FACILE METHODS TO MANUFACTURE INTELLIGENT GRAPHENE NANOMATERIALS AND THE USE OF FOR SUPER-LIGHT MACHINE AND VEHICLES

Abstract

This utility invention is to replace some of the parts of current vehicles and robotic machines with intelligent graphene-based fibers and nanocomposites to achieve significantly weight-decreasing and energy-savings. This invention also is related to the formation of new generation vehicles, machine parts including robotics, which include but not limited to all kinds of cars, trailers, trucks, vehicles on roads and in the sky, ships on the ocean, and intelligent robotics for Human, as well as computer parts, bicycles, and sports supplies.

Claims

1. A method of producing graphene-based carbon fiber comprising the steps of: creating a mixture; heating the mixture to a temperature of between 20° to 400° C.; forming a plurality of porous carbon fiber sheets, a pore size of the pores being in a range of 1 nm to 8 μm; and annealing the plurality of porous carbon fiber sheets at a temperature of 400° C. to 2000° C. after the heating step.

2. The method of claim 1 further comprising the step of dispersing a quantity of at least one of a graphene powder, graphene flakes, graphene oxide powder, or graphene oxide flakes into a solvent solution with a surfactant to form the mixture.

3. The method of claim 2 wherein the solvent solution is one of water, an alcohol, acetone, ketone, dimethyl formamide (DMF), ethylene glycol (EG), or DMSO.

4. The method of claim 1 further comprising the step of adding at least one of a nanocellulose fiber, a polymer, and a resin into a solvent solution with a surfactant to form the mixture.

5. The method of claim 4 wherein the adding step comprises adding the polymer to the solvent solution with the surfactant, wherein the polymer is one of polyacrylonitrile (PAN), polystyrene, portion of asphalt, epoxy, polycarbonate, and any kind of cellulose, polyvinyl alcohol (PVA), polyurethane, polyvinyl chloride (PVC), polyethylene (PE), polyethylene glycol, nylon, polydimethylsiloxane, polyacrylamide, and poly(methyl methacrylate) (PMMA).

6. The method of claim 4 wherein the adding step comprises adding the resin to the solvent solution with the surfactant, wherein the resin is one of a polyvinyl resin, polyester resin, epoxy, polycarbonate resin, polyurethane resin, silicone resin, poly(methyl methacrylate) resin, and an epoxy siloxane resin.

7. The method of claim 1 wherein the mixture comprises a quantity of at least one of a graphene powder, graphene flakes, graphene oxide power, or graphene oxide flakes in a solvent solution with a surfactant, and at least one of a nanocellulose fiber, a polymer, and a resin.

8. The method of claim 1 further comprising the steps of: dispersing a quantity of at least one of a graphene powder, graphene flakes, graphene oxide powder, and graphene oxide flakes into a solvent solution with a surfactant, and adding at least one of a nanocellulose fiber, a polymer, and a resin into the solvent solution with the surfactant to form the mixture.

9. The method of claim 8 wherein the mixture comprises the quantity of at least one of the graphene powder, graphene flakes, graphene oxide powder, and graphene oxide flakes in the solvent solution with the surfactant and the at least one of the nanocellulose fiber, the polymer, and the resin.

10. The method of claim 8 further comprising a step of adding an additive to the solvent solution with the surfactant, the additive being at least one of nanoparticles or nanowires of metal, steel nano-powder, carbon nanotubes, and a metal oxide, and combinations thereof.

11. The method of claim 1 further comprising the step of stirring the mixture to obtain a uniform viscosity mixture.

12. The method of claim 11 wherein the step of heating the mixture comprises the step of heating the uniform viscosity mixture.

13. The method of claim 1 wherein the step of forming the plurality of carbon fiber sheets further comprises using a 3D printing machine.

14. The method of claim 13 wherein the 3D printing machine is computerized and configured to perform the step of forcing the mixture through a nozzle onto a substrate.

15. The method of claim 14 wherein the forcing of the mixture through the nozzle forms a graphene-based composite filament.

16. The method of claim 1 wherein the step of forming the plurality of porous carbon fiber sheets is carried out under a vacuum.

17. The method of claim 16 further comprising the steps of placing the sheets in a mold, injecting a quantity of second resin into the mold, and drawing the vacuum on the sheets and the second resin.

18. The method of claim 17 further comprising the steps of curing the second resin at approximately 20° C.-400° C. forming a cured composition, the curing step forming chemical bonds to enhance mechanical strength.

19. A method of forming a carbon fiber item using a plurality of carbon fiber sheets comprising the steps of: layering the plurality of carbon fiber sheets; applying a resin to the plurality of carbon fiber sheets; and curing the resin; and annealing the cured resin and the plurality of carbon fiber sheets in an inert gas at a temperature of 1,800° C.

