vapor to a high shear environment comprising high-speed rotation, high-frequency oscillation or vibration, fluid dynamic extrusion, frictional collision with one or more moving parts, high-speed stirring, or any combination thereof; and collecting the surface graphitized abrasive nanoparticles. In one embodiment, the power furnace further comprises a surface topographical feature comprising fins, rods, bumps, recesses, holes, roughness, tunnels, and any combination thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be described with reference to the following drawings, in which like elements are represented by like numerals.

1A and 1B are schematic diagrams showing steps for preparing graphene/graphene oxide and surface graphitized abrasive nanoparticles (SGAN) according to one embodiment of the present invention, respectively.

FIG. 2A shows a flow chart of forming a graphene/graphene oxide reinforced/coated substrate from a carbonaceous or graphite starting material according to one embodiment of the present invention.

FIG. 2B shows a flow chart of forming a graphene/graphene oxide thin film coating substrate from a graphene/graphene oxide exfoliation vapor process according to an embodiment of the present invention.

FIG3 is a schematic diagram showing a graphene/graphene oxide/surface graphitized abrasive nanoparticle (SGAN) synthesis and collection system according to one embodiment of the present invention.

4 shows a scanning electron microscope (SEM) image of a sample area of a surface graphitized abrasive nanoparticle (SGAN) sphere on a SEM stub coated by a first vapor deposition method according to an embodiment of the present invention.

FIG5A shows a scanning electron microscope (SEM) image of a first sampling region of a surface graphitized abrasive nanoparticle (SGAN) spheroid on the SEM stub according to an embodiment of the present invention.

FIG. 5B shows a second sampling region of the surface graphitized abrasive nanoparticle (SGAN) spheroids of FIG. 5A .

FIG. 5C shows a third sampling region of the surface graphitized abrasive nanoparticle (SGAN) spheres of FIG. 5A .

FIG. 6 shows a scanning electron microscope (SEM) image of a sample region of a crystal structure on a SEM stub according to an embodiment of the present invention.

FIG. 7 shows a scanning electron microscope (SEM) image of a surface graphitized abrasive nanoparticle (SGAN) spheroid containing nano-steel according to an embodiment of the present invention.

FIG8 shows a scanning electron microscope (SEM) image of a sample area of a surface graphitized abrasive nanoparticle (SGAN) sphere on a SEM stub coated by a second vapor deposition method according to an embodiment of the present invention.

FIG. 9 shows a scanning electron microscope (SEM) image of another surface graphitized abrasive nanoparticle (SGAN) spheroid on the SEM stub.

FIG. 10 shows a scanning electron microscope (SEM) image of a region of the SEM stub with numerous surface graphitized abrasive nanoparticle (SGAN) spheroids.

FIG. 11 shows a scanning electron microscope (SEM) image of a gold/palladium coating region of the SEM stub.

FIG. 12 shows a transmission electron microscope (TEM) image of a first region of a graphene product on a carbon transmission electron microscope (TEM) grid according to an embodiment of the present invention.

FIG. 13 shows a transmission electron microscope (TEM) image of a second region of the graphene product of FIG. 12 .

FIG. 14 shows a transmission electron microscope (TEM) image of a third region of the graphene product of FIG. 12 .

FIG. 15 shows a transmission electron microscope (TEM) image of a fourth region of the graphene product of FIG. 12 .

FIG. 16 shows a transmission electron microscope (TEM) image of a fifth region of the graphene product of FIG. 12 .

FIG. 17 shows a transmission electron microscope (TEM) image of a sixth region of the graphene product of FIG. 12 .

FIG. 18 shows a transmission electron microscope (TEM) image of a region of a graphene product on a copper transmission electron microscope (TEM) grid according to an embodiment of the present invention.

FIG. 19 shows a transmission electron microscope (TEM) image of a region of another graphene product on a copper transmission electron microscope (TEM) grid according to an embodiment of the present invention.

FIG. 20 shows surface roughness measurements of a non-wearing surface of a machined stainless steel cam follower after exposure to a lubricant composition according to an embodiment of the present invention.

FIG. 21 shows surface roughness measurements of a worn surface of a machined stainless steel cam follower after exposure to a lubricant composition according to an embodiment of the present invention.

22 shows a scanning electron microscope (SEM) image of a first portion of a non-wear surface of a cam follower retaining ring after exposure to a lubricant composition in accordance with an embodiment of the present invention.

23 shows a scanning electron microscope (SEM) image of a second portion of the non-wear surface of the cam follower retaining ring.

24 shows a scanning electron microscope (SEM) image of a third portion of the non-wear surface of the cam follower retaining ring.

25 shows a scanning electron microscope (SEM) image of a fourth portion of the non-wear surface of the cam follower retaining ring.

26 shows a scanning electron microscope (SEM) electron micrograph of a fifth portion of the non-wear surface of the cam follower retaining ring.

27 shows a scanning electron microscope (SEM) image of a sixth portion of the non-wear surface of the cam follower retaining ring.

28 shows a scanning electron microscope (SEM) image of a seventh portion of the non-wear surface of the cam follower retaining ring.

29 shows a scanning electron microscope (SEM) image of an eighth portion of the non-wear surface of the cam follower retaining ring.

FIG30 shows a scanning electron microscope (SEM) image of a ninth portion of the non-wear surface of the cam follower retaining ring.

FIG31 shows a scanning electron microscope (SEM) image of a tenth portion of the non-wear surface of the cam follower retaining ring.

32 shows a scanning electron microscope (SEM) image of an eleventh portion of the non-wear surface of the cam follower retaining ring.

FIG33 shows a scanning electron microscope (SEM) image of a first close-up of the crystal structure on the left side of FIG32 .

FIG. 34 shows a scanning electron microscope (SEM) image of a twelfth portion of the non-wear surface of the cam follower retaining ring.

FIG. 35 shows a scanning electron microscope (SEM) image of the crystal structure on the left side of FIG. 32 .

FIG36 shows a scanning electron microscope (SEM) image of a second close-up of the crystal structure on the left side of FIG32.

FIG37 shows a scanning electron microscope (SEM) image of a thirteenth portion of the non-wear surface of the cam follower retaining ring.

38A shows a scanning electron microscope (SEM) image of a first sampling region of a spheroid on the non-wear surface of the cam follower retaining ring.

FIG. 38B shows a second sampling region of the surface graphitized abrasive nanoparticle (SGAN) spheroids of FIG. 38A .

FIG. 38C shows a third sampling region of the surface graphitized abrasive nanoparticle (SGAN) spheroids of FIG. 38A .

FIG39A shows a first sample region of the crystal structure of FIG35.

FIG39B shows a second sampling region of the crystal structure of FIG35.

FIG39C shows a third sampling region of the crystal structure of FIG35.

FIG39D shows a fourth sample region of the crystal structure of FIG35.

FIG39E shows a fifth sample region of the crystal structure of FIG35.

FIG39F shows a sixth sampling region of the crystal structure of FIG35.

FIG39G shows a seventh sample region of the crystal structure of FIG35.

FIG. 40A shows a first sampling area of another spherical body on the non-wear surface of the cam follower retaining ring.

FIG. 40B shows a second sampling region of the surface graphitized abrasive nanoparticle (SGAN) spheroids of FIG. 40A .

FIG. 40C shows a third sampling region of the surface graphitized abrasive nanoparticle (SGAN) spheroids of FIG. 40A .

41 shows a scanning electron microscope (SEM) image of a sample area of another spherical body on the non-wear surface of the cam follower retaining ring.

FIG42 shows a first transmission electron microscope (TEM) image of material from the surface of the cam follower.

FIG43 shows a second transmission electron microscope (TEM) image of material from the surface of the cam follower.

FIG44 shows a third transmission electron microscope (TEM) image of material from the surface of the cam follower.

45 shows a fourth transmission electron microscope (TEM) image of material from the surface of the cam follower.

46 shows a fifth transmission electron microscope (TEM) image of material from the surface of the cam follower.

FIG47 shows a sixth transmission electron microscope (TEM) image of material from the surface of the cam follower.

FIG. 48 shows a seventh transmission electron microscope (TEM) image of material from the surface of the cam follower.

FIG49A shows an eighth transmission electron microscope (TEM) image of material from the surface of the cam follower.

FIG49B shows an enlarged view of an upper left portion of the image of FIG49A.

Summary of the Invention

The present invention relates to the facile synthesis of graphene, graphene derivatives, and nanoparticles and their use as tribologically beneficial lubricant additives. The products of the methods of the present invention have numerous applications, including but not limited to molecular-level coatings for composite reinforcement, thermal insulation, ballistic transistors, integrated circuits, fiber and cable reinforcement, and nanopolishing agents.

As used herein, the term "cyclic" is used to describe any molecule having at least one ring of five or more members, wherein at least half of the atoms constituting the ring are carbon atoms. The ring may be aromatic or non-aromatic.

As used herein, the term "tribologically effective amount" is intended to refer to any amount of an additive or amounts of additives added to a lubricated system that is sufficient to tribologically benefit such lubricated system.

As used herein, the term "tribologically beneficial" is intended to refer to any additive that is created, present in, or used in a mechanical system and reduces friction in the mechanical system.

As used herein, "friction agent" refers to a molecule that is formed, present in, or used in a mechanical system and that measurably reduces friction in the mechanical system.

As used herein, "Bucky-diamond" or "nano-Bucky-diamond" refers to any nanoparticle having a nanodiamond core, which may include a plurality of non-carbon heterocyclic atoms, and a fullerene carbon shell formed around the core.

As used herein, surface graphitized abrasive nanoparticles (SGAN) refer to any nanoscale particle comprising at least one particle surrounded by a shell consisting primarily of carbon.

As used herein, "spheroid" refers to a particle that is shaped substantially like a sphere but is not necessarily perfectly round.

As used herein, "matrix material" refers to any material that forms a continuous phase in a composite of one or more materials.

As used herein, "spinel structure" refers to any cubic mineral crystal with the general chemical formula A ²⁺ B ₂ ³⁺ O ₄ ^2- , in which the oxide anions (O) are arranged in a cubic close-packed lattice, the A cations occupy all tetrahedral positions in the lattice, and the B cations occupy all octahedral positions in the lattice.

As used herein, "inverse spinel structure" refers to any cubic mineral crystal with the general chemical formula A ²⁺ B ₂ ³⁺ O ₄ ^2- , in which the oxide anions (O) are arranged in a cubic close-packed lattice, the A cations occupy half of the octahedral sites in the lattice, and the B cations occupy half of the octahedral sites and all tetrahedral sites in the lattice.

As used herein, "graphitic carbon" refers to any structure with a carbon lattice framework, including but not limited to graphite, graphene, graphene oxide, fullerene, fullerene-like structures, fullerene interiors, nano-onions, nano-peapods, nanotubes, nano-buds, reduced graphene oxide, lace carbon, and polycyclic aromatic compounds.

As used herein, "carbon lattice framework" refers to any two-dimensional polycyclic carbon structure formed by ^sp2- or ^sp3 -hybridized carbon atoms.

As used herein, "power furnace" refers to a heated nanoparticle synthesis furnace apparatus that utilizes an excitation force, sonic force, centrifugal force, centripetal force, pressure or shear force, or a combination of these forces, during the synthesis phase of nanoparticle product formation.

Non-graphene, graphene oxide, reduced graphene oxide and other graphene derivative structures and nanoparticles In situ synthesis method

In one aspect, the present invention relates to an ex-situ synthesis method for graphene, graphene oxide, reduced graphene oxide, and other graphene derivative structures and nanoparticles. Graphitic carbon can be formed from a carbonaceous material carbon source using an economical dehydration reaction or reflux pyrolysis method. The method disclosed in the present invention is scalable to industrial-scale industrial production. The carbon source is preferably a sugar containing a six-membered ring structure, although many other carbonaceous materials can be subjected to dehydration, pyrolysis, or oxidation and can be used. The carbon source is subjected to reflux pyrolysis, oxidation/reduction, or acid dehydration to form a graphitic carbon reactant starting material. In other embodiments, the dehydration/oxidation/pyrolysis synthesis steps for producing suitable graphitic carbon are omitted, and graphitic carbon itself is used as the reactant starting material. The graphitic carbon is subjected to reflux with a liquid solvent, and the graphene/graphene oxide (GO) is then emitted in the form of nanometer-scale or "nanoscale" structures suspended in a steam/water vapor. Alternatively or additionally, a graphitic carbon source can be subjected to a high-pressure liquid or vapor to produce graphene flakes without the need for pyrolysis, dehydration, or oxidation steps. The graphene/graphene oxide flakes obtained by the above method can be propagated in the vapor and collected by directly depositing onto a solid substrate in physical contact with the emitted vapor, or by applying the particle-containing vapor to an aqueous solution or liquid that promotes the "hydrophobic self-assembly" of the flakes into larger graphene/graphene oxide flakes.

In one embodiment, the reaction environment is controlled to limit the amount of ambient oxygen (O ₂ ) in the reaction chamber, thereby preventing the reactants from completely combusting during heating. In one embodiment, the reaction is carried out without the use of an added solvent. In one embodiment, the produced graphene oxide (GO) is converted into reduced graphene oxide (rGO) or graphene flakes suspended in a heated or unheated liquid collection medium. The large hydrophobic self-assembled flakes obtained by the above method can be easily reduced to reduced graphene oxide (rGO) or graphene, which can be used in industry to produce a wide range of useful products, including but not limited to protective coatings, low-weight/high-strength graphene-reinforced composites, filaments and fibers.

1A schematically illustrates the steps for preparing graphene/graphene oxide (GO) according to one embodiment of the present invention, wherein a reaction mixture primarily comprising a non-graphite carbonaceous material carbon source is subjected to pyrolysis, dehydration, an oxidation/reduction reaction, or incomplete combustion to form graphite carbon. In one embodiment, a graphite carbon starting material is used without the need for pyrolysis or dehydration steps.

In one embodiment, the reaction mixture is subjected to reflux to form a vapor. Graphene and graphene oxide (GO) nanoscale structures are transferred from the vapor emitted during the heating of the slurry or solution. The graphene/graphene oxide flakes are preferably collected by bubbling the vapor through a liquid that isolates and suspends the flakes. Alternatively, the graphene/graphene oxide flakes form on the surface of the liquid when the vapor is directed to the surface of the liquid. In a process referred to herein as "hydrophobic self-assembly," individual graphene and graphene oxide flakes combine at the surface of the liquid to form multilayer graphene and graphene oxide flakes.

In one embodiment, the carbon source is directly heated by an external heat source in a pyrolysis or dehydration reaction to form graphitic carbon and water. In one embodiment, the carbon source is sucrose. In one embodiment, the water formed acts as a solvent to allow reflux of the reaction products. In one embodiment, the reaction to form graphitic carbon is as follows:

In one embodiment, the carbon source is exposed to an acid in a pyrolysis or dehydration reaction to form graphite carbon and water. In one embodiment, the carbon source is sucrose and the acid is concentrated sulfuric acid. In one embodiment, the water formed acts as a solvent to allow reflux of the reaction product. In one embodiment, the reaction product is a graphite foam. In one embodiment, the reaction product is a graphite slurry. In one embodiment, the reaction to form graphene is as follows:

In one embodiment, the carbon source reacts with an oxidant to form graphitic carbon in the form of graphene oxide. In one embodiment, the reaction to form graphene oxide (GO) is as follows:

The applied heat drives the reaction, while the optional additives catalyze the reaction and/or improve the yield of the desired reaction product.

The graphene oxide (GO) reaction product is schematically shown as the following molecule (1):

In the above embodiments, the reaction conditions are selected so that the reaction does not result in complete combustion of the carbon source to form carbon dioxide or incomplete combustion to form carbon monoxide. The reaction conditions are preferably designed to form graphitic carbon-carbon bonds by controlling the reaction temperature. In some embodiments, a portion of the carbon source is intentionally burned to provide the heat required to convert another portion of the carbon source to form the desired graphitic bonds. In some embodiments, the reaction occurs under non-ideal combustion conditions (such as pyrolysis or smoldering).

As used herein, "pyrolysis" refers to the decomposition of a carbon source under conditions of low oxygen or other oxidizing agent levels and elevated temperature.

As used herein, "smoldering" refers to a slow, low temperature, flameless reaction sustained by heat from the direct reaction of oxygen with the surface of a solid or liquid fuel.

As used herein, "exfoliation" or "nanoscale structure" refers to discrete segments of graphene or graphene derivatives.

Efforts to improve combustion efficiency have obscured the true value of compounds previously considered useless waste, such as the carbonaceous "goo" from early coal-fired furnaces—for example, see Lunge's Coal - Tar and Ammonia, 5th ed., by D. Van Nostrand Co., New York, 1916. This carbonaceous "goo" contains graphitic materials, including graphene. Similarly, modern advances in combustion science have overlooked the value of many older processes, now considered obsolete, that could be purposefully adapted to maximize carbon black particle formation, ultimately yielding graphene, graphene derivatives, carbon-encapsulated metal nanoparticles, or nanosteel.

While the formation of polycyclic aromatic hydrocarbons (PAHs) as products of incomplete combustion in carbonaceous particulate matter "carbon black" is widely known, the usefulness of such PAHs has been minimal until now due to limited scale and trends reported in the art, often drifting from the synthesis conditions required for their continued growth. Wiersum et al., "The Formation of Polyaromatic Hydrocarbons, Fullerenes and Soot in Combustion: Pyrolytic Mechanisms and the Industrial and Environmental Connection," pp. 143-194 in Gas Phase Reactions in Organic Synthesis , ed. By Vallée, Gordon and Breach Science Publishers, Amsterdam, 1997, reported that many different gas-phase reactions form polycyclic aromatic hydrocarbons (PAHs). To date, none of the known gas-phase PAH synthesis methods produce graphene or any form of planar graphitic carbon with dimensions greater than 222 carbon atoms.

In one embodiment, the methods and processes disclosed herein promote the production of PAHs by allowing the generated PAHs to grow to sizes that exhibit the general characteristics of graphene by collecting and trapping the vapor products of the reaction mixture, thereby extending exposure to favorable synthesis conditions. Other embodiments, methods, and processes disclosed herein are directed to specifically promoting conditions for extended PAH growth by allowing them to self-assemble into large graphene sheets in vapor or aqueous solutions. These processes, which allow for graphene synthesis using PAH-promoting compounds alone or in combination with carbonaceous or graphitic reactant materials, can be scaled to industrial production.

In one embodiment, one or more compounds that promote the formation and growth of polycyclic aromatic hydrocarbons (PAHs) are used in the production of graphene, graphene derivatives, carbon-coated metal nanoparticles, or nanosteel. These compounds may include, but are not limited to, known intermediate chemicals in the formation of polycyclic aromatic hydrocarbons (PAHs), as well as chemicals that form intermediates in the formation of polycyclic aromatic hydrocarbons (PAHs).

In one embodiment, the initial reaction occurs in a solvent system under reflux conditions to promote the synthesis of PAH units, which subsequently self-assemble into larger graphene sheets. In some embodiments, the reflux conditions are azeotropic reflux conditions. For example, see Ydeye et al., “Ethanol Heterogeneous Azeotropic Distillation Design and Construction”, International Journal of Physical Sciences, Vol. 4, pp. 101-106, 2009; and Sun et al., “ZrOCl ₂ · _{8H 2 O} : An Efficient, Cheap and Reusable Catalyst for the Esterification of Acrylic Acid and Other Carboxylic Acids with Equimolar Alcohols”, Molecules, Vol. ₁₁ , pp. 263-271, 2006. with Equimolar Amounts of Alcohols", Molecules, Vol. 11, pp. 263-271, 2006). In some reflux conditions, a promoter is added. In some embodiments, the promoter is biochar, coal slurry, nanocoal, an activated form of nanocoal, activated charcoal, graphite particles, carbon black particulate material, or another form of chelated carbonaceous waste.

As used herein, "chelated carbonaceous waste" refers to any carbonaceous waste product of a synthesis, pyrolysis, or incomplete combustion reaction, which is typically collected and isolated to prevent conversion to or release as atmospheric greenhouse gases. In one embodiment, a chelated carbonaceous waste can be used as the carbon source in the reaction mixture, in which case the added carbon partially enhances the reaction by acting as a thermal conductivity enhancing heat transfer agent—for example, see Baby et al., "Enhanced Convective Heat Transfer Using Graphene Dispersed Nanofluids", Nanoscale Research Letters, Vol. 6, No. 289, 2011.

