Chemical-free production of graphene-reinforced inorganic matrix composites
Provided is a simple, fast, scalable, and environmentally benign method of producing a graphene-reinforced inorganic matrix composite directly from a graphitic material, the method comprising: (a) mixing multiple particles of a graphitic material and multiple particles of an inorganic solid carrier material to form a mixture in an impacting chamber of an energy impacting apparatus; (b) operating the energy impacting apparatus with a frequency and an intensity for a length of time sufficient for peeling off graphene sheets from the graphitic material and transferring the graphene sheets to surfaces of solid inorganic carrier material particles to produce graphene coated or graphene-embedded inorganic particles inside the impacting chamber; and (c) forming graphene-coated or graphene-embedded inorganic particles into the graphene-reinforced inorganic matrix composite. Also provided is a mass of the graphene-coated or graphene-embedded inorganic particles produced by this method.
1. A method of producing a graphene-reinforced inorganic matrix composite directly from a graphitic material, said method comprising: a) mixing components consisting essentially of multiple particles of a graphitic material and multiple particles of a solid inorganic material to form a mixture in an impacting chamber of an energy impacting apparatus, wherein said graphitic material has never been intercalated, oxidized, or exfoliated and does not include previously produced isolated graphene sheets and wherein no impacting balls are present in said impacting chamber; b) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for transferring graphene sheets directly from said graphitic material to surfaces of said solid inorganic material particles, to produce graphene-coated inorganic particles inside said impacting chamber; and c) forming said graphene-coated inorganic particles into said graphene-reinforced inorganic matrix composite.
2. The method of claim 1 , wherein said solid inorganic material is selected from iron, copper, aluminum, lead, tin, zinc, indium, iridium, vanadium, manganese, nickel, zirconia, technetium, silver, silicon, cadmium, gold, platinum, niobium, molybdenum, chromium, manganese, cobalt, alumina, zirconia, titanium dioxide, boron nitride, soda lime glass, lead containing glass, aluminosilicate containing glass, tellurite-containing glass, antimony-containing glass, arsenate-containing glass, titanate-containing glass, tantalite-containing glass, borosilicate-based glasses, silica, high silica content glass, amorphous silicon dioxide, quartz, fused quartz, alumina, beryllia, ceria, carbide, boride, nitride, silicide, carborundum, diamond, an alloy thereof, or a combination thereof.
3. A mass of graphene-coated inorganic particles produced by the method of claim 2 , wherein a graphene proportion is from 0.01% to 80% by weight based on the total weight of graphene and inorganic particles combined.
4. The mass of graphene-coated inorganic particles of claim 3 , which is fed into an extruder, a molding machine, or a selective laser sintering apparatus to make a graphene-reinforced inorganic composite part.
5. The method of claim 1 , wherein said solid inorganic material is selected from zirconium barium titanate, strontium titanate (ST), calcium titanate (CT), magnesium titanate (MT), calcium magnesium titanate (CMT), zinc titanate (ZT), lanthanum titanate (TLT), and neodymium titanate (TNT), barium zirconate (BZ), calcium zirconate (CZ), lead magnesium niobate (PMN), lead zinc niobate (PZN), lithium niobate (LN), barium stannate (BS), calcium stannate (CS), magnesium aluminium silicate, magnesium silicate, barium tantalate, titanium dioxide, niobium oxide, zirconia, silica, sapphire, beryllium oxide, and zirconium tin titanate, indium tin oxide (ITO), lanthanum-doped strontium titanate (SLT), yttrium-doped strontium titanate (SYT) yttria-stabilized zirconia (YSZ), gadolinium-doped ceria (GDC), lanthanum strontium gallate magnesite (LSGM), beta alumina, lead zirconate titanate (PZT), barium titanate (BT), strontium titanate (ST), quartz, ferrites, strontium carbonate, lanthanum strontium manganite, and combinations thereof.
6. A mass of graphene-coated inorganic particles produced by the method of claim 5 , wherein a graphene proportion is from 0.01% to 80% by weight based on the total weight of graphene and inorganic particles combined.
7. The method of claim 1 , wherein said solid inorganic material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 10 nm to 10 mm.
8. The method of claim 7 , wherein said diameter or thickness is from 1 μm to 100 μm.
9. The method of claim 1 , wherein said solid inorganic material includes micron- or nanometer-scaled particles that can be melted above a melting temperature, and said method includes a step of melting said solid inorganic carrier material for forming said inorganic matrix composites.
10. The method of claim 1 wherein said graphitic material is selected from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, graphitic nano-fiber, graphite fluoride, chemically modified graphite, meso-carbon micro-bead, partially crystalline graphite, or a combination thereof.
11. The method of claim 1 , wherein the energy impacting apparatus is a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, micro ball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill or resonant acoustic mixer.
