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

• US 8,865,113 B2
• Filed: 03/15/2012
• Issued: 10/21/2014
• Est. Priority Date: 03/15/2011
• Status: Active Grant

• Current Assignee: Peerless Worldwide LLC
• Original Assignee: Peerless Worldwide LLC
• Inventors: Shankman, Richard S.
• Primary Examiner(s): Rump, Richard M
• Application Number:
  US13/583,507
• Publication Number:
  US 20140134092A1
• Time in Patent Office: 950 Days
• Field of Search: 423/415.1, 423/460, 423/445.B, 977/755, 252/378.R
• US Class Current: 423/460
• CPC Class Codes: A61K 2800/10 General cosmetic use
• CPC Class Codes: A61K 2800/28 Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
• CPC Class Codes: A61K 2800/413 Nanosized, i.e. having sizes below 100 nm
• CPC Class Codes: A61K 8/0241 Containing particulates characterized by their shape and/or structure see also A61K8/04, A61K8/11, and A61K8/14, further aspects are classified in A61K2800/40 and subcodes
• CPC Class Codes: A61K 8/19 containing inorganic ingredients
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: B01J 13/0056 containing inorganic material and water
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 32/184 Preparation
• CPC Class Codes: C01B 32/186 by chemical vapour deposition [CVD]
• CPC Class Codes: C01B 32/192 starting from graphitic oxides
• CPC Class Codes: C01B 32/205 Preparation
• CPC Class Codes: C01B 32/21 After-treatment
• CPC Class Codes: C01B 32/225 Expansion; Exfoliation
• CPC Class Codes: C01B 32/23 Oxidation
• CPC Class Codes: C10M 103/02 Carbon; Graphite
• CPC Class Codes: C10M 125/02 Carbon; Graphite
• CPC Class Codes: C10M 125/04 Metals; Alloys
• CPC Class Codes: C10M 129/70 : of monocarboxylic acids
• CPC Class Codes: C10M 171/06 : Particles of special shape or size
• CPC Class Codes: C10M 177/00 : Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• CPC Class Codes: C10M 2201/041 : Carbon; Graphite; Carbon black
• CPC Class Codes: C10M 2201/0413 : used as base material
• CPC Class Codes: C10N 2020/06 : Particles of special shape or size
• CPC Class Codes: C10N 2030/06 : Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• CPC Class Codes: C22C 33/00 : Making ferrous alloys
• CPC Class Codes: C22C 33/006 : compositions used for making ferrous alloys
• CPC Class Codes: C22C 38/00 : Ferrous alloys, e.g. steel alloys cast-iron alloys C22C37/00
• CPC Class Codes: F16D 2300/06 : Lubrication details not provided for in group F16D13/74
• CPC Class Codes: F16D 2300/10 : Surface characteristics; Details related to material surfaces
• CPC Class Codes: Y10S 977/734 : Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
• CPC Class Codes: Y10S 977/755 : Nanosheet or quantum barrier/well, i.e. layer structure having one dimension or thickness of 100 nm or less
• CPC Class Codes: Y10S 977/843 : Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/902 : Specified use of nanostructure

Abstract

Methods of ex situ synthesis of graphene, graphene oxide, reduced graphene oxide, other graphene derivative structures and nanoparticles useful as polishing agents are disclosed. Compositions and methods for polishing, hardening, protecting, adding longevity to, and lubricating moving and stationary parts in devices and systems, including, but not limited to, engines, turbos, turbines, tracks, races, wheels, bearings, gear systems, armor, heat shields, and other physical and mechanical systems employing machined interacting hard surfaces through the use of nano-polishing agents formed in situ from lubricating compositions and, in some cases, ex situ and their various uses are also disclosed.

Claims

1. A method of synthesizing graphene comprising:

a) refluxing a reaction mixture comprising at least one solvent and at least one carbonaceous material promoting polycyclic aromatic hydrocarbon formation under conditions that inhibit complete combustion of the carbonaceous material;

b) thereafter collecting vapors produced by the reflux of the reaction mixture;

c) directing the vapors to a substrate, whereupon graphene is deposited on the surface of the substrate; and

d) recovering graphene from the surface of the substrate.