The sequestered carbonaceous waste can be collected from emissions of any process, including but not limited to emissions from diesel trucks or emissions from coal-fired power plants. In some embodiments, a diesel particulate filter is used to collect the carbonaceous waste as part of a diesel emissions control strategy. In other embodiments, a scrubber is used to collect the carbonaceous waste. Recent legislation by the California Air Resources Board (CARB) provides for the reduction of particulate and hazardous gas emissions (including those from diesel trucks and buses) by adding filters to the exhaust systems of trucks - see California Code of Regulations, Title 13, Div. 3, Ch. 14 et seq.

In some embodiments, a reusable filter is used that is designed as an alternative to so-called "regeneration" technologies that burn the collected carbon black and continue to release greenhouse gases into the environment. When a truck driver or other user needs to replace a dirty particulate filter, the driver or user exchanges the contaminated filter for a new filter, rather than discarding the dirty filter or purchasing a new filter. The chelated carbonaceous waste contained in the worn filter is preferably removed from the particulate filter or scrubber and then used as a carbon source for the synthesis of graphene or graphene derivatives. The filter or scrubber is preferably reused to collect additional carbonaceous waste from the emissions when the process is repeated, because the process seeks to incorporate most of the chelated carbon into the graphene product (rather than into greenhouse gas emissions). In some embodiments, the chelated carbon waste is harvested from the particulate filter or scrubber by dissolving it in an organic solvent. In some embodiments, the chelated carbon waste is harvested using water, a water mixture, or steam.

Compounds that promote the formation of polycyclic aromatic hydrocarbons used in the process include, but are not limited to, dimethyl ether, propyne, propadiene, alcohols (including but not limited to propargyl alcohol and isopropanol), acetylene, and compounds that promote the formation of _C1 to _C5 hydrocarbon groups (one to five carbon hydrocarbon groups).

It is known that methyl radicals (CH ₃ ·) promote the growth of polycyclic aromatic hydrocarbons (PAHs) (for details, see Shukla et al., “Role of Methyl Radicals in the Growth of PAHs”, Journal of The American Society for Mass Spectrometry, Vol. 21, pp. 534-544, 2010); and promote the growth of graphene (for details, see Wellmann et al., “Growth of Graphene Layers on HOPG via Exposure to Methyl Radicals”, Surface Science, Vol. 542, pp. 81-93, 2003). Science, Vol.542, pp.81-93, 2003).

Dimethyl ether forms methyl groups under combustion conditions in the presence of another carbon source and promotes the formation of polycyclic aromatic hydrocarbons (PAHs). For details, see Yoon et al., "Synergistic Effect of Mixing Dimethyl Ether with Methane, Ethane, Propane and Ethylene Fuels on Polycyclic Aromatic Hydrocarbon and Soot Formation", Combustion and Flame, Vol. 154, pp. 368-377, 2008. Other hydrocarbon radicals (including but not limited to _C2H ·, _C2H3 ·, _C3H3 ·, _C4H3 ·, _C4H5 ·, _{and C5H3} ·) can also nucleate or propagate polycyclic aromatic _hydrocarbons (PAHs)—for details _, see Pope et al., “Exploring Old and New Benzene Formation Pathways in Low-pressure Premixed Flames _of Aliphatic _Fuels ”, Proceedings of the Combustion Institute, Vol. 28, pp. 1519-1527, 2000.

Propargyl radicals (C ₃ H ₃ ·) have been proposed as the primary intermediate for the formation of polycyclic aromatic hydrocarbons (PAHs) in numerous kinetic studies—see McEnally et al., “Computational and Experimental Study of Soot Formation in a Coflow, Laminar Ethylene Diffusion Flame”, 27th Symposium (International) on Combustion, 1998, pp. 1497-1505; Shfir et al., “Kinetics and Products of the Self-reaction of Propargyl Radicals”, Journal of Physical Chemistry A, vol. 107, pp. 8893-8903, 2003. Radicals”, Journal of Physical Chemistry A, Vol. 107, pp. 8893-8903, 2003); Tang et al., “An Optimized Semi-detailed Sub-mechanism of Benzene Formation from Propargyl Recombination”, Journal of Physical Chemistry A, Vol. 110, pp. 2165-2175, 2006.

Propyne and propadiene also contribute to the formation of polycyclic aromatic hydrocarbons (PAHs). For details, see Gazi et al., “A Modeling Study of Allene and Propyne Combustion in Flames”, Proceedings of the European Combustion Meeting, 2011. Acetylene can also play a role in the nucleation and growth of polycyclic aromatic hydrocarbons (PAHs). For details, see Frenlach et al., "Aromatics Growth beyond the First Ring and the Nucleation of Soot Particles", Preprints of the 202nd ACS National Meeting, Vol. 36, pp. 1509-1516, 1991.

2A and 2B show flow charts for forming various graphene products from a non-graphitic carbonaceous starting material or a graphitic carbonaceous starting material.

2A , when a non-graphite carbonaceous material is used as the starting material, the carbonaceous material can be converted into a graphite material through several different pathways.

In one embodiment, the carbonaceous material is combined with an acid and then converted by dehydration (with or without heating and with or without refluxing the reactants). In one embodiment, the carbonaceous material is a sugar. In some embodiments, the sugar is sucrose. In one embodiment, the acid is concentrated sulfuric acid.

In one embodiment, the carbonaceous material is heated without using a solvent. The carbonaceous material can be heated with or without the addition of an additive (the additive can be an oxidant, a metal oxide or a catalyst), and then the generated gas or steam can be selectively collected or condensed to form the graphite material. The use of an oxidant or metal oxide tends to promote the formation of graphene oxide, while if an oxidant or metal oxide is not used, graphene is tended to be produced. In one embodiment, the carbonaceous material is preferably heated to a high temperature, such as by a direct or indirect flame. In one embodiment, the additive is a metal-containing compound. In one embodiment, the metal is iron. In some embodiments, the additive is a metal oxide. In one embodiment, the additive is ferric oxide. In other embodiments, the additive is ferrocene.

In one embodiment, the carbonaceous material is heated in a refluxing solvent to form the graphite material. The carbonaceous material may be combined with an additive, which may be an oxidant, a metal oxide, or a catalyst. The use of an oxidant or a metal oxide tends to promote the formation of graphene oxide, while if an oxidant or a metal oxide is not used, graphene is tended to be produced. In one embodiment, the additive is a metal catalyst mixture. In some embodiments, the metal is iron. In one embodiment, the additive is a metal oxide. In one embodiment, the metal oxide is ferric oxide. In some embodiments, the additive is ferrocene. In some embodiments, the solvent includes one or more of an alcohol, water, and a mineral oil. The solvent preferably allows the reaction mixture to reflux at high temperature. It is also preferred that the solvent helps dissolve the reactants to prevent combustion of the reactants and promote the generation of steam to collect the products. In some embodiments, the use of a solvent improves the reaction yield and increases the interaction between the reactants, thereby promoting the formation of graphene or graphene oxide.

In one embodiment, when the carbonaceous material is combined with a metal oxide in the reaction mixture, surface graphitized abrasive nanoparticles (SGANs) (including surface graphitized abrasive nanoparticle spheroids) are formed. The surface graphitized abrasive nanoparticles can be recovered for any purpose, such as as a nanopolishing agent or as an additive to a lubricant. It is expected that the surface graphitized abrasive nanoparticles can be recovered from the reaction mixture by using a magnet or an externally applied magnetic field. The surface graphitized abrasive nanoparticles can also be recovered by centrifugal filtration. In one embodiment, the reaction mixture including the surface graphitized abrasive nanoparticles can be used as an additive to a lubricant.

In one embodiment, a large-scale DC arc discharge apparatus, a chamber, or a cylinder can be used to promote the formation of surface graphitized abrasive nanoparticles (SGAN). In some embodiments, the ferric oxide is provided to the system in a powdered state to promote the formation of surface graphitized abrasive nanoparticles (SGAN). In one embodiment, the ferric oxide comprises a nanopowder. In one embodiment, a high carbon content steam can be provided to the system.

In one embodiment, the surface graphitized abrasive nanoparticles (SGANs) can be produced in a high-shear environment within a "power furnace." The high-shear environment within the power furnace can be provided by any method or combination of methods, including but not limited to high-speed rotation of the tubular furnace, high-frequency oscillation or vibration of the tubular furnace, sonication, hydrodynamic extrusion, frictional collision with one or more moving parts, and high-speed stirring of the contents of the power furnace. In one embodiment, the rotation speed of the power furnace can reach approximately 1,000 to 11,000 rpm. In one embodiment, the power furnace can also include surface topographical features (such surface topographical features can include but are not limited to fins, rods, bumps, dimples, holes, roughness, and tunnels) to provide additional shear forces, thereby increasing the shear of the reaction mixture. In one embodiment, a reaction gas can be supplied to the power furnace apparatus. In one embodiment, the synthesis of the surface graphitized abrasive nanoparticles (SGAN) can occur under elevated temperature, elevated pressure, or reduced pressure. The temperature within the power furnace can range from 200 to 800°F.

In one embodiment, the "power furnace" includes an embedded tubular furnace for forming surface graphitized abrasive nanoparticles (SGANs). An insulating portion can surround two concentric rotary furnace cylinders. The furnace cylinders can include multiple through holes to allow material to pass between an area outside an outer cylinder, an area between the two furnace cylinders, and an area inside the inner cylinder. The furnace cylinders can be coaxial and can rotate in different directions at high speed to generate high shear forces. The power tubular furnace can also include a liquid component delivery line to the main chamber and a preheater. A separate gas component delivery line can also be included. The main chamber can be a single chamber or a dual zone chamber.

The inner surface of the outer cylinder or the outer surface of the inner cylinder may include tail fins, pedals, rods, bumps or similar structures to provide shear force to the system. In one embodiment, the tubular furnace can be designed in the form of a "Wankel" engine to provide frictional contact, shear and extrusion to promote the formation of surface graphitized abrasive nanoparticles (SGAN). The "power furnace" may include a shell, a rotor, an eccentric wheel and an internal gear meshing with an external gear. When the rotor runs around in the "power furnace" shell, the frictional contact, shear and extrusion of the liquid between the rotor and the shell can promote the formation of surface graphitized abrasive nanoparticles (SGAN). In one embodiment, the surface of one or more of these structures is electrified or can be electrified. In one embodiment, the electrified surface can act as an electrified cathode in the entire tubular furnace.

In one embodiment, the carbonaceous material is a non-graphitic carbon source, and the non-graphitic carbon source includes but is not limited to a sugar, a sugar-like amphiphile, an amphiphile that promotes graphene formation, a sugar substitute, a starch, a cellulose, a paraffin, an acetate, one or more non-graphitic hydrocarbons, an alkane, an alkene, an alkyne, a ketone, toluene, gasoline, diesel, kerosene, coal, coal tar, coke, or a combination thereof. In one embodiment, coal and diesel are preferred carbon sources. In one embodiment, the coal is a pulverized coal. In one embodiment, the coal is a nanocoal, such as the nanocoal sold by Nano Fuels Technology, LLC of Reno, Nevada, USA, having a particle size in the submicron range.

A sugar amphiphile or a class of sugar amphiphiles can be any molecule having a hydrophilic sugar portion and a hydrophobic portion, including but not limited to those described by Fenimore, “Interfacial Self-assembly of Sugar-based Amphiphiles: Solid- and Liquid-core Capsules,” University of Cincinnati Ph.D. thesis dated October 16, 2009; and Jadhav et al., “Sugar-derived Phase-selective Molecular Gelators as Model Solidifiers for Oil Spill Treatment,” Engelvant Chemistry International, Vol. 49, pp. 7695-7698, 2010. Spills”, Angewandte Chemie International Edition, Vol. 49, pp. 7695-7698, 2010); Jung et al., “Self-assembling Structures of Long-chain Sugar-based Amphiphiles Influenced by the Introduction of Double Bonds”, Chemistry-A European Journal, Vol. 11, pp. 5538-5544, 2005; Paleta et al., “New amphiphilic fluoroalkylated derivatives of xylitol, D-glucose and D-galactose for medical applications: blood compatibility and emulsification properties”, Carbohydrate Research, Vol. 337, pp. 2411-2418, 2002. al., “Novel Amphiphilic Fluoroalkylated Derivatives of Xylitol, D-glucose and D-galactose for Medical Applications: Hemocompatibility and Co-emulsifying Properties”, Carbohydrate Research, Vol. 337, pp. 2411-2418, 2002); Germaneau, “Amphiphilic Sugar Metal Carbenes: From Fischer Type to N-Heterocyclic Carbenes (NHCs)”, PhD thesis by Germaneau, Rheinische Friederich-Wilhems University Bonn, 2007. Ph.D. thesis, 2007); and Ye et al., “Synthesis of Sugar-containing Amphiphiles for Liquid and Supercritical Carbon Dioxide”, Industrial & Engineering Chemistry Research, Vol. 39, pp. 4564-4566, 2000.

A graphene-promoting amphiphile can be any molecule having a graphene-promoting hydrophilic portion and a hydrophobic portion, including but not limited to those sold by The Dow Chemical Company of Midland, Michigan, USA under the TRITON ^™ or TERGITOL ^™ trademarks, including but not limited to the TRITON X series of octylphenol ethoxylates and the TERGITOL NP series of nonylphenol ethoxylates.

Alternatively, a graphite starting material may be used. The graphite material may be any material comprising graphitic carbon, including but not limited to natural graphite, synthetic graphite, one or more polycyclic aromatic hydrocarbons (PAHs), graphene, activated carbon, biochar, coal sputum, one or more benzene series, naphthalene, or any combination thereof.

Referring to FIG. 2A , a graphite material in a solvent is heated. In some embodiments, the solvent comprises one or more of an alcohol, water, and mineral oil. In some embodiments, the mixture is heated to a boiling temperature. In some embodiments, the boiling solvent is refluxed.

In one embodiment, the refluxing liquid graphene product from the reaction mixture is collected in a reaction vessel. The graphene-containing liquid can be applied directly to a material or substrate to form a graphene-enhanced material, a graphene-coated substrate, or a graphene oxide-enhanced material or a graphene oxide-coated substrate.

Optionally, the graphene-containing liquid can be further heated to form a vapor containing graphene/graphene derivative exfoliates. As used herein, "graphene/graphene derivative exfoliates" should be understood to mean one to several layers of graphene or graphene oxide transferred within the vapor of a refluxing solvent or solvent mixture. The graphene/graphene derivative layers in the exfoliates may be mostly planar, or they may wrinkle or fold within the vapor. The length and width of the layers are preferably significantly greater than their thickness.

2B , the vapor containing graphene/graphene derivative exfoliates may be applied to a solid or a liquid.

The graphene/graphene derivative containing flakes can be applied to a solid substrate by placing the solid substrate in the vapor, or by applying the vapor to the solid substrate, to form a graphene/graphene derivative thin film coating substrate. Preferably, any wrinkling or folding in the flake layer is reduced during deposition on the solid substrate. In some embodiments, the deposited flakes are annealed after deposition to improve their uniformity. In some embodiments, the deposited flakes are annealed by heating the substrate. In some embodiments, the reactive end groups on adjacent deposited flakes react with each other to form larger graphene/graphene derivative flakes. In some embodiments, a reducing agent is used to convert graphene oxide (GO) in the layer into reduced graphene oxide (rGO).

Alternatively, the steam containing graphene/graphene derivative exfoliates can be applied to a pool of aqueous solution. The steam can also be applied to the surface of the aqueous solution pool from above or by bubbling through the aqueous solution pool.

In one embodiment, the aqueous solution pool is an additive-free water pool. If the water pool does not contain additives, the graphene/graphene derivative flakes hydrophobically self-assemble into graphene/graphene derivative flakes on the water surface. In one embodiment, the deposited flakes are annealed on the water surface to improve their uniformity. In one embodiment, the reactive end groups on adjacent deposited flakes react with each other to form larger graphene/graphene derivative flakes on the water surface. In some embodiments, a reducing agent is used to convert graphene oxide (GO) in the assembling or assembled layers into reduced graphene oxide (rGO).

The aqueous solution pool may include one or more surfactants as additives to help the graphene/graphene derivative flakes hydrophobically self-assemble into graphene/graphene derivative flakes at the water surface. Preferably, any wrinkling or folding of the flake layer is reduced by interaction with the surfactant or upon reaching the water surface. In one embodiment, the deposited flakes are annealed at the water surface to improve their uniformity. In one embodiment, the reactive end groups on adjacent deposited flakes react with each other to form larger graphene/graphene derivative flakes at the water surface.

The aqueous solution pool may include one or more reducing agents to convert graphene oxide (GO) into reduced graphene oxide (rGO) during the hydrophobic self-assembly of the graphene oxide (GO) exfoliation into reduced graphene oxide (rGO) flakes at the water surface. In one embodiment, the reducing agent is hydrazine. Preferably, any wrinkling or folding of the exfoliated layer is reduced upon reaching the water surface. In one embodiment, the deposited exfoliates are annealed at the water surface to improve their uniformity. In one embodiment, the reactive end groups on adjacent deposited exfoliates react with each other to form larger graphene/graphene derivative flakes at the water surface.

The graphene/graphene-derivative flakes can be applied to the solid by contacting the solid with the graphene/graphene-derivative flakes on the water surface. The solid surface can be immersed in the liquid surface at a vertical, horizontal, or oblique angle. Alternatively, the solid surface can be initially placed in the water and then raised to the liquid surface at a vertical, horizontal, or oblique angle, or the water can be drained to bring the graphene/graphene-derivative flakes to the solid surface.

Optionally, some of the water from the aqueous solution pool is allowed to slowly evaporate, leaving behind a viscous colloidal graphene or graphene gel in the upper liquid portion of the pool.

The carbon source can exist in many forms, including but not limited to a liquefied state, a powdered solid, or a granular solid. In one embodiment, the carbon source preferably comprises at least one essentially non-graphitic carbonaceous material (such as sucrose) having a chemical structure containing at least one six-membered carbon ring, the structure of which is shown in the following molecule (2):

In one embodiment, the carbon source is present in a form with a substantial amount of graphitic carbon.

It is believed that the carbon-containing rings (particularly any aromatic carbocycles) in the carbonaceous material are preserved to some extent during the chemical reaction of the growing carbocyclic skeleton of the graphene or graphene oxide product; in other words, it is believed that the six-membered carbocyclic structure is retained to some extent in the graphene or graphene oxide product.

The essentially non-graphite carbonaceous material may include, but is not limited to, one of the following substances or any combination thereof:

1. Sugars, including but not limited to:

- molasses or molasses substitutes, including but not limited to sweet sorghum, beet molasses, pomegranate molasses, mulberry molasses, carob molasses, date molasses, grape molasses, straight cane molasses, blackstrap molasses, maple syrup, or corn syrup (including but not limited to high fructose corn syrup);

- Invert sugar, including but not limited to invert sugar syrup;

a deoxysugar, including but not limited to deoxyribose, fucose or rhamnose;

a monosaccharide, including but not limited to glucose, fructose, galactose, xylose or ribose;

a disaccharide including, but not limited to, sucrose, dicuculose, lactose, maltose, trehalose, or cellobiose;

a polysaccharide, including but not limited to starch, glycogen, arabinoxylan, cellulose, chitin or pectin;

a sugar alcohol, including but not limited to erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, tretol, iditol, isomalt, maltitol, or lactitol;

an amphiphile, including but not limited to a sugar amphiphile or an amphiphile that promotes graphene formation;

A sugar substitute, including but not limited to stevia, aspartame, sucralose, cyclamate, acesulfame potassium, saccharin or a sugar alcohol;

a hydrocarbon, including but not limited to naphthalene, diesel, kerosene, gasoline, or an alkane (including but not limited to methane, ethane, propane, cyclopropane, butane, isobutane, cyclobutane, pentane, isopentane, neopentane, cyclopentane, hexane, octane, kerosene, isoparaffin, liquid paraffin, or solid paraffin);

a coal component, including but not limited to peat, lignite, bituminous coal, sub-bituminous coal, pulverized coal, nano coal, candle coal, anthracite, charcoal, carbon black, activated charcoal, "activated nano coal" or sugar charcoal;

an alcohol, including but not limited to ethanol, methanol, or isopropanol; or

An oil, including but not limited to linseed oil, citronella oil, geraniol, or mineral oil.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a pyranose, a furanose, a carboxylic acid polyvinyl, or a benzene series (for details, see Katritzky et al., “Aqueous High-temperature Chemistry of Carbo- and Heterocycles. 20. ¹ Reactions ^of Some Benzenoid Hydrocarbons and Oxygen-containing Derivatives in Supercritical Water at 460° C.,” Energy & Fuels, Vol. 8, pp. 487-497, 1994), including but not limited to oxygen-containing benzene series.