12. The method of claim 1 , wherein said step (c) includes melting said inorganic particles to form a melt mixture with graphene sheets dispersed therein, forming said melt mixture into a desired shape and solidifying said shape into said graphene-reinforced inorganic-matrix composite.
13. The method of claim 1 , wherein said step (c) includes melting said inorganic particles to form a melt mixture with graphene sheets dispersed therein and extruding said mixture into a rod form or sheet form, spinning said mixture into a fiber form, spraying said mixture into a powder form, or casting said mixture into an ingot form.
14. The method of claim 1 , wherein said step (c) includes sintering said graphene-coated inorganic particles into a desired shape of said graphene-reinforced inorganic matrix composite, wherein said sintering device may be a selective laser sintering apparatus.
15. The method of claim 1 wherein said graphene sheets contain graphene fluoride, graphene fluoride with less than 5% fluorine by weight, graphene with a carbon content no less than 95% by weight, or chemically modified graphene.
16. The method of claim 1 wherein said graphene sheets contain single-layer graphene sheets.
17. The method of claim 1 wherein said graphene sheets contain at least 80% single-layer graphene or at least 80% few-layer graphene having no greater than 10 graphene planes.
18. The method of claim 1 , wherein said procedure of operating said energy impacting apparatus is conducted in a continuous manner using a continuous energy impacting device.
19. The method of claim 1 wherein said impacting chamber further contains a functionalizing agent and said step (b) of operating said energy impacting apparatus act to chemically functionalize said graphene sheets with said functionalizing agent.
20. The method of claim 19 wherein said functionalizing agent contains a chemical functional group selected from alkyl or aryl silane, alkyl or aralkyl group, hydroxyl group, carboxyl group, amine group, sulfonate group (—SO 3 H), aldehydic group, quinoidal, fluorocarbon, or a combination thereof.
21. The method of claim 19 wherein said functionalizing agent contains an oxygenated group selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde.
22. The method of claim 19 wherein said functionalizing agent contains a functional group selected from the group consisting of SO 3 H, COOH, NH 2 , OH, R′CHOH, CHO, CN, COCl, halide, COSH, SH, COOR′, SR′, SiR′ 3 , Si(—OR′—) y R′ 3-y , Si(—O—SiR′ 2 —)OR′, R″, Li, AlR′ 2 , Hg—X, TlZ 2 and Mg—X; wherein y is an integer equal to or less than 3, R′ is hydrogen, alkyl, aryl, cycloalkyl, or aralkyl, cycloaryl, or poly(alkylether), R″ is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate, and combinations thereof.
23. The method of claim 19 wherein said functionalizing agent contains a functional group is selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylene-tetramine (TETA), tetraethylene-pentamine (TEPA), polyethylene polyamine, polyamine epoxy adduct, phenolic hardener, non-brominated curing agent, non-amine curatives, and combinations thereof.
24. The method of claim 19 wherein said functionalizing agent contains a functional group selected from OY, NHY, O—C—OY, P═C—NR′Y, O═C—SY, O═C—Y, —CR′1-OY, N′Y or C′Y, and Y is a functional group of a protein, a peptide, an amino acid, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of an enzyme substrate or is selected from R′—OH, R′—NR′ 2 , R′SH, R′CHO, R′CN, R′X, R′N + (R′) 3 X − , R′SiR′ 3 , R′Si(—OR′—) y R′ 3-y , R′Si(—O—SiR′ 2 —) OR′, R′—R″, R′—N—CO, (C 2 H 4 O—) w H, (—C 3 H 6 O—) w H, (—C 2 H 4 O) w —R′, (C 3 H 6 O) w —R′, R′, and w is an integer greater than one and less than 200.
25. The method of claim 19 , wherein said step of operating said energy impacting apparatus is conducted in a continuous manner using a continuous energy impacting device.
26. A method of producing a graphene-reinforced inorganic matrix composite directly from a graphitic material, said method comprising: a) mixing multiple particles of a graphitic material and multiple particles of a solid inorganic material to form a mixture in an impacting chamber of an energy impacting apparatus, wherein said graphitic material has never been intercalated, oxidized, or exfoliated and does not include previously produced isolated graphene sheets; b) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for transferring graphene sheets directly from said graphitic material to surfaces of said solid inorganic material particles, to produce graphene-coated inorganic particles inside said impacting chamber; and c) forming said graphene-coated inorganic particles into said graphene-reinforced inorganic matrix composite, wherein a plurality of impacting balls or media are added to the impacting chamber of said energy impacting apparatus and wherein the contents of said impacting chamber consists essentially of said particles of graphitic material, said particles of inorganic material, said impacting balls or media and an inert gas.
27. The method of claim 26 , wherein a magnet is used to separate the impacting balls or media from the graphene-coated inorganic particles prior to step (c) of forming said graphene-coated inorganic particles into said graphene-reinforced inorganic matrix composite.