20. The method of claim 19 further comprising the step of cutting the carbon fiber item to a desired shape.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The utility method shall be hereby described in detail in the description with reference to the attached drawings, in which:

[0015] FIG. 1 is a flowchart showing a method of manufacturing graphene-based carbon fibers and its sheets by a “cotton-candy machine” through spinning, according to the present invention; and

[0016] FIG. 2 is a flowchart showing a method of manufacturing graphene carbon fiber-based vehicle parts and articles for robotics and ships through molding.

[0017] FIG. 3 is a flowchart showing a method of manufacturing graphene-nanocomposite parts or articles by a commercialized additive manufacturing 3D printing machine according to the present invention:

[0018] FIG. 4 is a flowchart showing a method of manufacturing porous graphene nanocomposite sheets or plates;

[0019] FIG. 5 is a flowchart showing a method of manufacturing graphene-based nanocomposite parts or articles using porous graphene sheets through molding;

[0020] FIG. 6 provides a view of graphene fibers for use in machine parts;

[0021] FIG. 7 provides a view of graphene gel and a cured graphene machine part;

[0022] FIG. 8 provides an example of Graphene-based wagon and trolley model: decreasing conventional steel wagon 80% body weight, and printed by graphene filament: C %=82% in atomic percentage; and

[0023] FIG. 9 shows graphene-plastic foams that can be cut into shapes to form intelligent machine parts or articles that lightens the weight of vehicles.

DETAILED DESCRIPTION OF THE INVENTION

[0024] The aforementioned goals are achieved by the present invention using graphene-based carbon fibers, graphene-based porous nanocomposite plates, or graphene-based nanocomposite suspensions for solution printing through additive manufacturing 3D printing technology controlled by computer software, respectively. The following sections give our three approaches to demonstrate our innovative technology for graphene applications to machine and vehicles.

Approach I

Using Graphene-Based Carbon Fibers as Starting Materials

[0025] Graphene flake powder or graphene oxide powder is used as graphene material to start this process. Disperse the graphene powder into solvent with the assistant of surfactants, and add a small amount of nanocellulose fibers, polymers, or resins plus additives into the solution under stirring to obtain a uniform viscosity mixture for spinning.

[0026] Examples of solvents that may be used in the present invention as noted above and elsewhere herein include, but are not limited to: water, alcohols, acetone, ketones, dimethyl formamide (DMF), ethylene glycol (EG). DMSO, and their co-solvents, but prefer water and alcohols for the green chemical manufacturing.

[0027] Examples of polymers that may be used as noted above and elsewhere herein include, but are not limited to: high carbon contented polymers are preferred to be additives, but not limited. Polymers can be such as polyacrylonitrile (PAN), polystyrene, portion of asphalt, epoxy, polycarbonate, and any kinds of celluloses, polyvinyl alcohol (PVA), polyurethane, polyvinyl chloride (PVC), polyethylene (PE), and polyethylene glycol, nylon, polydimethylsiloxane, polyacrylamide, and poly(methyl methacrylate) (PMMA), and the like.

[0028] Examples of resins that may be used as noted above and elsewhere herein include, but are not limited to: polyvinyl resin, polyester resin, epoxy, polycarbonate resin, polyurethane resins, silicone resin, poly(methyl methacrylate) resin, and epoxy siloxane resins.

[0029] Graphene-based carbon fibers can be prepared using solution spinning though a solution spinning machine like a cotton candy machine. Then, the cotton-candy-made graphene carbon fibers are first treated in reduction/functional gas flow environment for annealing at temperature from 200 to 2000° C., preferring 1800° C. for about 4 hours by programming control. The flow gases could be, but are not limited to methane, benzene, alkanes, and hydrogen, ammonia, and so on. This process is to enhance the carbon fibers' mechanical properties and the surface treatment for functional groups to enhance the interface chemical functional groups formation. In some cases, polymer with functional groups that can form passivation layers on those graphene-based carbon fibers will be employed for the surface treatment.

[0030] Graphene fiber sheets can be obtained by placing the treated cotton-candy graphene fibers under vacuum. The graphene carbon fiber sheets can be also prepared from our previous invention in non-provisional U.S. patent application Ser. No. 15/441,972 filed on Feb. 24, 2017. This application Ser. No. 15/441,972 filed on Feb. 24, 2017 is incorporated herein by reference in its entirety and for any and all purposes as if fully set forth herein. Similarly. U.S. provisional application No. 62/322,084 filed on Apr. 13, 2016 is incorporated herein by reference in its entirety and for any and all purposes as if fully set forth herein.

[0031] To prepare the graphene-based carbon fibers parts or articles for vehicles and machines, the treated graphene carbon fiber sheets are cut into desired shape and placed in vacuum for molding as desired models. Based on the thickness needs, three to five or more sheets may be stacked together in the models. Then, under vacuum, a resin, such as those discussed above will be injected to wet the entire graphene carbon fiber sheets. The resin may then be cured at about 20 to 400° C., preferring 250° C., the graphene-based carbon fibers part or article is formed, and ready to be used for machines or vehicles. The article has a similar mechanical strength as steel has.