In one embodiment, the essentially non-graphitic carbonaceous material comprises sugar. In one embodiment, the essentially non-graphitic carbonaceous material comprises sucrose. In one embodiment, the sugar comprises molasses or a molasses substitute, which may include but is not limited to sweet sorghum, beet molasses, pomegranate molasses, mulberry molasses, carob molasses, date molasses, grape molasses, straight cane molasses, blackstrap molasses, honey, maple syrup, or corn syrup (including but not limited to high fructose corn syrup). In some embodiments, the sugar comprises invert sugar, which may include but is not limited to invert sugar syrup.

In one embodiment, the sugar comprises a deoxy sugar, which may include but is not limited to deoxyribose, fucose, or rhamnose.

In one embodiment, the sugar comprises a monosaccharide, which may include but is not limited to glucose, fructose, galactose, xylose, or ribose.

In one embodiment, the sugar comprises a disaccharide, which may include, but is not limited to, sucrose, dicuculose, lactose, maltose, trehalose, cellobiose, or sophorose.

In one embodiment, the sugar comprises a polysaccharide, which may include but is not limited to starch, glycogen, arabinoxylan, cellulose, chitin, or pectin.

In one embodiment, the essentially non-graphitic carbonaceous material comprises a sugar alcohol, which may include but is not limited to erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, aspartate, iditol, isomalt, maltitol or lactitol.

In one embodiment, the intrinsically non-graphite carbonaceous material comprises a sugar substitute, which may include but is not limited to stevia, aspartame, sucralose, cyclamate, acesulfame potassium, or saccharin.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a sugar derivative, which may include but is not limited to sophoritol, a phenolic glycoside, a steviol glycoside, a saponin, a glycoside, or amygdalin.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a cyclopolydimethylsiloxane, which may include but is not limited to phenyltrimethylpolysiloxane or cyclopentasiloxane.

In one embodiment, the essentially non-graphitic carbonaceous material comprises a steroid, which may include but is not limited to sapogenin or diosgenin.

In one embodiment, the essentially non-graphite carbonaceous material comprises a cinnamate, which may include but is not limited to methyl cinnamate or ethyl cinnamate. In one embodiment, the essentially non-graphite carbonaceous material comprises cinnamic acid. In one embodiment, the additive comprises cinnamic oil.

In one embodiment, the intrinsically non-graphite carbonaceous material comprises a class of phenylpropanes, which may include but are not limited to cinnamic acid, coumaric acid, caffeic acid, 5-hydroxyferulic acid, sinapinic acid, cinnamaldehyde, umbelliferone, resveratrol, a monomeric ligninol (which may include but are not limited to coniferyl alcohol, coumarin or sinapyl alcohol) or a phenylpropene (which may include but are not limited to eugenol, chavicol, safrole or estragole).

In one embodiment, the essentially non-graphite carbonaceous material comprises a benzoate, which may include, but is not limited to, iron benzoate, benzyl benzoate, ethyl benzoate, methyl benzoate, phenyl benzoate, cyclohexyl benzoate, 2-benzyl benzoate, pentaerythritol tetrabenzoate, sodium benzoate, or potassium benzoate. In one embodiment, the essentially non-graphite carbonaceous material comprises aminobenzoic acid. In one embodiment, the essentially non-graphite carbonaceous material comprises methyl 2-hydroxymethylbenzoate. In one embodiment, the essentially non-graphite carbonaceous material comprises ubiquinone.

In one embodiment, the essentially non-graphite carbonaceous material comprises a carboxylate, which may include but is not limited to cis,cis-1,3,5-cyclohexanetricarboxylic acid methyl ester.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a benzopyran, which may include but is not limited to a chromene, an isochromene, or a substituted benzopyran.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a natural flavonoid or a synthetic flavonoid or an isoflavone, and the natural flavonoid or the synthetic flavonoid or the isoflavone may include but is not limited to flavan-3-ols or flavanones.

In one embodiment, the essentially non-graphitic carbonaceous material comprises a salicylate, which may include, but is not limited to, iron salicylate, methyl salicylate, ethyl salicylate, butyl salicylate, cinnamic salicylate, cyclohexyl salicylate, ethylhexyl salicylate, heptyl salicylate, isopentyl salicylate, octyl salicylate, benzyl salicylate, phenyl salicylate, p-cresol salicylate, o-cresol salicylate, m-cresol salicylate, or sodium salicylate. In one embodiment, the essentially non-graphitic carbonaceous material comprises salicylic acid. In one embodiment, the additive comprises aminosalicylic acid.

In one embodiment, the intrinsically non-graphite carbonaceous material includes an antioxidant. In one embodiment, the antioxidant is a cyclic antioxidant. In one embodiment, the antioxidant is a phenolic antioxidant, which may include but is not limited to 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-p-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-l-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecylmethylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxyphenol. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecylepoxyphenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol) , 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α-α-dimethylbenzyl)-4-nonylphenol], 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-di-tert-butyl-2-methylphenol), 1,3-bis(5-tert-butyl-4-hydroxybenzoate), phenol), 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenol)-butane, and any natural plant-based phenolic oxidants, which may include but are not limited to ascorbic acid, tocopherol, tocotrienol, rosmarinic acid, and other phenolic acids and flavonoids, such as those found in grapes, berries, olives, soybeans, tea, rosemary, basil, oregano, cinnamon, cumin, and turmeric.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises 4-vinylphenol, anthocyanidin, or benzopyrylium.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a cyclic amino acid, which may include but is not limited to phenylalanine, tryptophan, or tyrosine.

In one embodiment, the intrinsically non-graphite carbonaceous material comprises a cyclohexane derivative, which may include but is not limited to 1,3-cyclohexadiene or 1,4-cyclohexadiene.

In one embodiment, the intrinsically non-graphite carbonaceous material comprises a benzene derivative, which may include but is not limited to a polyphenol, benzaldehyde, benzotriazole, benzyl l-naphthyl carbonate, benzene, ethylbenzene, toluene, styrene, benzonitrile, phenol, phthalic anhydride, phthalic acid, terephthalic acid, p-toluic acid, benzoic acid, aminobenzoic acid, benzyl chloride, isoindole, ethylphthaloyl ethyl glycolate, N-phenylaniline, methoxybenzoquinone, benzyl acetone, benzylidene acetone, hexyl cinnamaldehyde, 4-amino-2-hydroxytoluene, 3-aminophenol or vanillin.

In one embodiment, the benzene derivative includes catechol, which may include but is not limited to 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol) or 1,4-dihydroxybenzene (hydroquinone, hydroquinone).

In one embodiment, the intrinsically non-graphite carbonaceous material comprises a naphthoate ester, which may include but is not limited to methyl 2-methoxy-1-naphthoate or methyl 3-methoxy-2-naphthoate.

In one embodiment, the intrinsically non-graphite carbonaceous material comprises an acrylate, which may include but is not limited to 2-propylbenzyl acrylate or 2-naphthyl methacrylate.

In one embodiment, the essentially non-graphite carbonaceous material comprises a phthalate ester, which may include but is not limited to diallyl phthalate.

In one embodiment, the intrinsically non-graphite carbonaceous material comprises a succinate, which may include but is not limited to bis(2-carbonyloxybenzyl)succinate.

In one embodiment, the essentially non-graphite carbonaceous material comprises an acid ester, which may include but is not limited to methyl O-methyl podocarpate.

In one embodiment, the intrinsically non-graphitic carbonaceous material includes a fluorophore, which may include but is not limited to fluorescein isothiocyanate, rhodamine, phthalocyanine, or copper phthalocyanine.

In one embodiment, the intrinsically non-graphitic carbonaceous material includes a drug, which may include but is not limited to acetylsalicylic acid (aspirin), acetaminophen (paracetamol), ibuprofen, or a benzodiazepine.

In one embodiment, the intrinsically non-graphite carbonaceous material comprises a phosphate, which may include but is not limited to diphenyl cresyl phosphate, monodiphosphate, tri-o-cresyl phosphate, p-cresyl phosphate, mono-o-cresyl phosphate, or monomethylcresyl phosphate.

In one embodiment, the essentially non-graphite carbonaceous material comprises a compound that degrades under the heat of the operating conditions of the engine or mechanical system to one or more of the above-mentioned additives, such as certain terpenes or certain natural aromatic esters or non-aromatic cyclic esters, ketones or aldehydes, which compounds may include but are not limited to methyl salicylate (wintergreen oil), cinnamon leaf/bark oil (cinnamaldehyde), biphenyl (dipentene), pinene and camphene.

In one embodiment, the essentially non-graphitic carbonaceous material comprises a commercial personal/sexual lubricant composition comprising a sugar substitute amphiphile.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a commercial UV sunscreen formulation comprising octyl methoxycinnamate, butyl methoxydibenzoylmethane (B-MDM, avobenzone), octyl-dimethyl-p-aminobenzoic acid (OD-PABA), octocrylene, oxybenzone, alkyl benzoate, diethylhexyl 2,6-naphthalene dicarboxylate, phenoxyethanol, homosalate, ethylhexyl triazone, 4-methylbenzylidene camphor (4-MBC), or a polysorbate.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a commercial skin cream formulation, which may include, but is not limited to, carbopol, ascorbyl palmitate, tocopheryl acetate, ketoconazole, or mineral oil.

In one embodiment, the essentially non-graphitic carbonaceous material comprises a commercial hand sanitizer formulation, which may include carbopol, tocopheryl acetate, or propylene glycol.

In one embodiment, the essentially non-graphitic carbonaceous material comprises a commercial human or animal hair care product, which may include benzophenone, alkyl benzoate, phenoxyethanol, sorbitan oleate, a styrene copolymer, propylene glycol, hydroxyisohexyl 3-cyclohexenyl carboxaldehyde, dibutyl hydroxytoluene, ketoconazole, petrolatum, mineral oil, or liquid paraffin.

In one embodiment, the commercial hair care product is a curl activator or soothing lotion, which may include carbopol, hexyl cinnamaldehyde, benzyl salicylate, triethanolamine salicylate, benzyl benzoate, eugenol, 1,3-dihydroxymethyl-5,5-dimethylhydantoin (DMDM hydantoin), para-aminobenzoic acid (PABA), 2-ethylhexyl 4-dimethylaminobenzoate (padimate-O), butylphenyl methylpropional, propylparaben, phenolsulfonphthalein (PSP, phenol red) or a polysorbate.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a commercial hair dye formulation, which may include hydrated iron oxide (Fe(OH) ₃ ), p-phenylenediamine, o-aminophenol, m-aminophenol, p-aminophenol, 4-amino-2-hydroxytoluene, trideceth-2-carboxamide MEA (monoethanolamine), phenylmethylpyrazolone, phenoxyethanol, polyquaternium salt, hexylcinnamaldehyde, butylphenylmethylpropional, phenolsulfonphthalein (PSP, phenol red), hydroxyisohexyl 3-cyclohexenylcarboxaldehyde, titanium dioxide, or iron oxide.

In one embodiment, the intrinsically non-graphitic carbonaceous material comprises a commercial pesticide, which may include but is not limited to o-phenylphenol (OPP), phenylhydroquinone (PPQ), or diphenoquinone (PBQ).

The oxidant may be in many forms, including but not limited to gaseous, liquefied, powdered, or granular forms. In one embodiment, the oxidant may include but not limited to one of the following substances or any combination thereof: potassium nitrate, gaseous oxygen, sodium nitrate, ammonium dichromate, ammonium nitrate, ammonium perchlorate, potassium perchlorate, potassium permanganate, calcium nitrate, hydrogen peroxide, sodium bicarbonate, or mercuric thiocyanate.

In one embodiment, the reaction mixture includes a solvent. The solvent may include an alcohol, which may include, but is not limited to, one or any combination of the following: methanol, ethanol, isopropyl alcohol, n-propyl alcohol, or a gelled alcohol formulation, including, but not limited to, a solidified denatured alcohol formulation, such as the formulation containing ethanol and methanol found in canned fuel sold under the trademark "Sterno Group, LLC" of Des Plaines, Illinois, or a gelled alcohol formulation found in hand sanitizers, including formulations containing polyacrylic acid or propylene glycol.

In one embodiment, the reaction mixture includes one or more catalysts or other additives. The additive or catalyst may include, but is not limited to, one of the following substances or any combination thereof: sodium bicarbonate, aluminum bicarbonate, sodium aluminum phosphate, sodium aluminum sulfate, potassium carbonate, potassium phosphate, potassium hydroxide, aluminum hydroxide, magnesium hydroxide, magnesium sulfate, magnesium phosphate, potassium hydrogen tartrate, citric acid, ascorbic acid, sucrase, invertase, ferrocene or a transition metal oxide catalyst (which may be in a nanopowder state), and the metal oxide catalyst includes, but is not limited to, one of the following substances or any combination thereof: iron (II) oxide, iron (II, III) oxide, iron (III) oxide, iron (II) hydroxide, iron (III) hydroxide, or iron (III) oxide hydrate, aluminum oxide, a copper oxide (including a copper (I) oxide or a copper (II) oxide), a nickel oxide (including nickel (I) oxide or nickel (II) oxide), a titanium oxide (including but not limited to titanium dioxide, titanium (I) oxide or titanium (II) oxide), a lead oxide (including but not limited to lead (II) oxide, lead (IV) oxide, lead tetroxide) or a lead sesquioxide.

In one embodiment, sucrose and sodium bicarbonate are combined in a volume ratio of about 4:1, and ethanol is added as a solvent to form the reaction mixture.

In one embodiment, the reactants are mixed with a flammable solvent, such as methanol, ethanol, or isopropanol. In some embodiments, the carbon source is dissolved in the flammable solvent. In other embodiments, the reactants and the solvent form a slurry.

In one embodiment, the reaction is carried out without using a solvent.

In one embodiment, powdered sugar and sodium bicarbonate powder are combined in a 4:1 volume ratio and then mixed with a metal oxide catalyst before exposure to heat.

In one embodiment, the reaction mixture may additionally or alternatively include one or more of sodium bicarbonate, naphthalene, and linseed oil.

In one embodiment, sucrose and potassium nitrate are combined in a ratio of about 35:65 to form the reaction mixture, as described in " Rocket Manual for Amateurs by B.R. Brinley, Ballantine Books, New York, New York, 1960; and " Amateur Experimental Rocketry , Vol. 7 by Richard Nakka, self-published on CD only, January 2011." In one embodiment, the reaction mixture further comprises a metal oxide in an amount ranging from 1% to about 30% (preferably about 5%).

In one embodiment, powdered sugar and an alcohol (preferably ethanol or isopropanol) are placed in a reaction vessel and mixed to form a paste-like reaction mixture. The reaction mixture is heated to produce a steam-exfoliated graphene/graphene derivative exfoliate containing steam. In some embodiments, the reaction mixture further comprises iron oxide in the form of an iron oxide powder pigment from Lanxess, Cologne, Germany. In other embodiments, the iron oxide is in the form of a high-purity ferrosoferric oxide ( _Fe₃O₄ ) (15-20 _nm ) nanopowder supplied by US Research Nanomaterials, Inc., Houston, Texas, USA.

In one embodiment, powdered sugar and a gelling alcohol in the form of a conventional hand sanitizer comprising water, polyacrylic acid, and ~60% isopropyl alcohol are placed in a reaction vessel and mixed together to form a reaction mixture. The reaction mixture is heated to produce a steam-containing steam-exfoliated graphene/graphene derivative exfoliate. In some embodiments, the reaction mixture further comprises iron oxide in the form of an iron oxide powder pigment from Lanxess, Cologne, Germany. In other embodiments, the iron oxide is in the form of a high-purity ferrosoferric oxide ( _Fe₃O₄ ) (15-20 nm) nanopowder supplied by US Research Nanomaterials, Inc., Houston, _Texas , USA.

In one embodiment, a reaction mixture of powdered sugar and an alcohol (preferably ethanol) is heated on a hot plate to a temperature lower than that achieved using direct flame heating in previously described embodiments. The reaction mixture is heated to a temperature that causes the formation of a vapor containing exfoliated graphene/graphene derivatives. In one embodiment, the reaction mixture further comprises iron oxide in the form of an iron oxide powder pigment from Lanxess, Cologne, Germany. In one embodiment, the iron oxide is in the form of high-purity ferrosoferric oxide ( _Fe₃O₄ ) (15-20 _nm ) nanopowder supplied by US Research Nanomaterials, Inc., Houston, Texas, USA.

In one embodiment, the iron oxide source is a substrate on which the other reactants are placed. In one embodiment, the iron oxide source is a rusted iron-based metal part. The reactants are then heated as in one of the previously described embodiments.

In one embodiment, the carbonaceous material is coal or a coal derivative. In one embodiment, the coal is pulverized coal. In one embodiment, the coal is nanocoal. In one embodiment, the carbonaceous material is one or more of coal, coke, and coal tar. In one embodiment, the coal or coal derivative is heated to reflux temperature in a high-boiling-point solvent. In one embodiment, the process is performed using a crude or informal coal tar distillation furnace or coke furnace, where the reaction gases are recondensed and dripped back into the reaction mixture.

In one embodiment, the carbonaceous material is sucrose. In some embodiments, concentrated sulfuric acid converts the sucrose into graphite carbon, and the graphite carbon can be formed from bubbles from the isolated reaction gas by a dehydration reaction as shown in the following reaction formula (4):

In one embodiment, an excess of concentrated sulfuric acid is used so that any water vapor or other gases formed during the dehydration reaction are released from the reaction mixture and the graphitic carbon product is not in the form of foam. In one embodiment, superheat is provided to the system to facilitate the release of all reaction gases.

In one embodiment, heat is used to convert the sucrose into carbon via a dehydration reaction as shown in the following reaction (5):

In one embodiment, a graphite carbon source and a liquid are placed in a reaction vessel and mixed together to form a slurry mixture. The graphite carbon source can be any material comprising graphite carbon, including but not limited to natural graphite, synthetic graphite, one or more polycyclic aromatic hydrocarbons (PAHs), graphene, activated carbon, biochar, coal slurry, one or more benzene series, or any combination thereof. In one embodiment, the graphite is natural graphite or synthetic graphite. In one embodiment, the graphite is ground into a fine powder. In one embodiment, the graphite carbon source is an activated carbon. In one embodiment, the liquid comprises one or any combination of an alcohol, water, or mineral oil. In one embodiment, the liquid is an acid or a strong acid liquid. In one embodiment, the alcohol is methanol. The slurry mixture is heated to produce a steam-containing steam-exfoliated graphene/graphene derivative exfoliation. In one embodiment, the reaction mixture further comprises iron oxide in the form of iron oxide powder pigment from Lanxess, Cologne, Germany. In other embodiments, the iron oxide is in the form of high-purity ferrosoferric oxide (Fe ₃ O ₄ ) (15-20 nm) nanopowder supplied by US Research Nanomaterials, Inc. in Houston, Texas, USA.

In one embodiment, a graphitic carbon product from the dehydration reaction of sucrose and a solvent are placed in a reaction vessel and mixed together to form a slurry mixture. In one embodiment, the solvent can include one or any combination of an alcohol, water, or mineral oil. In one embodiment, the alcohol is methanol, ethanol, or isopropanol. The slurry mixture is heated to produce a steam-containing steam-exfoliated graphene/graphene derivative exfoliation. In some embodiments, the reaction mixture further includes iron oxide in the form of an iron oxide powder pigment from Lanxess, Cologne, Germany. In one embodiment, the iron oxide is in the form of high-purity ferrosoferric oxide ( _Fe3O4 ) (15-20 _nm ) nanopowder supplied by US Research Nanomaterials, Inc. of Houston, Texas, USA.

In one embodiment, the heat source is a direct open flame. In one embodiment, the heat source is a fuel mixed with the reactants and ignited by an ignition source. In one embodiment, the heat source is a hot plate. In one embodiment, an additional reactant is added to promote the formation of a reaction gas. In one embodiment, the additional reactant is sodium bicarbonate and the reaction gas is carbon dioxide. In one embodiment, the reactants are heated until they auto-ignite.