2. The method of claim 1, wherein the at least one carbonaceous material promoting polycyclic aromatic hydrocarbon formation comprises pyranose, a furanose, a cyclic carbomer, a benzenoid, a sugar, a sugar alcohol, a sugar substitute, a sugar derivative, a cyclomethicone, a steroid, a cinnamate, a phenylphopanoid, a benzoate, a carboxylate, a benzopyran, a naturally-occurring or synthetic flavone or isoflavone, a salicylate, an antioxidant, a cyclic antioxidant, 4-vinylphenol, anthocyanidin, or chromenylium, a cyclic amino acid, a cyclohexane derivative, a benzene derivative 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone), a naphthoate, an acrylate, a phthalate, a succinate, a carpate, a fluorophore, a pharmaceutical, a phosphate, a commercial edible personal/sexual lubricating composition including a sugar or sugar-substitute amphiphile, a commercial ultraviolet ray 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 pesticide, a compound that degrades to one or more of the above-mentioned additives during refluxing of the reaction mixture, or combinations thereof.

3. The method of claim 2, wherein the at least one carbonaceous material promoting polycyclic aromatic hydrocarbon formation comprises a compound that promotes the formation of at least one C1 to C5 hydrocarbon radical.

4. The method of claim 2, wherein the solvent comprises mineral oil, water, an alcohol, methanol, synthetic methanol, ethanol, isopropanol or combinations thereof.

5. The method of claim 2, wherein the reaction mixture further comprises at least one supplemental carbon source.

6. The method of claim 5, wherein the supplemental carbon source comprises natural graphite, synthetic graphite, one or more polycyclic aromatic hydrocarbons, graphene, activated carbon, nano-coal, “

activated nano-coal”

, biochar, sugar char, coal phlegm, one or more benzenoids, naphthalene, an alcohol, methanol, synthetic methanol, ethanol, isopropanol, sugar, sucrose, a starch, cellulose, an olefin, an acetate, one or more non-graphitic hydrocarbons, an alkane, an alkene, an alkyne, a ketone, toluene, gasoline, diesel fuel, kerosene, coal, coal tar, coke, or combinations thereof.

7. The method of claim 1, wherein the substrate comprises a hydrophilic substrate.

8. The method of claim 1, wherein the conditions comprise pyrolysis.

9. The method of claim 1, wherein the reaction mixture further comprises a metal-containing compound.

10. The method of claim 9, wherein the metal-containing compound comprises a metal oxide.

11. The method of claim 10, wherein the metal oxide comprises iron oxide, aluminum oxide, copper oxide, nickel oxide, titanium oxide, or lead oxide.

12. The method of claim 1, wherein the reaction mixture further comprises nanodiamonds.

13. The method of claim 1, wherein the substrate comprises an aqueous pool, wherein the graphene comprises aqueous gelled graphene.

14. A method of graphene oxide production comprising:

a) refluxing a reaction mixture comprising at least one solvent, at least one oxidizer and at least one compound promoting polycyclic aromatic hydrocarbon formation under conditions to prevent the complete combustion of the carbon source into carbon dioxide or carbon monoxide;

b) thereafter collecting a vapor stream produced by the reflux of the reaction mixture;

c) thereafter directing the vapor stream to a substrate, whereupon graphene oxide is deposited on the surface of the substrate; and

d) recovering graphene oxide from the surface of the substrate.

15. The method of claim 14, wherein the conditions comprise pyrolysis.

16. The method of claim 14, wherein the reaction mixture further comprises a metal-containing compound.

17. The method of claim 16, wherein the metal-containing compound comprises a metal oxide.

18. The method of claim 17, wherein the metal oxide comprises iron oxide, aluminum oxide, copper oxide, nickel oxide, titanium oxide, or lead oxide.

19. The method of claim 14, wherein the reaction mixture further comprises nanodiamonds.

20. The method of claim 14, wherein the substrate comprises an aqueous pool, wherein the graphene oxide comprises aqueous gelled graphene oxide.