In one embodiment, the chemical reaction can be intentionally performed under pyrolysis conditions. In one embodiment, a reaction can be intentionally performed under conditions of insufficient oxygen for combustion, minimal oxygen, or in a partial vacuum chamber. In one embodiment, at least some of the reactants are subjected to heat during formation in a controlled low oxygen environment. In one embodiment, a reaction can intentionally utilize an additive to promote incomplete combustion and the formation of carbon black or other products of incomplete combustion or pyrolysis. In one embodiment, the reaction can be rapidly completed by exposing the reaction mixture to the heat of a direct flame.

In one embodiment, the solid reactants are mixed and then heated in a reaction vessel (such as a crucible) with a direct flame. Although the fuel used to generate the flame can be any fuel within the spirit of the present invention, the fuel used in these embodiments is preferably a relatively cleanly burning fuel such as methane, ethane, propane or butane.

In one embodiment, the heat source is a direct flame.

In one embodiment, the system is externally heated to a temperature slightly below the auto-ignition temperature required for the system to begin forming products.

In one embodiment, the graphene or graphene oxide (GO) is formed as a product of heating an expansion material. The expansion material is generally used as a flame retardant. As used herein, the term "expansion material" may include, but is not limited to, one of the following substances or any combination thereof: ditolyl phosphate, tritolyl phosphate (including but not limited to p-tolyl phosphate, o-tolyl phosphate, m-tolyl phosphate), polymer resin precursors or certain epoxy resins, including but not limited to thermosetting resins (including but not limited to phenol formaldehyde resins, melamine resins, cyanate resins, or polycyanate esters, polyphenylene ether resins, ethylene propylene diene monomer resins, or polyolefin plastomer resins).

In one embodiment, heating the intumescent material produces a light coke having poor thermal conductivity. In one embodiment, heating the intumescent material produces a heavy coke. In one embodiment, the resulting coke is subjected to solvent attack and reheated to produce the graphene or graphene oxide product. In one embodiment, the resulting coke can then function as the carbonaceous material, added to and reacted with an oxidant. In one embodiment, the coke can be combined with an oil and then heated to produce the graphene or graphene oxide product.

In one embodiment, as described above, the carbon source of the carbonaceous material added to the reactant or additive may include, but is not limited to, one of the following substances or any combination thereof: linseed oil, a light paraffin oil, a naphthalene-type compound, a resin, a resin precursor, an alkyd resin or an alkyd precursor, including but not limited to a polyol (including but not limited to maltitol, sorbitol, isomaltol, pentaerythritol, ethylene glycol, glycerol or polyester).

In one embodiment, the reactants include one or more polyols, one or more acid anhydrides, or one or more unsaturated fatty acid triglycerides.

It is envisioned that modifying the above method can make it easier to collect the graphene or graphene oxide, and can achieve a higher yield.

In one embodiment, no liquid or gel mixing medium is used. In one embodiment, the mixing medium is methanol. In one embodiment, the mixing medium is water. In one embodiment, the mixing medium is a solid, semi-solid or gel-like combustible material that can be mixed with the carbon source. In one embodiment, the combustible material is a gel fuel made from denatured alcohol, water and a gel, such as the canned fuel supplied by The Sterno Group, LLC of Des Plaines, Illinois. In one embodiment, the denatured alcohol includes ethanol to which one or more additives are added, and the additives can include one or any combination of the following substances: methanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, or denatonium benzoate.

In one embodiment, the gel fuel is made from vinegar, calcium carbonate, and isopropyl alcohol. In such an embodiment, the gel fuel can be gradually heated to increase its fluidity and facilitate mixing with the reactants, and then cooled to re-gel. In such an embodiment, a direct flame can only be used initially to ignite the gel fuel and initiate the reaction, and the flame is maintained by the combustion of the gel fuel itself.

In one embodiment, the vapor-belt graphene or graphene derivative flakes are collected by deposition onto a solid surface in contact with the vapor-belt flakes.

In one embodiment, the vapor-borne graphene or graphene-derivative flakes are collected using clean coal technology. In one embodiment, a scrubber (preferably a wet scrubber) is used to collect any vapor-borne graphene or graphene-derivative flakes—for example, see Semrau, "Practical Process Design of Particulate Scrubbers," Chemical Engineering, Vol. 84, pp. 87-91, 1977. In one embodiment, the vapor-borne particles, including any vapor-borne graphene or graphene oxide flakes, are collected by treating the exhaust gas with steam.

In one embodiment, the steam-belt graphene or graphene derivative exfoliation is collected by bubbling the generated steam through a liquid. In one embodiment, the liquid is water. In other embodiments, the liquid is an oil, which may include but is not limited to a vegetable oil or a lubricating oil. In one embodiment, a surfactant is added to the water to promote the formation of a uniform layer of graphene or graphene derivatives at the water surface. In one embodiment, the liquid is heated to promote the formation of a uniform layer of graphene or graphene derivatives by hydrophobic self-assembly at the water surface. In one embodiment, the liquid is heated to a temperature close to its boiling point. In one embodiment, an additive is used to increase the boiling point of the liquid. In one embodiment, ultrasound is applied to the liquid to promote the hydrophobic self-assembly of graphene or graphene derivatives at the water surface. In one embodiment, ultraviolet light is applied to the liquid to promote the hydrophobic self-assembly of graphene or graphene derivatives at the water surface. In one embodiment, an argon environment above the liquid promotes the hydrophobic self-assembly of graphene or graphene derivatives at the water surface. In one embodiment, a reduced pressure is used to promote the hydrophobic self-assembly of graphene or graphene derivatives, as described in Putz et al., “Evolution of Order During Vacuum-assisted Self-assembly of Graphene Oxide Paper and Associated Polymer Nanocomposites”, ASC Nano, Vol. 5, pp. 6601-6609, 2001.

In one embodiment, the solvent containing the graphite material remaining in the reaction vessel after the pyrolysis step is applied as a coating to form a composite material reinforced with the graphite material. In one embodiment, the graphite-containing solvent is applied by immersing the material to be coated in the graphite-containing solvent. In one embodiment, the coating is a fiber web. In one embodiment, multiple layers of the deposit cover any cracks in the graphite material, thereby strengthening the coating.

In one embodiment, the graphite-containing solvent is mixed with a structural material to form a graphene-reinforced composite material. In one embodiment, the graphite-containing solvent is combined with pre-impregnated composite fibers to form a graphene-reinforced composite material. In one embodiment, the carbon source of the graphite material is a resin precursor of a specific resin to be reinforced by the graphite material.

In one embodiment, an aqueous collection fluid for accumulating the combustion product vapors is used in a mold to facilitate the fabrication of a solid composite material utilizing the combustion products.

In one embodiment, the reaction vapors are collected and directed directly onto the inner or outer surface of a mold without the use of a liquid collection medium.

In one embodiment, the reaction vapors are collected and directed onto the surface of a solid substrate. In one embodiment, the solid substrate is a fiber, and a graphene-reinforced fiber composite is formed as deposition occurs. In one embodiment, the fibers are carbon fibers. In one embodiment, the fibers are polymers. The graphene coating can be applied to the fibers before or after the individual fibers are woven together, depending on the intended use and the desired properties of the graphene fiber composite. In one embodiment, multiple layers of the deposition cover any cracks in the graphene sheet, thereby reinforcing the coating.

In one embodiment, the collected vapor is suspended in a liquid that is subsequently drained, evaporated, or eliminated, causing the graphene, graphene oxide, or reduced graphene oxide flakes to coat the interior of a mold, or to be deposited onto a solid or liquid matrix already within such a mold, or to be introduced into the mold, to produce a composite material.

In the system of FIG3 , a reaction mixture is placed in a reaction vessel 10. Heat is applied to the reaction vessel 10 via a heating element 12. The generated reaction gas and gaseous products build pressure in the reaction vessel 10 and exit the reaction vessel through a conduit 14. The reaction gas vapor exits the conduit 14 above the surface of a liquid 16. In another embodiment (not shown), the conduit 14 directs the vapor below the surface 18 of the liquid 16, whereupon the vapor bubbles to the surface 18 of the liquid 16. In one embodiment (not shown), a sparger connected to the end of the conduit 14 provides multiple release points to distribute the bubbles of the reaction gas vapor below or above the surface of the liquid. The reaction gas is released into the atmosphere 22 above the liquid surface 18, while the graphene/graphene-derivative product remains in the liquid, accumulating primarily at the liquid surface 18. Alternatively, the conduit 14 can release the reaction gas vapor into the atmosphere 22 directly above the liquid surface 18. In some such embodiments, the reactant gas vapor is directed from the conduit 14 toward the liquid surface 18 .

A temperature control element 24 can control the temperature of the liquid by providing heat or cooling to promote the formation of larger graphene oxide flakes on the surface of the liquid through hydrophobic self-assembly. The temperature control element 24 or a separate ultrasonic element can provide ultrasonic vibrations to promote the formation of larger graphene oxide flakes on the surface of the liquid. A lid (not shown) can be used to cover the liquid 16 to create a closed, controlled environment 22 above the liquid 16. In one embodiment (not shown), an increased pressure is maintained in the environment 22 by a pressure source through a valve. In one embodiment, the pressure source is an inert gas (such as argon) to provide an inert environment above the liquid. In one embodiment (not shown), a vent valve allows excess pressure to be released from the atmosphere 22. The reaction vessel 10 preferably includes a pressure equalization valve 34 to relieve the ultra-vacuum formed in the reaction vessel 10, thereby preventing the liquid from being introduced into the conduit 14 during reflux and reaction.

In one embodiment, the reaction vessel is a Büchner flask. In one embodiment, the top of the flask is stoppered, and a conduit is connected to a fitting on the flask. In one embodiment, the other end of the conduit is placed below a liquid, and the other end is free of any type of sparger. In one embodiment, the pressure equalizing valve is connected to a line extending through the stopper on the top of the Büchner flask.

In one embodiment, the graphene or graphene derivative formed on the surface of the liquid is transferred to the solid substrate simply by contacting the solid substrate with the surface of the liquid, such as by deposition using Langmuir-Blodgett (LB) film induced deposition - for example, see Blodgett, "Films built by depositing successive monomolecular layers on a solid surface", Journal of the American Chemical Society, Vol. 57, pp. 1007-1022, 1935.

In one embodiment, the collected graphene oxide (GO) or graphene product is further reduced or treated to eliminate residual impurities from the product.

In one embodiment, the graphene oxide (GO) reaction product is converted into reduced graphene oxide (rGO). In one embodiment, the graphene oxide (GO) is chemically reduced to reduced graphene oxide as summarized by the following reaction formula (6):

Graphene oxide + reducing agent → reduced graphene oxide (rGO) (6)

In one embodiment, the graphene oxide (GO) is colloidally dispersed in water or another liquid and then chemically reduced to reduced graphene oxide (rGO) using hydrazine hydrate. For details, see Stankovich et al., “Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide”, Carbon, Vol. 45, pp. 1558-1565, 2007; Gao et al., “Hydrazine and Thermal Reduction of Graphene Oxide: Reaction Mechanisms”, Journal of Physical Chemistry C, Vol. 114, pp. 832-842, 2010. C, Vol. 114, pp. 832-842, 2010); Si et al., “Synthesis of Water Soluble Graphene”, Nano Letters, Vol. 9, pp. 1679-1682, 2008. In one embodiment, the graphene oxide (GO) is chemically reduced to reduced graphene oxide (rGO) using hydroquinone. For details, see Wang et al., “Facile Synthesis and Characterization of Graphene Nanosheets”, Journal of Physical Chemistry C, Vol. 112, pp. 8192-8195, 2008. In one embodiment, the graphene oxide (GO) is chemically reduced to reduced graphene oxide (rGO) using gaseous hydrogen, as described in Wu et al., “Synthesis of high-quality graphene with a pre-determined number of layers”, Carbon, Vol. 47, pp. 493-499, 2009. In other embodiments, a strongly alkaline solution is used to chemically reduce the graphene oxide (GO) to reduced graphene oxide (rGO)—for details, see Fan et al., “Deoxygenation of Exfoliated Graphite Oxide under Alkaline Conditions: A Green Route to Graphene Preparation,” Advanced Materials, Vol. 20, pp. 4490-4493, 2008; and Boehm et al., “Adsorption Behavior of Ultrathin Carbon Foils,” Journal of Inorganic and General Chemistry, Vol. 306, pp. 119-127, 1962. und allgemeine Chemie, Vol.306, pp.119-127, 1962).

In one embodiment, the graphene oxide (GO) is reduced to reduced graphene oxide (rGO) by applying heat or an electric current. In one embodiment, when subjected to heating to 1050° C. and compression, the graphene oxide is thermally exfoliated and reduced to rGO, eliminating generated carbon dioxide (see McAllister et al., “Single Sheet Functionalized Graphene by Oxidation and Thermal Expansion of Graphite”, Chemistry of Materials, Vol. 19, pp. 4396-4404, 2007). In one embodiment, graphene oxide (GO) is electrochemically reduced to reduced graphene oxide (rGO) by placing electrodes at opposite ends of a graphene film on a non-conductive substrate and applying a current. For details, see Zhou et al., “Controlled Synthesis of Large-Area and Patterned Electrochemically Reduced Graphene Oxide Films”, Chemistry-A European Journal, Vol. 15, pp. 6116-6120, 2009.

In one embodiment, the graphene oxide product is converted to self-assembled films of reduced graphene oxide platelets at the air-water interface by adding hydrazine hydrate to water through which the produced graphene oxide is bubbled, and then heating the aqueous solution to ˜80° C. (see Zhu et al., “Transparent self-assembled films of reduced graphene oxide platelets,” Applied Physics Letters, Vol. 95, pp. 103, 104-1-103, 104-3, 2009). Additional external forces may be applied to the liquid to stimulate the reduced graphene oxide platelets to self-assemble, including but not limited to ultrasonic vibrations or ultraviolet light.

In one embodiment, the above product is combined with a polymer resin to form a high-strength composite material. The polymer resin is preferably an epoxy polymer resin. In some embodiments, the composite material further includes carbon fibers.

In one embodiment, the polymer resin and the graphene/graphene derivative form alternating layers in the composite material. In one embodiment, a graphene/graphene derivative layer is deposited as a vapor onto a polymer resin layer. In one embodiment, a graphene/graphene derivative layer is deposited onto a polymer resin layer from an aqueous surface. In one embodiment, a graphene/graphene derivative paste is applied to a polymer resin layer.

In one embodiment, the graphene/graphene derivative is formed directly on the polymer resin layer by dehydrating sucrose using concentrated sulfuric acid, wherein the polymer resin material has high sulfuric acid resistance. Polymer materials with high sulfuric acid resistance include, but are not limited to, polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polychlorofluoroethylene (PCTFE), epoxy resin fibers, and EP21AR epoxy resin from Master Bond, Inc. of Hackensack, New Jersey, USA.

In one embodiment, the resin is one of the following polymer resins or a mixed combination thereof: (1) one or more alkylphenol resins generally used in tire manufacturing; (2) one or more p-octylphenol (POP)-like formaldehyde resins; (3) one or more p-tert-butylphenol (PTBP)-like formaldehyde non-heat-sensitive tackifying resins; (4) one or more polyparaphenylene ethylene (PPE) resins; and (5) one or more polyphenylene ether (PPO) resins, including but not limited to one or more silicone polyphenylene ether resins.

In one embodiment, the graphene/graphene derivative is mixed with the polymer resin prior to solidification. In one embodiment, the carbon fibers are also mixed with the graphene/graphene derivative and dissolved in the polymer resin. The type of polymer resin and the relative levels of graphene/graphene derivative and carbon fibers are preferably selected to provide an appropriate balance of strength and flexibility depending on the specific use and application of the final composite product.

In one embodiment, the resin used for the polymer of the composite material is also the carbon source for the graphene/graphene derivative portion of the composite material.

In one embodiment, the graphene/graphene oxide enhanced polymer composite is used in structural applications that are traditionally limited to metal materials (such as the frame of a vehicle). In one embodiment, the polymer composite can be re-molded and thus reused from one structure to another.

In a method for forming gel graphene or graphene jelly, a pool of aqueous solution containing exfoliated graphene/graphene derivatives is allowed to evaporate gradually. In one embodiment, the starting materials used to produce the reaction mixture to produce the exfoliated graphene/graphene derivatives include sucrose, sodium bicarbonate, ethanol, and iron oxide. In one embodiment, the water in the aqueous solution pool evaporates very slowly, and after about a month at a temperature close to room temperature, a volume of liquid half the initial volume of ~800 mL remains in the conical cup. A layer of viscous gel that can be peeled off forms on top of the liquid. Beneath this top layer is a milky white layer about 1 1/2" (inches) thick with the consistency of a thin jelly. Although these graphene jellies have not been further tested, it is expected that these forms of graphene have useful physical and chemical properties.

In one embodiment, the pool of aqueous solution containing hydrogel graphene or the collected graphene/graphene derivative is used to replace water in the formation of a composite material. In one embodiment, the pool of aqueous solution containing hydrogel graphene or the collected graphene/graphene derivative is used to replace water in a cement mixture to form graphene-enhanced concrete having higher strength than conventional concrete. In one embodiment, the pool of aqueous solution containing hydrogel graphene or the collected graphene/graphene derivative is used to form asphalt concrete to form graphene-enhanced asphalt concrete having higher strength than conventional asphalt concrete.

In one embodiment, carbon dioxide or carbon monoxide is used as a carbon source for the production of graphene, a graphene derivative, a carbon-coated metal nanoparticle or nanosteel, thereby potentially eliminating excess carbon in the environment. Carbon monoxide and carbon dioxide can be converted into a variety of products suitable as carbonaceous feedstocks for the synthetic methods encompassed herein, such as the synthesis of methanol—for example, see Sakakura et al., “Transformation of Carbon Dioxide”, Chemical Reviews, Vol. 107, pp. 2365-2387, 2007; Yu et al., “Copper- and copper-N-heterocyclic carbene-catalyzed C—H activating carboxylation of terminal alkynes with CO at ambient conditions”, Proceedings of the National Academy of Sciences, Vol. 107, pp. 20184-20189, 2010. National Academy of Sciences (PNAS), Vol. 107, pp. 20184-20189, 2010); Jiang et al., “Turning carbon dioxide into fuel”, Philosophical Transactions of the Royal Society A, Vol. 368, pp. 3343-3364, 2010. In one embodiment, the carbon monoxide or carbon dioxide is first converted into one or more forms of carbonaceous materials capable of undergoing combustion or pyrolysis reactions to incorporate carbon atoms from such gases into useful carbon-carbon graphitic bonds. In one embodiment, an intermediate in such conversion is an alcohol formed by the reaction of carbon dioxide with hydrogen. In one embodiment, the carbon dioxide is supplied directly to the reflux mixture to react with hydrogen generated by the reflux of the reflux mixture, thereby forming the synthetic methanol in situ.

In one embodiment incorporating iron oxides, the process operates like a nanoscale "Bessember furnace" to form nanosteel. Referring to Figure 7, significant charging is observed throughout the sample, particularly at the edges of the spheroids. Since the sample is charged overall, the likely cause of this charging is the presence of a non-conductive material throughout the sample. Based on basic analysis, the only possible non-conductive material is an oxide. Therefore, a layer of oxide is inferred to be present throughout the column. As for the charging of the spheroids, since no sharp edges are observed in the images, the spheroids must contain both conductive and non-conductive materials. The most likely cause of this phenomenon is the sequestration of elemental iron within a non-conductive carbon oxide matrix.

Elemental iron conducts electricity and generates heat under a scanning electron microscope (SEM), but the non-conductive carbon oxide matrix is strong enough to prevent the spheroid structure from breaking apart, despite being non-conductive and unable to transfer charge to the oxide layer throughout the sample. It is inferred that, given that energy dispersive spectroscopy (EDS) reveals only the presence of iron, carbon, and oxygen, the outer oxide layer is graphene oxide, and the conductive material is iron. If the outer shell of the spheroid were pure carbon (for example, if the structure were graphene or a fullerene), the spheroid would be conductive, and no charging of the sample would be observed, as is the case with carbon nanotubes or ribbons commonly used as SEM accessories. Since the outer layer is charged, it must be non-conductive, making graphene oxide the most likely form of carbon. Furthermore, as mentioned above, the entire column is charged to some degree, as shown in the SEM images. Therefore, it is inferred that multilayer graphene oxide is present throughout the sample.

In one embodiment, the nanosteel is machined to form a nanocircuit or other nanostructure. In some embodiments, a laser etching nanobeam is used to shape the nanosteel.

Test results

Several experiments were conducted to produce and recover graphene and its derivatives according to the present invention, as well as to generate surface graphitized abrasive nanoparticles (SGANs).

Test 1

In one method for synthesizing surface graphitized abrasive nanoparticles (SGANs), a reaction mixture is heated using a direct flame. Iron oxide powder pigment from Lanxess, Cologne, Germany, powdered sugar, and ethanol are placed in a reaction vessel and mixed to form a paste-like reaction mixture. The reaction mixture is then heated with the direct flame of a propane torch. A scanning electron microscope (SEM) column is then positioned above the heated reaction mixture in the fumes and/or vapors generated by the heating of the reaction mixture.

The surfaces of the SEM pillars were then observed using an XL30 ESEM-FEG scanning electron microscope (FEI ^™ Company, Hillsboro, Oregon, USA) using Genesis ^™ version 4.61 software and a Scandium Imaging Platform (Electron Microscope, ^Inc. , Mahwah, New Jersey, USA). Electron microscope images of the pillar surfaces are shown in Figures 4 to 7. Concomitant elemental analysis of the sample regions by energy dispersive spectroscopy (EDS), eliminating copper and aluminum readings from the pillars, revealed only the weight percent (wt%) and atomic percent (at%) of carbon, oxygen, and iron for the sample regions of Figures 4 to 7, as shown in Table 1. Figures 4 to 6 show spheroidal structures with diameters ranging from 2 to 5 microns, and the figures all show non-spherical, irregularly shaped structures with lengths ranging from 1 to 5 microns.

Table 1

The sampled areas of the spheroids in Figures 4 through 5C all show primarily carbon and oxygen, with similarly low iron values. Referring to Figure 4 , the electron beam was aimed at a large area of a spheroidal structure with a diameter of approximately 5 μm. Referring to Figure 5A , the electron beam was aimed at a small patch on the surface of a spheroid with a diameter between 2 and 3 μm. Referring to Figure 5B , the electron beam was aimed at a small white area on the surface of the spheroid in Figure 5A . This image clearly demonstrates the spheroidal nature of the structure and the presence of surface defects. Referring to Figure 5C , the electron beam was aimed at a larger portion of the spheroid in Figure 5A . It is believed that this structure contains much higher levels of internal iron than those measured by energy dispersive spectroscopy (EDS), and the low EDS readings indicate that the electron beam penetrated the outer shell to a low depth into the spheroid's cortex. It is believed that the spheroidal structure is a multilayer graphene oxide nano-onion, and that the multilayer graphene oxide shields the internal iron, making it undetectable by EDS.

Figure 6 shows one of the non-spherical features observed on the surface of the pillar sample. These structures are believed to be morphologically characteristic of graphene oxide paper. The brighter areas of this image indicate a higher concentration of iron. Energy dispersive spectroscopy (EDS) measurements indicate that the amount of iron in this structure is almost ten times greater than that measured in the spheroids. It is believed that the electron beam is able to penetrate this thin graphene oxide paper to a greater extent than the multilayered spheroids, leading to the reported high iron content in this sample.

The observed spheroid structures were determined to be highly stable, as no significant effects were observed on the structures after the electron beam was directed at them for more than 20 minutes.

In some scanning electron microscope (SEM) images, a square shaded area was observed on the stem, indicating electronic excitation and a non-conductive surface presumably coated with a graphene oxide film.

Test 2

In another synthesis method for surface graphitized abrasive nanoparticles (SGANs), a reaction mixture is heated using a direct flame. Iron oxide powder pigment from Lanxess, Cologne, Germany, powdered sugar, and a gelling alcohol in the form of a common hand sanitizer containing water, polyacrylic acid, and ~60% isopropyl alcohol are placed in a reaction vessel and mixed together to form a reaction mixture. The reaction mixture is heated with the direct flame of a propane torch. A scanning electron microscope (SEM) column is then mounted above the heated reaction mixture in the fumes and/or vapors generated by the heating of the reaction mixture.

The images were taken using an XL30 ESEM-FEG scanning electron microscope (FEI ^™ Company, Hillsboro, Oregon, USA) with Genesis ^™ version 4.61 software and a Scandium Imaging Platform (Scandium Imaging, ^Inc. , Mahwah, New Jersey, USA). The surfaces of the SEM pillars were studied using a scanning electron microscope (SEM) platform. Electron microscope images of the surfaces of the pillars are shown in Figures 8 to 11. Concomitant element analysis by energy dispersive spectroscopy (EDS), which eliminated the copper and aluminum readings from the pillars, showed only carbon (64.40 wt%/79.37 At%), oxygen (16.95 wt%/15.68 At%), and iron (18.65 wt%/4.94 At%) in the sample area of Figure 8. The structures observed on the surface of the SEM pillars were generally smaller than those observed according to the previous synthesis method using ethanol (rather than gelling alcohol). It was observed that the relative ratio of the number of spherical structures to the number of lamellar structures was much higher compared to the synthesis using ethanol. Figure 10 shows a highly concentrated area of spherical structures.

Figure 11 shows a larger area of the SEM column at a lower magnification. The image shows that a very thin film has been deposited continuously over a large area of the SEM column. For imaging purposes, a gold/palladium coating was vapor-deposited onto the sample. However, it was observed that the gold/palladium coating was much thicker than the graphene oxide vapor coating, resulting in any graphene oxide vapor coating details being completely obscured by the gold/palladium coating. It is important to note that the gold/palladium coating shows that the graphene oxide vapor coating is intact across the entire column.

Test 3

In another synthesis method for surface graphitized abrasive nanoparticles (SGANs), a direct flame is used to heat a reaction mixture. Iron oxide powder pigment from Lanxess, Cologne, Germany, ethanol, and mineral oil are placed in a reaction vessel and mixed together to form a reaction mixture. The reaction mixture is heated with the direct flame of a propane torch. A scanning electron microscope (SEM) column is then mounted above the heated reaction mixture in the fumes and/or vapors generated by the heating of the reaction mixture.

The surfaces of the SEM pillars were investigated using an XL30 ESEM-FEG scanning electron microscope from FEI ^™ Company, Hillsboro, Oregon, USA, using Genesis ^™ version 4.61 software and a Scandium Imaging Platform from FEI ^Inc. , Mahwah, New Jersey, USA. Electron microscopy images of the pillar surfaces revealed structures similar in appearance to those described in the experiments above, including spheroids with diameters between 5 and 15 μm and larger irregular crystalline structures with minimum widths between 10 and 50 μm. Concomitant elemental analysis by energy dispersive spectroscopy (EDS), which eliminated copper and aluminum readings from the pillars, revealed numerous impurities, including calcium, copper, sodium, silicon, and lead, in addition to carbon, oxygen, and iron, all of which can form face-centered cubic (FCC) crystals.

Test 4

In another method for synthesizing nanoparticles, a reaction mixture is heated on a hot plate to a temperature lower than that achieved by direct flame heating in the previously described method. Iron oxide powder, powdered sugar, and ethanol are placed in a Büchner flask. The top of the flask is stoppered, and plastic tubing is connected to the nipple of the flask. The other end of the plastic tubing is placed under water in a conical beaker of distilled water. The reaction mixture is heated, causing steam to form, which is bubbled through the distilled water. After the reaction is complete, the water is allowed to evaporate slowly in the conical beaker, and the surface of the water has a viscosity, and as the water evaporates, a white residue is deposited on the wall of the conical beaker above the water surface. Although the white residue has not been characterized, it is believed to be formed by surface graphitized abrasive nanoparticles (SGANs).

Test 5

In another method for synthesizing nanoparticles, 365 Organic Powdered Sugar (ingredients: organic cane sugar, organic tapioca starch) from Whole Foods Market in Austin, Texas, USA; Instant Hand Sanitizer (ingredients: 62% ethanol, water, triethanolamine glycerol, propylene glycol, tocopheryl acetate, aloe vera gel, carbopol, fragrance) from Greenbrier International, Inc. in Chesapeake, Virginia, USA; and 99% Isopropyl Alcohol (ingredients: 99% Isopropyl Alcohol) from Meijer Distributing, Inc. in Grand Rapids, Michigan, USA were used as the raw materials for the synthesis of nanoparticles. Alcohol; Dr. Oetjer Baking Powder (ingredients: sodium pyrophosphate, sodium bicarbonate, corn starch) from Dr. Oetjer Canada, Ltd. of Mississauga, Ontario, Canada; and Walgreens Mineral Oil Intestinal Lubricant (ingredients: mineral oil) from Walgreen Company of Deerfield, Illinois, USA, were combined in a flask. The flask was heated with a direct flame to convert the sugar into graphitic carbon. The top of the flask was stoppered, and a tube was used to bubble the reaction gas containing the steam-exfoliated graphene flakes into a water bath. Mineral oil was added to the beaker as needed to maintain fluidity.

A metal spatula was brought into contact with the surface of the water bath to collect the reaction product that had formed there after the gas vapor transfer. After allowing the metal spatula to dry overnight, a distinct film was observed on the spatula. Although the metal spatula was immersed in the liquid at an angle, the reaction product could alternatively be transferred to the solid surface by immersing it parallel or perpendicular to the liquid surface, depending on the solid surface and the desired surface coating. Alternatively, the solid surface could be pulled upward from below the liquid surface across the interface, or the liquid could be drained to deposit the product onto the solid surface in the liquid.

The coated metal surface was then rubbed against a carbon transmission electron microscope (TEM) grid to transfer some of the graphene coating to the TEM grid. The coating on the ^TEM grid was observed using a TEM transmission electron microscope (Serial No. D609) from FEI ^™ Company of Hillsboro, Oregon, USA, and the images of Figures 12 to 17 were recorded. These structures are similar in composition and morphology to structures known as holey carbon or lace carbon. Figure 12 shows the morphological features of a relatively large and uniform graphene sheet. Figure 13 shows the morphological features of a relatively large graphene sheet with a tendril extending to the left of the image. Figure 14 shows a folded multilayer graphene sheet. Figures 16 and 17 show graphene filaments connecting larger sheet areas, while Figure 15 shows a higher magnification image of multiple layers of such graphene filaments. With the exception of the images in Figures 12 to 17, portions of the TEM grid appeared completely black under the TEM due to the deposited layer being too thick for the electron beam to pass through. In some other areas, the film appeared incompletely dry, and the graphene coating was observed to change shape under the electron beam.

Test 6

In one method for forming graphene flakes, activated charcoal, water, mineral oil, and isopropyl alcohol are heated in a capped Büchner flask. As the mixture begins to boil and reflux, a white smoke begins to be produced along with the steam. The white smoke and steam are transported out of the beaker through a plastic tube and then applied to the surface of a pool of aqueous solution, where an opaque film forms. After waiting a few minutes after the film has formed, sections of the film are transferred to copper transmission electron microscope (TEM) grids for further study.

The copper transmission electron microscope (TEM) grids were studied using a Tecnai F20(S) TEM transmission electron microscope from ^{FEI ™} Company of Hillsboro, Oregon, USA. Representative images of the samples are shown in Figures 18 and 19. For elemental analysis, the electron beam was used to determine the carbon-oxygen ratio at eight different points in the sample. The analysis results showed that the carbon-oxygen ratio in the samples ranged from 97.4:2.6 At% (atomic percentage) to 99.1:0.9 At% (atomic percentage), with an average of 98.4:1.6 At% (atomic percentage) for the eight samples. Compared to experiments with iron oxide in the reaction mixture, the final product of the experiments without iron oxide was graphene that was almost pure carbon.

In situ generation of tribologically effective amounts of beneficial carbonaceous deposits in lubricant compositions

Embodiments of the present invention utilize a cyclic carbon-containing additive as a base lubricant that is designed to rapidly pyrolyze in situ within an engine or mechanical system and produce tribologically effective amounts of beneficial carbonaceous deposits and molecules. In one embodiment, the additive forms beneficial abrasive graphite particles in situ within the lubricant composition. These beneficial abrasive graphite particles act as a nanopolishing agent, nanopolishing friction surfaces and removing asperities before the base lubricant begins to effectively degrade. Once the friction surface has undergone nanopolishing to near-atomic-perfect smoothness, there are no more asperities on the friction surface to harbor harmful deposits. Consequently, harmful deposits on internal system components and the need for traditional detergent additives in lubricant compositions can be significantly reduced or even eliminated.

The additives disclosed herein are not selected to improve or protect the base lubricant. Instead, the additives are selected to promote the rapid in-situ formation of polycyclic aromatic hydrocarbons or other graphitic carbon constructs containing tribologically effective amounts of nanoparticles or microparticles of tribologically useful graphitic carbon. In one embodiment, the additive comprises a carbon-containing ring additive composed solely of carbon, hydrogen, and oxygen atoms. In one embodiment, the carbon-containing ring additive is a hydrocarbon. Any base groups in the lubricant composition aid in the formation of the useful graphitic carbon particles. In one embodiment, the nanoparticles act as nanopolishes, nanopolishing friction surfaces to a high degree of smoothness by reducing or eliminating asperities, thereby reducing friction between worn surfaces. Conventional base lubricants tend to lose viscosity over time, placing friction surfaces at risk of damage. Using embodiments of the present invention, friction surfaces experience a higher degree of nanopolishing, so any dilution of the base lubricant through continued use allows the mechanical system to operate more efficiently by reducing the viscosity of the base lubricant. In one embodiment, the base lubricant starts as a heavier oil and then gradually dilutes to a lighter oil over time while the friction surface is nanopolished. In one embodiment, the lubricant composition effectively lubricates despite an extended drain interval or replacement interval compared to conventional base lubricants.

Instead of gradually promoting degradation to form compounds that convert to an amorphous carbon slurry, at least one of the additives promotes the formation of one or more tribologically useful graphitic carbon formations described herein.

The lubricant composition of the present invention preferably includes an additive selected to act as a sacrificial carbon source, which acts in the in situ formation of graphitic carbon while the base lubricant continues to lubricate a running engine or other mechanical system. The base lubricant can be a petroleum refined oil or a synthetic oil, grease or liquid. The additive can pyrolyze to form graphitic carbon under the operating conditions of the running engine or other mechanical system. In one embodiment, the additive can pyrolyze at a temperature between 50°C and 550°C. In one embodiment, the additive can pyrolyze at a temperature below 50°C or above 550°C. In a running engine, such temperature conditions can be achieved locally on the friction surface, or on the surface of the internal combustion engine, supercharger, turbine or gear.

The additive is provided in a tribologically effective amount so that the in-situ structure is formed and present in the lubricant composition so as to initially provide a sufficiently effective friction coating on the friction surfaces of a lubricated system. The amount of additive added to the lubricant can vary, depending on the desired rate of change in performance of the operating engine or other mechanical system and the amount of base lubricant required to keep the base lubricant undiluted. Adding a larger amount of additive can increase the rate of formation of the in-situ structure, but will also dilute the base lubricant. An effective amount of additive therefore includes a range of ~10 mg of additive per liter of base lubricant to ~500 g of additive per liter of base lubricant. These amounts are not intended to limit the present invention in any way and can be determined by the manufacturer on a case-by-case basis.

In one embodiment, the tribologically effective amount of the additive reduces friction in the lubricated system as compared to lubrication of the system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces friction in the lubricated system by at least 1% as compared to lubrication of the system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces friction in the lubricated system by at least 2% as compared to lubrication of the system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces friction in the lubricated system by at least 3% as compared to lubrication of the system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces friction in the lubricated system by at least 4% as compared to lubrication of the system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces friction in the lubricated system by at least 5% as compared to lubrication of the system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces friction in the lubricated system by at least 10% as compared to lubrication of the system lubricated by a conventional lubricant.

In one embodiment, a tribologically effective amount of the additive reduces negative horsepower in the lubricated system, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive increases measured horsepower in the lubricated system by at least 1%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive increases measured horsepower in the lubricated system by at least 2%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive increases measured horsepower in the lubricated system by at least 5%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive increases measured horsepower in the lubricated system by at least 10%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive increases measured horsepower in the lubricated system by at least 20%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive increases measured horsepower in the lubricated system by at least 50%, as compared to lubrication of the system by a conventional lubricant.

In one embodiment, a tribologically effective amount of an additive increases the output torque of a lubricated system compared to lubrication of a system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of an additive increases the output torque of a lubricated system by at least 1% compared to lubrication of a system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of an additive increases the output torque of a lubricated system by at least 2% compared to lubrication of a system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of an additive increases the output torque of a lubricated system by at least 5% compared to lubrication of a system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of an additive increases the output torque of a lubricated system by at least 10% compared to lubrication of a system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of an additive increases the output torque of a lubricated system by at least 20% compared to lubrication of a system lubricated by a conventional lubricant. In one embodiment, the tribologically effective amount of an additive increases the output torque of a lubricated system by at least 50% compared to lubrication of a system lubricated by a conventional lubricant.

In one embodiment, a tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system by at least 5%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system by at least 5%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system by at least 10%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system by at least 20%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system by at least 50%, as compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system by at least 75% compared to lubrication of the system by a conventional lubricant. In one embodiment, the tribologically effective amount of the additive reduces the surface roughness of an internal friction surface in the lubricated system by at least 90% compared to lubrication of the system by a conventional lubricant.

In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 100 hours of operation of the lubricated system after addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 80 hours of operation of the lubricated system after addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 60 hours of operation of the lubricated system after addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 40 hours of operation of the lubricated system after addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 20 hours of operation of the lubricated system after addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 10 hours of operation of the lubricated system following addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 5 hours of operation of the lubricated system following addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 2 hours of operation of the lubricated system following addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 1 hour of operation of the lubricated system following addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 30 minutes of operation of the lubricated system following addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 10 minutes of operation of the lubricated system after addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs within 5 minutes of operation of the lubricated system after addition of the tribologically effective amount of the additive. In one embodiment, a measurable change in friction, a measurable reduction in negative horsepower, or a measurable reduction in surface roughness occurs substantially immediately after addition of the tribologically effective amount of the additive.

As described herein, a lubricant composition comprising at least one additive improves engine performance and nanopolishes lubricated metal surfaces. At least one of the additives undergoes in-situ chemical modification to form lubricating and nanopolishing particles, a phenomenon observed on the lubricated metal surfaces using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The spherical structures observed on the non-friction surfaces were generally in the 1-10 micron size range and were determined to be primarily composed of carbon, oxygen, and iron. These micronized particle structures were isolated into elementary particles no larger than ~3 nm (nanometers) in size and sufficiently hard to nanopolish a steel structure with a measured roughness ( _Ra ) of 3.44 nm.

In one embodiment, the elementary particle has been determined to be a surface graphitized abrasive nanoparticle (SGAN), and more specifically, a metal surface graphitized abrasive nanoparticle. In some embodiments, the metal surface graphitized abrasive nanoparticle is an iron surface graphitized abrasive nanoparticle. The core of the surface graphitized abrasive nanoparticle (SGAN) can be a cubic close-packed crystal structure with a face-centered cubic metal. The cubic close-packed crystals may be a metal oxide from the spinel family, including but not limited to magnetite (Fe ₃ O ₄ ), magnesium aluminum spinel (MgAl ₂ O ₄ ), zinc aluminum spinel (ZnAl ₂ O ₄ ), iron aluminum spinel (FeAl ₂ O ₄ ), copper iron spinel (CuFe ₂ O ₄ ), zinc iron manganese spinel, manganese iron magnesium aluminum spinel, manganese iron spinel (MnFe ₂ O ₄ ), nickel iron spinel (NiFe ₂ O ₄ ), titanium iron spinel (TiFe ₂ O ₄ ), zinc iron spinel, iron chromium spinel (FeCr ₂ O ₄ ), and magnesium chromium spinel (MgCr ₂ O ₄ ). In other embodiments, the core may have a non-spinel cubic crystal structure.

The cubic crystal structure may include at least one iron atom. In some embodiments, the crystal core may be ferric hydroxide in the form of spinel, as described in Belleville et al., "Crystallization of ferric hydroxide into spinel by adsorption on colloidal magnetite," Journal of Colloid and Interface Science, Vol. 150, pp. 453-460, 1992. In one embodiment, the crystal core may be _{Fe2Cu1 -xRh2Se4 in} the _form of spinel, where 0<x≤0.3 _. For details, see Kim et al., “Magnetic properties of the spinel phase _{for FexCu1 -xRh2Se4 ” ,} Journal of Applied Physics, _Vol . 64, 342190, ₁₉₈₈ .

In one embodiment, the crystal nucleus is formed in situ. In one embodiment, the additive comprises a crystal nucleus. In some embodiments, the crystal nucleus may be formed by one or more structures, as described in the following documents - see "Chapter 5: Deoxidation in Low Carbon Steel Killed with Aluminum" in Ph.D. Thesis, Katholieke Universiteit Leuven, Leuven, pp. 43-65, Belgium, 2002 by Dekker; "Mechanochemical Synthesis of Hercynite", Materials Chemistry and Physics, Vol. 76, pp. 104-109 by Botta et al. Physics, Vol. 76, pp. 104-109); or Chen et al., “Synthesis of Hercynite by Reaction Sintering”, Journal of the European Ceramic Society, Vol. 31, pp. 259-263, 2011.

In one embodiment, the outer shell of the surface graphitized abrasive nanoparticle (SGAN) is believed to be a carbon fullerene or fullerene-like structure. In some embodiments, the carbon source is believed to be converted in situ to polycyclic aromatic hydrocarbons (PAHs) to form graphene sheets, as disclosed in Bohme, “PAH and Fullerene Ions and Ion/Molecule Reactions in Interstellar and Circumstellar Chemistry,” Chem. Rev. Vol. 92, pp. 1487-1508, 1992; and Mansurov, “Formation of Soot from Polycyclic Aromatic Hydrocarbons as well as Fullerenes and Carbon Nanotubes in Combustion of Hydrocarbons,” Journal of Engineering Physics and Thermodynamics, vol. 84, pp. 125-159, 2011. Nanotubes in the Combustion of Hydrocarbon”, Journal of Engineering Physics and Thermodynamics, Vol. 84, pp. 125-159, 2011; or Ravindra et al., “Atmospheric polycyclic aromatic hydrocarbons: Source attribution, emission factors and regulation”, Atmospheric Environment, Vol. 42, pp. 2895-2921, 2008, wherein the graphene is then converted to a fullerene in the presence of iron via the mechanism disclosed in the following article: Chuvilin et al., “Direct Transformation of Graphene into Fullerenes”, Nature Chemistry, Vol. 2, pp. 450-453, 2010. In one embodiment, the carbon deposits on the surface of the iron particles are believed to be in the form of coke, as described in Meima et al., “Catalyst Deactivation Phenomena in Styrene Production”, Applied Catalysis A: General, Vol. 212, pp. 239-245, 2001. In one embodiment, the polycyclic aromatic hydrocarbons are believed to be surface-graphitized.

In one embodiment, the carbon may be deposited on the surface of an iron particle in the form of cross-linked styrene spheres, such as by Friedel-Crafts alkylation, cross-linking, and polymerization reactions, as described in Barar et al., “Friedel-Crafts Cross-linking for Polystyrene Modification,” Industrial & Engineering Chemistry Product Research and Development, Vol. 22, pp. 161-166, 1983.

In the observed surface graphitized abrasive nanoparticles (SGANs), at least some of the measured iron is expected to be in the form of magnetite, which would make the surface graphitized abrasive nanoparticles (SGANs) ferromagnetic. In other embodiments, the surface graphitized abrasive nanoparticles (SGAN) or cross-linked styrene spheres may include one or more ferromagnetic, paramagnetic, or superparamagnetic particles. In one embodiment, the surface graphitized abrasive nanoparticles (SGANs) are believed to form agglomerates in situ and are coated with a graphitic carbon coating in the form of one or any combination of polycyclic aromatic hydrocarbons (PAHs), graphene, graphene oxide, microtubes, and fullerenes to form larger micron particles. Under shear, these agglomerates are believed to break down into smaller units or detached surface layers, but will reagglomerate once they migrate from the high shear environment.

The magnetic properties of the surface graphitized abrasive nanoparticles (SGANs) or iron-containing cross-linked styrene spheres create an attractive force between them, the graphite carbon, the iron-containing surface, and the iron-containing particles suspended in the lubricant composition. When an iron surface graphitized abrasive nanoparticle or larger aggregate approaches a steel friction surface, the particle is attracted to the surface and helps lubricate and micro-polish it. The core supporting the shell of the surface graphitized abrasive nanoparticle (SGAN) provides the strength required to polish steel parts.

The surface-graphitized abrasive nanoparticles (SGANs) disclosed herein are superior nanopolishing agents to nanodiamonds. Since the core of the surface-graphitized abrasive nanoparticles is not believed to be chemically bonded to its shell, the shell is believed to be able to rotate independently outside the core, acting as a nanoball bearing. Furthermore, the unconstrained shell of the surface-graphitized abrasive nanoparticles is believed to be less rigid than that of nanodiamonds, thus better dissipating impact forces.

In one embodiment, instead of the above-mentioned core containing crystalline metal, the surface graphitized abrasive nanoparticles (SGAN) may have a core containing an aromatic carbocycle. In one embodiment, the core containing an aromatic carbocycle may be a core containing styrene or a styrene derivative. In one embodiment, the core containing an aromatic carbocycle may be formed in situ in the lubricant composition by self-assembly of amphiphilic molecules containing aromatic carbocycles. In one embodiment, the amphiphilic molecules containing aromatic carbocycles may be amphiphilic molecules of styrene or styrene derivatives. In one embodiment, the self-assembly core may include reactive groups that allow the molecules to cross-link with each other when the self-assembly is completed. In one embodiment, a fullerene shell may be formed around the self-assembly core to form a nanoparticle similar to the above-mentioned surface graphitized abrasive nanoparticles (SGANs) to form a nanopolishing agent.

In addition to the additives tested, many other types of additives can be used in the lubricant composition to achieve similar results. Preferably, the additive has a structure having at least one ring, which can be aromatic or non-aromatic, and at least one functional group extending from the ring or from a bond extending from the ring. In one embodiment, the structure comprises a fused ring. Preferably, the additive structure includes at least one oxygen atom in addition to carbon and hydrogen atoms. In one embodiment, other heteroatoms may be present in the chemical structure, although they may not be required to achieve the desired structure and may be undesirable.

In one embodiment, the additive is dissolved in the lubricant composition. In one embodiment, the additive is a liquid that can be easily mixed with the lubricant. In one embodiment, the additive includes a particulate matter. Since traditional engine oil filters are designed to filter all particles larger than 40 μm, half of the particles 20 μm and about 10-20% of the particles 10 μm, the particulate additive added to the engine preferably has an average particle size of less than 10 μm to prevent clogging of the engine oil filter. In one embodiment, substantially all particles have a particle size of less than 10 μm. In one embodiment, the average particle size of the particulate additive is less than 5 μm. In one embodiment, substantially all particles have a particle size of less than 5 μm. In one embodiment, the average particle size of the particulate additive is less than 1 μm. In one embodiment, substantially all particles have a particle size of less than 1 μm.

In one embodiment, the additive comprises powdered sugar (sucrose). Powdered sugar is commercially available in a variety of finenesses and is often used in baking. 6X powdered sugar has an average particle size of less than ~200 μm. 10X powdered sugar has an average particle size of less than ~150 μm. Soft candy is powdered sugar with an average particle size of less than ~50 μm. Commercially available soft candies include "Celebration," a product of British Sugar of Peterborough, UK, which is an ultrafine sugar with an average particle size of ~11 μm; "Silk Sugar," a product of British Sugar, Peterborough, UK, which is an extremely fine sugar with an average particle size of ~8 μm; and "C&H Baker's Driver," a product of C&H Sugar Company, Inc. of Crockett, California, USA, which has an average particle size of ~5-7 μm.

In one embodiment, the powdered sugar has an average particle size of less than ~5 μm. In one embodiment, substantially all of the particles have a particle size of less than ~5 μm. In some embodiments, the powdered sugar has an average particle size of less than ~1 μm. In one embodiment, substantially all of the particles have a particle size of less than ~1 μm. In some embodiments, the powdered sugar is formed to a predetermined particle size by grinding crystalline sucrose in a dry environment. In one embodiment, the powdered sugar is ground using a known dry micro-grinding technique for grinding crystals into micron or sub-micron particles. In one embodiment, the powdered sugar is formed to a predetermined particle size by an evaporation technique, such as evaporating a solvent from droplets of a dissolved sugar solution or freeze-drying a dissolved sugar solution.

In one embodiment, sugar (preferably micronized or nanopowdered sucrose) is added to a conventional base lubricant as a carbon source for in-situ graphitic carbon formation when the lubricant composition lubricates an operating engine. In one embodiment, sugar alone is added to a conventional base lubricant. In one embodiment, sugar and Mystery Oil (original formulation, hydrocarbon and terpene source) from Turtle Wax, Inc. of Westmont, Illinois, are added to a conventional base lubricant. In one embodiment, sugar and mineral oil are added to a conventional base lubricant. In one embodiment, sugar is combined with an oil surfactant to compatibilize the sugar prior to addition to the base lubricant—for details, see Hiteshkumar et al., “Self-assembly in Sugar-Oil Complex Glasses,” Nature Materials, vol. 6, 2007, pp. 287-290. Materials, 6, pp. 287-290, 2007). In one embodiment, the compatibilization of the sugar prevents the sugar from clogging filters in the lubricated system in the form of a gel or solid. In one embodiment, the oil surfactant is a terpene. In one embodiment, the terpene is dipentene. In one embodiment, the sugar and oil surfactant are combined in a ratio of less than 1:1. In one embodiment, the sugar-oil surfactant mixture is in a liquid state when added to the lubricating fluid. In one embodiment, the sugar is a sugar amphiphile.

In one embodiment, the additive comprises a pyranose, a furanose, a carboxylic acid polyol, or a benzene series compound (for details, see Katritzky et al., “Aqueous High-temperature Chemistry of Carbo- and Heterocycles. 20. ¹ Reactions of Some Benzenoid Hydrocarbons and Oxygen-containing Derivatives in Supercritical Water at 460° C.,” Energy & ^Fuels , Vol. 8, pp. 487-497, 1994), including but not limited to oxygen-containing benzene series compounds.

In one embodiment, the additive comprises a sugar other than sucrose. In one embodiment, the sugar comprises molasses or a molasses substitute, which may include but is not limited to sweet sorghum, beet molasses, pomegranate molasses, mulberry molasses, carob molasses, date molasses, grape molasses, straight cane molasses, blackstrap molasses, honey, maple syrup, or corn syrup (including but not limited to high fructose corn syrup). In some embodiments, the sugar comprises invert sugar, which may include but is not limited to invert sugar syrup.

In one embodiment, the sugar comprises a deoxy sugar, which may include but is not limited to deoxyribose, fucose, or rhamnose.

In one embodiment, the sugar comprises a monosaccharide, which may include but is not limited to glucose, fructose, galactose, xylose, or ribose.

In one embodiment, the sugar comprises a disaccharide, which may include, but is not limited to, sucrose, dicuculose, lactose, maltose, trehalose, cellobiose, or sophorose.

In one embodiment, the sugar comprises a polysaccharide, which may include but is not limited to starch, glycogen, arabinoxylan, cellulose, chitin, or pectin.

In one embodiment, the additive comprises a sugar alcohol, which may include but is not limited to erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, aspartate, iditol, isomalt, maltitol or lactitol.

In one embodiment, the additive comprises a sugar substitute, which may include but is not limited to stevia, aspartame, sucralose, cyclamate, acesulfame potassium or saccharin.

In one embodiment, the additive comprises a sugar derivative, which may include but is not limited to sophoritol, a phenolic glycoside, a steviol glycoside, a saponin, a glycoside or amygdalin.

In one embodiment, the additive includes a cyclomethicone, which may include but is not limited to phenyl trimethicone or cyclopentasiloxane.

In one embodiment, the additive includes a steroid, which may include but is not limited to sapogenin or diosgenin.

In one embodiment, the additive comprises a cinnamate, which may include but is not limited to methyl cinnamate or ethyl cinnamate. In one embodiment, the additive comprises cinnamic acid. In one embodiment, the additive comprises cinnamic oil.

In one embodiment, the additive includes a phenylpropane, which may include but is not limited to cinnamic acid, coumaric acid, caffeic acid, 5-hydroxyferulic acid, sinapinic acid, cinnamaldehyde, umbelliferone, resveratrol, a monomeric lignin alcohol (which may include but is not limited to coniferyl alcohol, coumarin or sinapyl alcohol) or a phenylpropene (which may include but is not limited to eugenol, chavicol, safrole or estragole).

In one embodiment, the additive comprises a benzoate, which may include but is not limited to iron benzoate, benzyl benzoate, ethyl benzoate, methyl benzoate, phenyl benzoate, cyclohexyl benzoate, 2-benzyl benzoate, pentaerythritol tetrabenzoate, sodium benzoate or potassium benzoate. In one embodiment, the additive comprises aminobenzoic acid. In one embodiment, the additive comprises methyl 2-hydroxymethyl benzoate. In one embodiment, the additive comprises ubiquinone.

In one embodiment, the additive includes a monocarboxylate, which may include but is not limited to cis,cis-1,3,5-cyclohexanetricarboxylic acid methyl ester.

In one embodiment, the additive includes a benzopyran, which may include but is not limited to a chromene, an isochromene, or a substituted benzopyran.

In one embodiment, the additive comprises a natural flavonoid or a synthetic flavonoid or an isoflavone, and the natural flavonoid or the synthetic flavonoid or the isoflavone may include but is not limited to flavan-3-ol or flavanone.

In one embodiment, the additive comprises a salicylate, which may include, but is not limited to, iron salicylate, methyl salicylate, ethyl salicylate, butyl salicylate, cinnamic salicylate, cyclohexyl salicylate, ethylhexyl salicylate, heptyl salicylate, isopentyl salicylate, octyl salicylate, benzyl salicylate, phenyl salicylate, p-cresol salicylate, o-cresol salicylate, m-cresol salicylate, or sodium salicylate. In one embodiment, the essentially non-graphite carbonaceous material comprises salicylic acid. In one embodiment, the additive comprises aminosalicylic acid.

In one embodiment, the additive includes an antioxidant. In one embodiment, the antioxidant is a cyclic antioxidant. In one embodiment, the antioxidant is a phenolic antioxidant, and the phenolic antioxidant may include but is not limited to 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-p-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-l-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecylmethylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxy 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecylepoxyphenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol) , 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α-α-dimethylbenzyl)-4-nonylphenol], 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-di-tert-butyl-2-methylphenol), 1,3-bis(5-tert-butyl-4-hydroxybenzoate), phenol), 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenol)-butane, and any natural plant-based phenolic oxidants, which may include but are not limited to ascorbic acid, tocopherol, tocotrienol, rosmarinic acid, and other phenolic acids and flavonoids, such as those found in grapes, berries, olives, soybeans, tea, rosemary, basil, oregano, cinnamon, cumin, and turmeric.

In one embodiment, the additive includes 4-vinylphenol, anthocyanidin, or benzopyrylium.

In one embodiment, the additive includes a cyclic amino acid, which may include but is not limited to phenylalanine, tryptophan, or tyrosine.

In one embodiment, the additive includes a cyclohexane derivative, which may include but is not limited to 1,3-cyclohexadiene or 1,4-cyclohexadiene.

In one embodiment, the additive includes a benzene derivative, which may include but is not limited to a polyphenol, benzaldehyde, benzotriazole, benzyl l-naphthyl carbonate, benzene, ethylbenzene, toluene, styrene, benzonitrile, phenol, phthalic anhydride, phthalic acid, terephthalic acid, p-toluic acid, benzoic acid, aminobenzoic acid, benzyl chloride, isoindole, ethylphthaloyl ethyl glycolate, N-phenylaniline, methoxybenzoquinone, benzyl acetone, benzylidene acetone, hexyl cinnamaldehyde, 4-amino-2-hydroxytoluene, 3-aminophenol or vanillin.

In one embodiment, the benzene derivative additive includes catechol, which may include but is not limited to 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol) or 1,4-dihydroxybenzene (hydroquinone, hydroquinone).

In one embodiment, the additive includes a naphthoate ester, and the naphthoate ester may include but is not limited to 2-methoxy-1-naphthoic acid methyl ester or 3-methoxy-2-naphthoic acid methyl ester.

In one embodiment, the additive includes an acrylate, and the acrylate may include but is not limited to 2-propylbenzyl acrylate or 2-naphthyl methacrylate.

In one embodiment, the additive includes a phthalate ester, which may include but is not limited to diallyl phthalate.

In one embodiment, the additive includes a succinate, and the succinate may include but is not limited to bis(2-carbonyloxybenzyl)succinate.

In one embodiment, the additive includes an acid ester, which may include but is not limited to methyl O-methyl podocarpate.

In one embodiment, the additive includes a fluorophore, which may include but is not limited to fluorescein isothiocyanate, rhodamine, phthalocyanine, or copper phthalocyanine.

In one embodiment, the additive comprises a drug, which may include but is not limited to acetylsalicylic acid (aspirin), acetaminophen (paracetamol), ibuprofen or a benzodiazepine.

In one embodiment, the additive includes a monophosphate, which may include but is not limited to diphenyl cresyl phosphate, monodiphosphate, tri-o-cresyl phosphate, p-cresyl phosphate, mono-o-cresyl phosphate, or monomethylcresyl phosphate.

In one embodiment, the additive comprises a compound that degrades under the heat of the operating conditions of the engine or mechanical system to one or more of the above additives, such as certain terpenes or certain natural aromatic esters or non-aromatic cyclic esters, ketones or aldehydes, which compounds may include but are not limited to methyl salicylate (wintergreen oil), cinnamon leaf/bark oil (cinnamaldehyde), biphenyl (dipentene), pinene and camphene.

In one embodiment, the additive comprises a commercial personal/sexual lubricant composition comprising a sugar substitute amphiphile.

In one embodiment, the additive comprises a commercial UV sunscreen formulation comprising octyl methoxycinnamate, butyl methoxydibenzoylmethane (B-MDM, avobenzone), octyl-dimethyl-p-aminobenzoic acid (OD-PABA), octocrylene, oxybenzone, alkyl benzoate, diethylhexyl 2,6-naphthalene dicarboxylate, phenoxyethanol, homosalate, ethylhexyl triazone, 4-methylbenzylidene camphor (4-MBC) or a polysorbate.

In one embodiment, the additive comprises a commercial skin cream formulation, which may include, but is not limited to, carbopol, ascorbyl palmitate, tocopheryl acetate, ketoconazole, or mineral oil.

In one embodiment, the additive comprises a commercial hand sanitizer formulation, which may include carbopol, tocopheryl acetate, or propylene glycol.

In one embodiment, the additive comprises a commercial human or animal hair care product, which may include benzophenone, alkyl benzoate, phenoxyethanol, sorbitan oleate, a styrene copolymer, propylene glycol, hydroxyisohexyl 3-cyclohexenyl carboxaldehyde, dibutyl hydroxytoluene, ketoconazole, petrolatum, mineral oil or liquid paraffin.

In one embodiment, the commercial hair care product is a curl activator or soothing lotion, which may include carbopol, hexyl cinnamaldehyde, benzyl salicylate, triethanolamine salicylate, benzyl benzoate, eugenol, 1,3-dihydroxymethyl-5,5-dimethylhydantoin (DMDM hydantoin), para-aminobenzoic acid (PABA), 2-ethylhexyl 4-dimethylaminobenzoate (padimate-O), butylphenyl methylpropional, propylparaben, phenolsulfonphthalein (PSP, phenol red) or a polysorbate.

In one embodiment, the additive comprises a commercial hair dye formulation, which may include hydrated iron oxide (Fe(OH) ₃ ), p-phenylenediamine, o-aminophenol, m-aminophenol, p-aminophenol, 4-amino-2-hydroxytoluene, trideceth-2 carboxamide MEA (monoethanolamine), phenylmethylpyrazolone, phenoxyethanol, monoquaternary ammonium salt, hexyl cinnamaldehyde, butylphenyl methylpropional, phenolsulfonphthalein (PSP, phenol red), hydroxyisohexyl 3-cyclohexenyl carboxaldehyde, titanium dioxide or iron oxide.

In one embodiment, the additive includes a commercial pesticide, which may include but is not limited to o-phenylphenol (OPP), phenylhydroquinone (PPQ), or diphenoquinone (PBQ).

In one embodiment, the additive includes a compound with a two-dimensional structure, which may include but is not limited to lignin, graphene, or graphene oxide.

In one embodiment, the additive includes a carbon constituent, including but not limited to peat, lignite, bituminous coal, sub-bituminous coal, pulverized coal, nano coal, candle coal, anthracite, charcoal, carbon black, activated charcoal, activated nano coal, or sugar charcoal. In one embodiment, the carbon constituent acts as a thermal conductivity agent in the lubricant composition.

In one embodiment, the carbon construct comprises a nanopowder. In one embodiment, the carbon construct has an increased surface area. In one embodiment, the carbon construct comprises activated charcoal particles that have been ground from a conventional activated charcoal to nanoparticle size. The activated charcoal can be ground using any conventional method to produce nanoscale particles. In one embodiment, the activated charcoal is ground using wet or dry nano-grinding techniques known for grinding solids into sub-micron particles. In one embodiment, the nano-activated charcoal has an average particle size of less than ~100 nm. In one embodiment, substantially all of the particles have a particle size of less than ~100 nm. In one embodiment, the particulate additive has an average particle size of less than ~50 nm. In one embodiment, substantially all of the particles have a particle size of less than ~50 nm.

In one embodiment, the carbon constituent comprises graphite carbon. In one embodiment, the graphite carbon comprises at least one polycyclic aromatic hydrocarbon (PAH), and the PAH may include but is not limited to naphthalene, acene, acene, fluorine, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[j]fluoranthene, benzo[a]pyrene, benzo[e]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]pyrene, indeno[1,2,3-c,d]pyrene, tetracene, hexabenzone, cyclopentene, pentacene, triphenylene, and ovalene.

In one embodiment, the carbon constituent comprises a biochar or biocoal product of a hydrothermal carbonization process.

In one embodiment, the additive provides the same benefits to the lubrication system as those provided by tricresyl phosphate (TCP), which is considered a carcinogen and a factor in aerotoxic syndrome and is being phased out of many lubrication systems.

In one embodiment, the additive comprises a "dirty" or crudely refined form of mineral oil contaminated with high levels of polycyclic aromatic hydrocarbons (PAHs). Industrially produced white mineral oils contain very low levels of PAHs, which must be substantially completely removed before the mineral oil can be sold as "USP" (United States Pharmacopeia) or "food grade." In one embodiment, the separated waste mineral oil from these processes (where PAH concentrations are highest) is used untreated and used directly as an additive or in combination with other additives. The white mineral oil component of this waste acts as a wetting agent in the lubricant composition, while the PAHs act as a thermal conductivity agent and a source of graphitic carbon in the formation of surface graphitized abrasive nanoparticles (SGANs) and microsphere agglomerates containing surface graphitized abrasive nanoparticles (SGANs).

In one embodiment, the additive comprises a compatibilizer. As used herein, the term "compatibilizer" refers to a compound that helps disperse a carbon source in a lubricant or lubricant composition. In some embodiments, the compatibilizer is an amphiphilic. In some embodiments, the compatibilizer comprises a surfactant. In some embodiments, the compatibilizer comprises a grease. In some embodiments, the compatibilizer comprises a polymer. In some embodiments, the compatibilizer also serves as a carbon source.

In one embodiment, the compatibilizer comprises a sugar amphiphile. A sugar amphiphile or class of sugar amphiphiles can be any molecule having a hydrophilic sugar portion and a hydrophobic portion, including but not limited to those described by Fenimore, “Interfacial Self-assembly of Sugar-based Amphiphiles: Solid- and Liquid-core Capsules,” University of Cincinnati Ph.D. thesis dated October 16, 2009; and Jadhav et al., “Sugar-derived Phase-selective Molecular Gelators as Model Solidifiers for Oil Spills,” Angewandte Chemie International, Vol. 49, 2010, pp. 7695-7698. Chemie International Edition, Vol. 49, pp. 7695-7698, 2010); Jung et al., “Self-assembling Structures of Long-chain Sugar-based Amphiphiles Influenced by the Introduction of Double Bonds”, Chemistry-A European Journal, Vol. 11, pp. 5538-5544, 2005; Paleta et al., “New amphiphilic fluoroalkylated derivatives of xylitol, D-glucose and D-galactose for medical applications: blood compatibility and emulsification properties”, Carbohydrate Research, Vol. 337, pp. 2411-2418, 2002. =Amphiphilic Fluoroalkylated Derivatives of Xylitol, D-glucose and D-galactose for Medical Applications: Hemocompatibility and Co-emulsifying Properties”, Carbohydrate Research, Vol. 337, pp. 2411-2418, 2002); Germaneau, “Amphiphilic Sugar Metal Carbenes: From Fischer Type to N-Heterocyclic Carbenes (NHCs)”, a doctoral dissertation published by Germaneau at Rheinische Friederich-Wilhems University Bonn in 2007. and Ye et al., “Synthesis of Sugar-containing Amphiphiles for Liquid and Supercritical Carbon Dioxide”, Industrial & Engineering Chemistry Research, Vol. 39, pp. 4564-4566, 2000. Sugar amphiphiles may also include, but are not limited to, sophorolipids, as described in Zhang et al., “Synthesis and Interfacial Properties of Sophorolipid Derivatives”, Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 240, pp. 75-82, 2004; or rhamnolipids, as described in Christova et al., “Rhamnolipid Biosurfactants Produced by Renibacterium salmoninarum 27BN During Growth on Hexadecane”, Nature Research, Part C: Biochemistry, Biophysics, Biology, Microbiology, Vol. 59, pp. 70-74, 2004. by Renibacterium salmoninarum27BN During Growth on n-Hexadecane", Zeitschrift für Naturforshung Teil C Biochemie Biophysik Biologie Virologie, Vol. 59, pp. 70-74, 2004).

In one embodiment, the compatibilizer comprises an amphiphilic compound that promotes the formation of non-sugar graphene. An amphiphilic compound that promotes graphene formation can be any molecule having a hydrophilic portion that promotes graphene formation and a hydrophobic portion, including but not limited to cetyltrimethylammonium bromide (CTAB) or those sold by Dow Chemical Company of Midland, Michigan under the TRITON ^™ or TERGITOL ^™ trademarks, including but not limited to the TRITON X series of octylphenol ethoxylates and the TERGITOL NP series of nonylphenol ethoxylates. In some embodiments, the amphiphilic compound that promotes graphene formation is a nonionic amphiphilic compound. Amphiphilic compounds that promote graphene formation can also include but are not limited to glyceryl monostearate and non-oxygenated phenol surfactants.

In one embodiment, the compatibilizer comprises polyethylene glycol.

In one embodiment, the compatibilizer is used in combination with a particulate additive. In one embodiment, the compatibilizer promotes dissolution of the particulate additive in the base lubricant.

In one embodiment, the additive includes a metal oxide, which may include but is not limited to iron oxide, aluminum oxide, copper oxide, nickel oxide, titanium oxide, and lead oxide.

In one embodiment, the additive includes a form of iron. In some lubrication systems (such as in many jet engine turbines), little or no iron is inherently present. However, it is believed that the in situ formed carbon-encapsulated iron particles provide the nanopolishing capabilities of the lubricant composition of the present invention. Therefore, in one embodiment, the lubricating fluid is supplemented with an iron-containing additive.

In one embodiment, the iron-containing additive comprises an iron oxide. In one embodiment, the iron oxide is an iron oxide powder pigment from Lanxess, Cologne, Germany. In one embodiment, the iron-containing additive comprises an iron oxide nanopowder. In one embodiment, the iron source comprises a complex molecule.

In one embodiment, the additive comprises a cyclic iron compound, the cyclic iron compound including but not limited to (η ² -trans-cyclooctene) ₂ Fe(CO) ₃ ; (benzylideneacetone) tricarbonyl iron; enterocin iron; tricarboxybis[(1,2-h)-cyclooctene]-iron; iron (4+) bicyclooctane-1,2-ide-carbon monoxide; sodium ferrate (1-); sodium-bis(3-(4,5-dihydro-4-((2-hydroxy-5-nitrophenyl)azo)-3-methyl-5-oxo-1H-pyrazol-1-yl)benzene-1-benzenesulfonamide (2-)) ferrate (1-); ferritin; (cyclo-1,3-C ₄ H ₈ -S ₂ )FeCO) ₄ ; iron phthalocyanine; ferrocene; iron benzoate; iron salicylate; cyclic ferrate; or iron protein succinate.

In one embodiment, the additive comprises an acyclic iron-containing compound, including but not limited to nonacarbonyl iron, pentacarbonyl iron, acyclic ferrate, molten iron, iron oxalate, hydrated iron oxide (Fe(OH) ₃ ), or an iron-containing nutritional supplement. In one embodiment, the iron-containing complex is a catechol-iron complex.

In one embodiment, the additive includes a siderophore, which may include but is not limited to 2,3-dihydroxybenzoic acid (2-3'-DHB), N,N',N"-((3S,7S,11S)-2,6,10-trioxo-1,5,9-trioxacyclododecane-3,7,11-triyl)tris(2,3-dihydroxybenzamide) (enterostatin), or 2,4-dihydroxybenzoic acid (2-4'-DHB).

In one embodiment, the additive includes an insect repellent, including but not limited to 2-deoxy-paraherquamide (PHQ).

In one embodiment, the additive comprises an aromatic amino acid precursor, including but not limited to (3R,4R)-3-[(1-carboxyvinyl)oxy]-4-hydroxycyclohexyl-1,5-diene-1-carboxylic acid (chorismic acid).

In one embodiment, the additive comprises a molecule capable of chelating iron, which may include, but is not limited to, ethylenediaminetetraacetic acid (EDTA), 2-aminophenol (see Pulgarin et al., “Iron Oxide-mediated Degradation, Photodegradation, and Biodegradation of Aminophenols”, Langmuir, Vol. 11, pp. 519-526, 1995) and Andreozzi et al., “Iron(III) (hydr) oxide-mediated photo-oxidation of 2-aminophenol in aqueous solution: a kinetic study”, Water Research, Vol. 37, pp. 3682-3688, 2003). study", Water Research, Vol. 37, pp. 3682-3688, 2003), or tetraphenyloxy-metalloporphyrin.

In one embodiment, the additive comprises nanodiamonds, which act as

Forming nuclei of graphitic carbon-bound nanoparticles or microparticles formed in situ in the lubricant composition.

The ex-situ pyrolysis synthesis of the surface graphitized abrasive nanoparticles (SGANs) and agglomerates containing surface graphitized abrasive nanoparticles (SGANs) also allows the use of such molecules in non-lubricating applications. In one embodiment, the particles or agglomerates can be applied as a coating to the surface of a material to enhance the material or improve the thermal shielding or heat absorption of the material. In one embodiment, the coating can be a thermal coating, a drill bit coating, or a fire retardant coating. In one embodiment, the material can be a ballistic projectile, which can include but is not limited to bullets and missiles. In one embodiment, the material can be a bulletproof device, including but not limited to military tank armor or personal armor, including bulletproof vests or bulletproof vest plates. In one embodiment, the material can be a tool, including but not limited to a cutter head, a tunneling device, a nanopolisher, an abrasive paper, or a boring device. In one embodiment, the material can be a thermal shield, such as a reentry heat shield, a drill, or a rocket engine nose cone for a spacecraft. In one embodiment, the particles or agglomerates can be combined with a material to form a composite material having a higher strength, heat shielding or heat absorption than the base material itself. In some embodiments, the material can be a tire, fire protection equipment, firefighting equipment or firefighting clothing.

In one embodiment, the surface graphitized abrasive nanoparticles (SGANs) and agglomerates containing surface graphitized abrasive nanoparticles (SGANs) of the present invention can be used in electrochemical systems. In one embodiment, the surface graphitized abrasive nanoparticles (SGANs) and agglomerates containing surface graphitized abrasive nanoparticles (SGANs) of the present invention can be used as nanobatteries to store electrical charge.

Test results

Several lubricant compositions, including a sacrificial carbon source that is expected to promote graphitic carbon formation under engine operating conditions, were tested on a series of motorcycles or motocross vehicles. These tests were conducted to test the efficacy of the lubricant compositions in small internal combustion engines, engines of a size and configuration such that the improvement in friction reduction would be noticeable enough to a mechanic or operator without the use of an external dynamometer to measure the change.

Test 7

A conventional 10W-40 engine oil from Ashland Inc. of Lexington, Kentucky, USA, was replaced with the lubricant composition of the present invention in a 1999 Honda Elite 80 (Model CH80) motorcycle manufactured by Honda de Mexico, S.A. de C.V. of Guadalajara, Jalisco–Mexico, with 8,850 miles. Prior to the addition of the lubricant composition, the motorcycle's engine could barely maintain idle speed. When tested, the motorcycle would start but would quickly stall. While the motorcycle was operating, the instrument panel indicated a top speed of approximately 30 mph.

The lubricant composition tested included a mixture of several hundred milliliters of "Organic Powdered Sugar" (ingredients: powdered cane sugar and tapioca) from Whole Foods Market, Austin, Texas, USA, and "Walgreens Intestinal Lubricant" (USP mineral oil) from Walgreen Company, Deerfield, Illinois, USA, and 5100 10W-40 semi-synthetic motor oil from Motul, Aubervilliers, France. The lubricant composition had an opaque appearance due to the large amount of sugar suspended in the liquid.

Upon adding the lubricant composition to the motorcycle, the engine was started and was able to maintain idle speed at that time. The motorcycle was then subjected to a performance evaluation test ride. The lubricant composition was found to almost immediately increase the motorcycle's top instrument speed from 30 mph to 35 mph. A noticeable difference in the engine's sound was also noted, with the lubricant composition making the engine sound much smoother and quieter than before. After the test ride, the lubricant composition was drained from the engine, at which point a typical epoxy-like odor was noted in the oil. This typical epoxy-like odor was expected and is believed to indicate the presence of epoxy precursor compounds in the oil, which are formed due to incomplete thermal decomposition of some residual sugar molecules in the lubricant composition.

Test 8

Another lubricant composition tested on the same 1999 Honda Elite 80 (Model CH80) motorcycle manufactured by Honda de Mexico, S.A. de C.V. of Guadalajara, Jalisco–Mexico, consisted of a single-serving packet (one gram) of Sweet'n Zero Calorie Sweetener (ingredients: dextrose, saccharin, potassium bitartrate, calcium silicate) from Cumberland Packing Corporation of Brooklyn, New York, USA, combined with a few milliliters of a natural cleaning and degreaser from Danbury, Connecticut, USA, and 10W-40 conventional motor oil from Ashland Inc. of Lexington, Kentucky, USA.

The motorcycle operated similarly to the aforementioned sugar-containing lubricant composition when using the saccharin-containing lubricant composition. After the test, when the saccharin-containing lubricant composition was drained from the motorcycle, very few visible particulates were observed. Aside from a strong citrus odor from the biphenyl-containing natural cleaning and degreasing agent, the drained oil was otherwise unremarkable.

Test 9

Yet another lubricant composition tested on the same 1999 Honda Elite 80 (Model CH80) motorcycle manufactured by Honda de Mexico, S.A. de C.V. of Guadalajara, Jalisco–Mexico, included an additive consisting of "organic powdered sugar" (ingredients: powdered cane sugar and cassava) mixed with an activated charcoal additive from Whole Foods Market of Austin, Texas, and 10W-40 conventional motor oil from Ashland Inc. of Lexington, Kentucky, USA.

According to the oil's Material Safety Data Sheet, the oil has a reported flash point of 240°C (399.2°F) and a reported boiling point of 299°C (570.2°F). The normal operating temperature of the cylinder head of the air-cooled engine was measured to be ~80°C (176°F).

During the test, the engine's cowling was modified to completely block all airflow from the cooling fan to the cylinder head. This meant that as the engine ran, air around the cylinder head became trapped and began to heat up. A Cen-Tech non-contact infrared thermometer with laser positioning, manufactured by Zhangzhou Dongfang Intelligent Instrument Co., Ltd. in Zhangzhou, Fujian, China, was used to monitor the cylinder head's temperature rise.

The engine was operated under these conditions until the cylinder head temperature reached approximately 255°C (437°F). Upon reaching this temperature, heavy smoke was observed billowing from the crankcase breather valve, and the plastic cowling surrounding the engine was seen to begin melting. At this condition and temperature, the engine was operated at wide-open throttle and continued to run without binding. Shortly thereafter, the engine was shut off and allowed to cool. The motorcycle was subsequently test-ridden for several miles, during which time the motorcycle was observed to operate perfectly smoothly, with no performance degradation noted.

Test 10

In another lubricant composition, 200 mL of almond oil (a source of amygdalin) from Whole Foods Market, Austin, Texas, was combined with 550 mL of 10W-40 conventional motor oil from Ashland Inc., Lexington, Kentucky, U.S. This lubricant composition was placed on a 2011 JMStar 150cc GY-6 motorcycle manufactured by Shanghai JMStar Motorcycle Co., Ltd., Shanghai, China, with 125 miles on it.

Although no improvement in the instrument-indicated top speed of the motorcycle was observed during the evaluation test ride, the sound of the engine when using the lubricant composition was better in quality than when using the conventional engine oil alone.

Test 11

In another lubricant composition, a few ounces of Roddenberry's Cane Patch Invert Sugar Cane Syrup from Bay Valley Foods, LLC, Green Bay, Wisconsin, and ~100 mL of Mystery Oil (a naphthenic carbon source) from Turtle Wax, Inc., Westmont, Illinois, were combined with 10W-40 conventional motor oil from Ashland Inc., Lexington, Kentucky. This lubricant composition was placed in a motorcycle owned by Baja Motorcycles, Inc., Phoenix, Arizona. Sports) produced the DirtRunner 125cc motocross bike.

Prior to the test, the motocross vehicle operated normally, but not particularly well. Once the lubricant composition was added to the engine, the engine sounded and ran more smoothly than when using the conventional lubricant. At the end of the performance evaluation test ride, the oil was drained from the motocross vehicle's engine, and the expected and typical epoxy-like odor was again noted, indicating the presence of phenolic resin/epoxy precursors in the lubricant.

Test 12

In another lubricant composition, approximately 50 mL of USP-grade benzyl benzoate from Spectrum Chemical Manufacturing Corporation of New Brunswick, New Jersey, was mixed with approximately 50 mL of 5W-30 Ultimate Biodegradable Green Motor Oil, a traditional tallow-based motor oil, from Green Earth Technologies of Celebration, Florida. Approximately 100 mL of this lubricant composition was then added to the existing engine oil of a 2011 JMStar 150cc GY-6 motorcycle manufactured by Shanghai JMStar Motorcycle Co., Ltd., China, which had logged 125 miles. This lubricant composition appeared to be the best performing lubricant composition tested.

A significant improvement in engine noise was observed after addition of the lubricant composition, and it was noted that the maximum revolutions per minute (RPM) of the engine had increased from approximately 10,000 RPM to 11,000 RPM, an increase of 1,000 RPM.

Test 13

In another lubricant composition, approximately 20 drops of Aura Organic Cinnamon Leaf Oil (a source of methyl cinnamate) from Frontier Natural Products Co-op of Celebration, Iowa, and approximately -100 mL of Walgreens Intestinal Lubricant (USP mineral oil) from Walgreen Company of Deerfield, Illinois, were combined with approximately -200 mL of 5W-30 Ultimate Biodegradable green motor oil from Green Earth Technologies of Celebration, Florida. The lubricant composition was placed in a Dirt Runner 125cc motocross vehicle manufactured by Baja MotorSports, Inc. of Phoenix, Arizona, U.S.A. The performance of the lubricant composition was similar to that of the previous lubricant composition (including benzyl benzoate), but a pungent cinnamon odor was noted during operation.

Test 14

In another lubricant composition, approximately 100 mL of a mixture of USP-grade benzyl benzoate from Spectrum Chemical Manufacturing Corporation of New Brunswick, New Jersey, Walgreens Intestinal Lubricant (USP-grade mineral oil) from Walgreen Company of Deerfield, Illinois, and Lucas Automatic Transmission Fluid Conditioner from Lucas Oil Products, Inc. of Corona, California, was added to a 2-mile-mile motorcycle produced by Taizhou Zhongneng Motorcycle Co., Ltd. of Taizhou, China. A new 2011 50cc GMW-M2 motorcycle with a modified transmission and exhaust system was tested. The engine's horsepower was observed to increase almost immediately, and the motorcycle's top speed increased from 33 mph to 39 mph, representing an 18% increase in top speed.

Test 15

In another lubricant composition, a lubricant comprising 3 quarts of a premium synthetic motorcycle oil containing zinc dialkyl dithiophosphate (ZDDP) was mixed with Mystery Oil (original formulation) from Turtle Wax, Inc. of Westmont, Illinois, USA, Lucas Synthetic Oil Stabilizer from Lucas Oil Products, Inc. of Corona, California, USA, Lucas Automatic Transmission Fluid Conditioner from Lucas Oil Products, Inc. of Corona, California, USA, and Oil-Chem Research, Inc. of Bedford Park, Illinois, USA. A formulation comprising approximately one quarter of a mixture of lubricants from Yamaha Corporation (formerly known as Yamaha Motor Corporation) in a volume ratio of approximately 60:17:70:30 was used to replace the existing oil in the engine of a 1999 1,000 cc Yamaha R1 test motorcycle manufactured by Yamaha Motor Co., Ltd. of Iwata, Japan. Engine performance testing using this formulation was conducted by measuring rear wheel power and torque output of the test motorcycle using a Dynojet 250i dynamometer from Dynojet Research Inc. of Las Vegas, Nevada, USA, 10 minutes after the oil change and one week after the oil change. The test configurations for these two tests conducted by the dynamometer are shown in Tables 2(a) and 2(b) below:

Table 2(a): Power meter test results - maximum output

Output power initial 10 minutes 1 week Maximum power (HP) 135.14 136.08 138.49 Maximum torque (ft/lb) (ft/lb) 73.06 74.04 75.31

Table 2(b): Power meter test results - maximum measured increase

As shown in Table 2(a), an increase in power of approximately 1 HP and an increase in torque of approximately 1 foot/pound (ft/lb) were observed in the 10-minute test compared to the use of another commercially available premium motorcycle oil on the motorcycle. The effect of the new lubricant composition was even more dramatic after seven days of use. When tested one week later, additional increases of 3% to 4% in both power and torque were observed over the 10-minute test values. Specifically, the recorded power increased by approximately 3 to 5 HP across the entire engine speed range tested (from 4,500 RPM to approximately 7,500 RPM). As shown in Table 2(b), the power output measured at 7,500 RPM during the 10-minute test was 102.96 HP, while the power output measured at 7,500 RPM during the one-week test was 107.90 HP. From the test after 10 minutes to the test after 1 week, the maximum torque increased from approximately 74.04 feet per pound (ft/lb) to approximately 75.31 feet per pound (ft/lb).

Test 16

In another lubricant composition, Mystery Oil (original formulation) from Turtle Wax, Inc. of Westmont, Illinois, USA, Lucas Synthetic Oil Stabilizer from Lucas Oil Products, Inc. of Corona, California, USA, Lucas Automatic Transmission Fluid Conditioner from Lucas Oil Products, Inc. of Corona, California, USA, and Oil-Chem Research Inc. of Bedford Park, Illinois, USA, were used. A mixture of approximately three to four ounces of lubricants from Audi Corporation, mixed in a volume ratio of approximately 12:3:14:9 and added to the existing engine lubricant in a 2006 Audi 4 2.0L Turbo test vehicle manufactured by Audi AG of Ingolstadt, Germany, produced significant performance and fuel economy benefits. This additive package and similar concentrated formulations can be added directly to a vehicle's existing motor oil to improve engine performance without replacing the existing oil.

Test 17

In yet another lubricant composition, a concentrated additive package that is not intended to affect the performance of any existing base lubricant or its additives is prepared by mixing Mystery Oil (original formulation) from Turtle Wax, Inc. of Westmont, Illinois, U.S.A., Lucas Synthetic Oil Stabilizer from Lucas Oil Products, Inc. of Corona, California, U.S.A., Lucas Automatic Transmission Fluid Conditioner from Lucas Oil Products, Inc. of Corona, California, U.S.A., and AirTool Oil from Turtle Wax, Inc. of Westmont, Illinois, U.S.A. Oil) in a volume ratio of approximately 12:3:14:16.

The concentrated additive package was added to a high-quality synthetic motor oil that does not contain zinc dialkyldithiophosphate (ZDDP) and then introduced into the engine of a 2006 Audi 4 2.0L Turbo test vehicle manufactured by Audi AG of Ingolstadt, Germany, producing significant performance and fuel economy benefits. This additive package and similar concentrated formulations can be added directly to a vehicle's existing motor oil to improve engine performance without replacing the existing oil.

Experimental Observation of Lubricant Compositions in Tests 16 and 17

Subsequently, metal engine components from the Audi 4 test vehicle from Audi AG of Ingolstadt, Germany, were disassembled and subjected to various nondestructive analyses. In this case, a machined steel camshaft cam follower and a cam follower retaining ring were removed from the test vehicle after 150,000 miles of use with the lubricant composition's various formulations. According to the manufacturer, these components were made of stainless steel. The results of these analyses are shown below.

The first scientific analysis performed on the engine components was a surface roughness analysis using a NewView ^™ 7300 white light optical surface characterization interferometer manufactured by Radiall Corporation of Middlefield, Connecticut. The interferometer was used to evaluate and compare the friction and non-friction surfaces of the disassembled cam followers. The arithmetic mean ( _Ra ), peak-to-valley (PV), and root mean square (RMS) surface roughness were determined. The results and inferences are shown in Figures 20 and 21 and Table 3.

Table 3: Optical surface characteristics test results

As shown in the table above, using the formulation of the present invention, an improvement in surface roughness of almost two orders of magnitude was achieved. The average surface roughness ( _Ra ) was reduced from a minimum initial value of at least _Ra = 221.6 nm to a final measured value of _Ra = 3.44 nm.

FIG20 shows that the _Ra value for the non-wearing surface, which did not repeatedly contact the cylinder wall during vehicle operation, was measured to be 221.6 nm. This value is typical for such an engine component in a high-quality vehicle (average automotive cam follower tolerance _Ra = 300 nm to 400 nm). The graph in the lower left quadrant of FIG20 shows what can be considered an estimate of the approximate initial surface roughness measurement of the evaluated cam follower portion; in other words, the graph can be considered an estimate of the relative condition of the evaluated cam follower portion when assembled in the engine of the test vehicle.

However, FIG21 shows that the _Ra value of the wear surface, which was in constant frictional contact with the cylinder wall during vehicle operation, was measured to be 3.44 nm, two orders of magnitude lower than the measured roughness of the friction surface, indicating the approximate and estimated initial state of the cam follower during engine manufacture and assembly. The orientation of the initial machined roughness observed in FIG20 is perpendicular to the roughness observed in FIG21, indicating that the initial machined roughness in the wear surface was completely removed at some point during the polishing process.

These data indicate that the cam follower has been superpolished during operation of the engine. While it is possible to superpolish surfaces of materials such as fused silica, silicon, and silicon carbide to a surface roughness value _Ra of 0.4 nm under highly controlled laboratory conditions, the _Ra values of polished metal surfaces are generally higher, in the range of hundreds of nanometers. Liu et al., "SIMTech Technical Reports", Vol. 8, No. 3, pp. 142-148, July-Sept 2007, report a two-step superpolishing process capable of producing (under laboratory conditions) stainless steel lens mold inserts with a surface roughness value _Ra of 8.5 nm.

Because two pieces of metal in contact cannot produce a surface as smooth as that shown in FIG. 21 without the use of a polishing agent, further testing was conducted on the worn surface of the cam follower in an attempt to identify polishing agents in the lubricant composition that could produce a surface as smooth as that achieved in the present invention's experiments. The worn surface of a cam follower is typically made of case-hardened steel and various nanoparticle polishing agents, one of which is referred to herein as surface graphitized abrasive nanoparticles (SGAN). To polish the surface, the surface graphitized abrasive nanoparticles are expected to be harder than the surface being polished. The two-dimensional surface topology of the worn surface in FIG. 21 shows numerous circular features with diameters in the range of one or two nanometers, which is on the expected size scale for the surface graphitized abrasive nanoparticles (SGAN) or other abrasive nanoparticles necessary to achieve such low surface roughness _Ra values.

The non-friction surface of a retaining ring of the cam follower was studied using an XL30 ESEM-FEG scanning electron microscope from FEI ^™ Company of Hillsboro, Oregon, USA, using Genesis ^™ version 4.61 software and a Scandium Imaging Platform from ^Inc. of Mahwah, New Jersey, USA. Electron microscope images of the surface of the retaining ring are shown in Figures 22 to 41. In addition to showing less than 1 At% of potassium and chromium, the accompanying element analysis of the four surfaces by energy dispersive X-ray spectroscopy (EDS) showed only the weight percentage (wt%) and atomic percentage (At%) of carbon, oxygen, and iron in the sample areas in the black boxes of Figures 22 to 25, as shown in "Table 4(a)". The images show spheroidal structures with diameters ranging from 2 to 3 microns on the non-friction surface.

Table 4(a): Preliminary elemental analysis data

Figures 26 to 37 show additional scanning electron microscope (SEM) images of the cam follower retaining ring surface. The length scale "Mm" in Figures 29 to 37 is actually micrometers. During the lubrication process, these larger structures break down into smaller nanostructures.

Since the sampled areas in Figures 22 to 25 showed varying carbon, oxygen, and iron ratios, multiple experiments were subsequently conducted to sample different areas of the same structure to determine whether the structure was uniform. Figures 38A-C, 39A-G, and 40A-C show that the areas within the black boxes are the structures of the sampled areas.

Table 4(b): Elemental analysis data of the first spheroid

Figures 38A, 38B, and 38C show three different sampling areas of a single large sphere with a diameter of ~2 microns. As shown in Table 4(b), only carbon, oxygen, and iron were detected. In Figure 38A, an average was taken over most of the surface, while in Figure 38B, a smaller portion of the surface was sampled, yielding similar results. Finally, as shown in Figure 38C, a small protrusion extending from the bottom of the sphere was sampled. This small protrusion contained almost ten times as much iron as the other two sampling areas.

Table 4(c): Crystal structure element analysis data

Figures 39A, 39B, 39C, 39D, 39E, 39F, and 39G show seven different sampled areas of a large, irregular crystalline structure exceeding 13 microns in width. As shown in Table 4(c), carbon, oxygen, calcium, and iron were detected in all samples, with the exception of Figure 39E, which lacked iron. Furthermore, chlorine was detected in each of these samples, in amounts that just made up the respective totals to 100%. The calcium-to-chlorine ratio ranged from 1:1 to 6:1. Within this range, calcium-to-chlorine ratios of approximately 1.5:1, approximately 2:1, and approximately 3:1 were also observed. With the exception of 12.69 At% in the sample area of Figure 39C, the amount of iron detected was minimal compared to the Figure 38 series.

Table 4(d): Elemental analysis data of the second spheroid

Figures 40A, 40B, and 40C show three different sampling areas of a relatively small, single spheroid with a diameter of approximately 1.3 microns. As shown in Table 4(d), only carbon, oxygen, and iron were detected. As shown in Figure 40A, the spheroid was sampled in the middle portion, and the results were similar to those in the middle portion of Figure 38A, although with higher iron content and lower oxygen content. As shown in Figure 40B, the spheroid was sampled at the upper right edge, and the iron content was five times higher than the area shown in Figure 40A, which is similar to what was observed in Figure 38C. Finally, as shown in Figure 40C, the spheroid was sampled at the left edge, and the iron content was almost twice that of the area shown in Figure 40A, but lower than the area shown in Figure 40B.

Finally, Figure 41 shows a large sample area of a large rhombohedral crystal structure with a width between 4 and 5 microns. As shown in Table 4(c), only carbon, oxygen, and iron were detected. Their ratios are similar to those of the low-iron region of the spheroid, except that the iron content is lower.

Hexane was then added to a sample of the used lubricant composition. The mixture was subjected to centrifugation, and a precipitate and a liquid portion of the centrifuged mixture were then subjected to time-of-flight (TOF) secondary ion mass spectrometry (SIMS) and transmission electron microscopy (TEM) using a FEI ^™ CM20TEM with Genesis ^™ software. While these tests did not identify any specific structure in the lubricant composition, interestingly, no detectable iron was detected in either the precipitate or liquid portion of the oil. Only carbon, oxygen, and in some cases, zinc, calcium, or chromium were detected in the samples. From these tests, it was clear that the features observed on the surface of the cam follower retaining ring by scanning electron microscopy (SEM), as evidenced by the lack of iron, were not present at detectable levels in the liquid.

A sample of the material on the surface of the cam follower was obtained and transmission electron microscopy (TEM) observations were performed by gently rubbing a TEM grid against the surface of the cam follower and then observing features on the grid using the TEM. Representative images of the observed features are shown in Figures 42 to 49B, which show a number of different morphological features and structures. The images confirm the presence of graphene or graphene oxide flakes, carbon nanotubes, carbon nanospheres, carbon nanoonions, and other fullerene structures and precursors. Based on elemental analysis, it is believed that the dark areas in the images represent higher concentrations of iron. Graphene is known to encapsulate iron particles—for example, see Cao et al., "Synthesis and Characterization of Graphene Encapsulated Iron Nanoparticles," Nanoscience, Vol. 12, No. 1, pp. 35-39, 2007. FIG. 42 shows a relatively flat sheet morphology in the lower portion of the image, and a more wrinkled sheet in the upper portion of the image. Smaller spherical structures with diameters ranging from ~5 nm to ~50 nm are also visible in the image. FIG. 43 generally shows a moderately wrinkled sheet morphology, with nanotube structures near the folds of the sheet.

FIG44 shows a higher magnification of an area with similar morphological features to FIG43. In FIG44, spheroid, tube, and flake morphological features are evident. FIG45 shows a higher magnification of some tortuous tube structures. FIG46 shows a higher magnification of a dark spherical mass with indistinct morphological features, which may be surface graphitized abrasive nanoparticles (SGAN) based on the dark interior of the dark spherical mass structure. FIG47 shows a large carbon nanotube structure. FIG48 shows two carbon nano-onion structures. Finally, FIG49A and 49B show a quasi-crystal mass with tube and spheroid morphological features but without obvious flake morphological features.

Therefore, it should be understood that the embodiments of the present invention set forth herein are merely illustrative of the application of the principles of the present invention. Reference herein to details of the illustrated embodiments is not intended to limit the claims, which themselves recite those features regarded as essential elements of the present invention.

Claims (31)

1. A method for synthesizing graphene, comprising: (a) Reflux a reaction mixture comprising at least one solvent and at least one carbonaceous material that promotes the formation of polycyclic aromatic hydrocarbons under conditions where complete combustion is inhibited, wherein the at least one solvent comprises water; (b) Then, the vapor generated by the reflux of the reaction mixture is collected; (c) The vapor is then directed to a substrate, whereby graphene is deposited on the surface of the substrate; and (d) Re-obtaining graphene from the surface of the matrix. 2. The method of claim 1, wherein the at least one carbonaceous material that promotes the formation of polycyclic aromatic hydrocarbons comprises pyranose, furanose, cyclic polycarboxylate, benzene derivative, sugar, sugar alcohol, sugar substitute, sugar derivative, cyclic polydimethylsiloxane, steroid, cinnamate, phenylpropane, carboxylate, benzo[a]pyran, natural or synthetic flavonoids or isoflavones, antioxidant, 4-vinylphenol, anthocyanin or benzo[a]pyran salt, cyclic amino acid, cyclohexane derivative, benzene derivative, 1,2- Dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, a phthalate, a succinate, an ester, a fluorophore, a pharmaceutical product, a commercial edible personal or sexual lubricant composition comprising a sugar or a sugar substitute amphiphilic compound, a commercial ultraviolet sunscreen formulation, a commercial skin cream formulation, a commercial hand sanitizer formulation, a commercial human or animal hair care product, a commercial hair dye formulation, a commercial insecticide, a compound that degrades into one or more of the above-mentioned carbonaceous materials during the reflux of the reaction mixture, or a combination thereof. The sugar substitutes mentioned include stevia, aspartic acid methyl ester, sucralose, acetylsupan potassium, saccharin, or sugar alcohols. The sugar derivatives mentioned above include sophoritol or glycosides. The cyclohexane derivatives mentioned above include 1,3-cyclohexadiene or 1,4-cyclohexadiene, and The benzene derivatives mentioned therein include polyphenols, benzaldehyde, benzotriazole, benzyl 1-naphthyl carbonate, benzene, ethylbenzene, toluene, styrene, benzyl nitrile, phenol, phthalic anhydride, phthalic acid, terephthalic acid, p-toluic acid, benzoic acid, aminobenzoic acid, benzyl chloride, isoindole, ethyl phthaloyl ethyl glycolate, N-phenylaniline, methoxybenzoquinone, benzyl acetone, benzyl acetone, hexyl cinnamaldehyde, 4-amino-2-hydroxytoluene, 3-aminophenol, or vanillin. 3. The method of claim 2, wherein the carboxylate comprises benzoate, salicylate and acrylate. 4. The method of claim 2, wherein the antioxidant is a cyclic antioxidant. 5. The method of claim 2, wherein the at least one carbonaceous material that promotes the formation of polycyclic aromatic hydrocarbons comprises a compound that promotes the formation of at least one _C1 to _C5 hydrocarbon group. 6. The method of claim 2, wherein the solvent further comprises mineral oil, an alcohol, or a combination thereof. 7. The method of claim 6, wherein the alcohol comprises methanol, ethanol or isopropanol. 8. The method of claim 7, wherein the methanol comprises synthetic methanol. 9. The method of claim 2, wherein the reaction mixture further comprises at least one supplementary carbon source. 10. The method of claim 9, wherein the supplementary carbon source comprises natural graphite, synthetic graphite, one or more polycyclic aromatic hydrocarbons, graphene, activated carbon, nano-coal, coal slurry, one or more benzene compounds, naphthalene, an alcohol, sugar, starch, cellulose, paraffin, acetate, alkane, olefin, acetylene, ketone, toluene, gasoline, diesel, kerosene, coal, coal tar, or combinations thereof. 11. The method of claim 10, wherein the alcohol comprises methanol, ethanol or isopropanol. 12. The method of claim 11, wherein the methanol comprises synthetic methanol. 13. The method of claim 10, wherein the activated carbon comprises biochar or sugar char. 14. The method of claim 10, wherein the sugar comprises sucrose. 15. The method of claim 10, wherein the coal comprises coking coal. 16. The method of claim 10, wherein the nano-coal comprises activated nano-coal. 17. The method of claim 1, wherein the matrix comprises a hydrophilic matrix. 18. The method of claim 1, wherein the conditions include pyrolysis. 19. The method of claim 1, wherein the reaction mixture further comprises a metal-containing compound. 20. The method of claim 19, wherein the metal-containing compound comprises a metal oxide. 21. The method of claim 20, wherein the metal oxide comprises iron oxide, aluminum oxide, copper oxide, nickel oxide, titanium oxide, or lead oxide. 22. The method of claim 1, wherein the reaction mixture further comprises nanodiamond. 23. The method of claim 1, wherein the substrate comprises a water tank, and wherein the graphene comprises hydrogel graphene. 24. The method of claim 2, wherein the ester comprises naphthate or phosphate. 25. A method for producing graphene oxide, comprising: (a) Reflux a reaction mixture comprising at least one solvent including water, at least one oxidant and at least one compound that promotes the formation of polycyclic aromatic hydrocarbons under conditions that prevent the carbon source from being completely burned into carbon dioxide or carbon monoxide. (b) Then, the vapor generated by the reflux of the reaction mixture is collected; (c) The vapor is then directed to a substrate, whereby graphene oxide is deposited on the surface of the substrate; and (d) Re-obtain graphene oxide from the surface of the substrate. 26. The method of claim 25, wherein the conditions include pyrolysis. 27. The method of claim 25, wherein the reaction mixture further comprises a metal-containing compound. 28. The method of claim 27, wherein the metal-containing compound comprises a metal oxide. 29. The method of claim 28, wherein the metal oxide comprises iron oxide, aluminum oxide, copper oxide, nickel oxide, titanium oxide, or lead oxide. 30. The method of claim 25, wherein the reaction mixture further comprises nanodiamond. 31. The method of claim 25, wherein the substrate comprises a water tank, and wherein the graphene oxide comprises hydrogel graphene oxide.