Approach II

Using Graphene Flakes or Graphene Oxide Flakes as Starting Materials

[0032] Graphene flake powder or graphene oxide powder is used as graphene material to start this process. Disperse the graphene powder into solvent, such as those discussed above, with the assistance of surfactants, and add a small amount of nanocellulose fibers, polymers, such as those discussed above, or resins, such as the ones noted above, plus additives into the solution under stirring to obtain the uniform viscosity mixture for solution printing. These materials may be similar or the same as the options noted above for Approach 1.

[0033] Next, inject the mixed solutions for additive manufacturing 3D printing and print it as inks through nozzles to form the designed parts or articles for robotics, vehicles, tram (e.g. side walls or hoods), and ship parts or electrical cars, airplane, or trains with railway or no track-railway advanced trains (e.g. non-railway track magnetic trains that is under developed in USA). In a particular embodiment, the graphene based carbon fiber material may be formed into a filament for use in a 3D printer. As such, intelligent articles can be constructed by 3D printing using graphene-based composite filament via 3D printers or using non-solvent graphene-epoxy composites for 3D printing using light curing.

[0034] Third, after printing, slightly heat the printed wet parts to about 20 to 400° C. (preferring 250° C.), the wet parts become hard due to the curing of the resin from the mixture in the graphene nanocomposites. The formation of 3D networks through chemical bonds after the curing significantly enhances the mechanical strength and other properties. The structures of this type of graphene-based nanocomposites are of three-dimensional chemically bonded networks inside the nanostructures, which makes the composites uniform in molecular level, and crosslinked tightly, mechanical strength that is competed with steel, which are essential to the parts of heavy duty vehicles that ensures its durable and lifespan.

[0035] Further, to achieve unexpected new properties, the mixture may further contain small amount of additives such as nanoparticles or nanowires of metal or non-metals, or steel nano-powder, and metal oxide. Examples may include but are not limited to carbon nanotubes, Mg, Al, steel alloy powder, ZrO.sub.2, Fe.sub.3O.sub.4, or MoS.sub.2, WS.sub.2, their combination would be used to mix with graphene flakes, proper polymer, and cellulose to form the mixed suspensions before 3D printing.

[0036] Examples of the small amount of additives to achieve unique properties of the graphene nanocomposite parts or articles for vehicles may include, but are not limited to: nanoparticles or nanowires of metal or steel nano-powder, and metal oxide, examples are not limited to carbon nanotubes, Mg, Al, steel alloy powder, ZrO.sub.2, Fe.sub.3O.sub.4, or MoS.sub.2, WS.sub.2, MgO, Al.sub.2O.sub.3, or their combination. These additives may, among other uses, be used to mix with graphene flakes, proper polymer, and nanocellulose to form the mixed suspensions before 3D printing.

Approach III

Using Graphene-Based Porous Nanocomposites as Starting Materials

[0037] Based on the processing temperature and additives, different mechanical properties of graphene-based carbon nanoporous composite sheets can be formed through the use of suspensions by adding additional foam-agents to the mixture of Approach II. The porous sheets can be prepared by directly pouring the pore-forming-agent-containing suspensions into a mold, leaving it or heating it from room temperature 20 to 400° C. to form porous sheets, preferring 250° C. The porous sheets are then annealed in inert or flow gases and special reduction gas flow in a temperature range of 400° C. to 2000° C., preferring 1800° C. The prepared graphene porous sheet has high surface area, extremely high tensile and Young's modulus. Pore sizes are in the range of 1 nm to 8 μm.

[0038] Examples of the foam/pore forming agent may include but are not limited to any substances generally releasing a gas. These may be an organic polymeric material or an organic small-molecule material having a decomposition temperature lower than 2000° C. or inorganic small molecules; these can include, but are not limited to: colophony, helium, ammonium carbonate, carbon dioxide, tetramethyl ammonium acetate, hydrogen, nitrogen, sodium bicarbonate, ammonium acetate, peroxide, ammonium nitrate, basic cupric carbonate, and the like.

[0039] To prepare the graphene-based carbon nanocomposite parts or articles for vehicles and machines, the treated graphene porous carbon sheets are cut into desired shape and placed in vacuum for molding as desired. Based on the thickness needs, three to five or more sheets may be stacked together in the mold. Then, under vacuum, resin, such as those noted above, will be injected to wet the entire graphene carbon fiber sheets. After the resin is cured at room temperature to about 400° C. (preferring 250° C.), the graphene-based carbon fibers part or article is formed, and ready to be used for machines or vehicles. The articles have compete mechanical strength as steel has, light weight as carbon fibers, much lighter than alloy of Al—Mg, and have a variety of unique properties. It has excellent mechanical properties such as strength, and adjustable properties for thermal and electrical conductivities, shielding radiations, and electromagnetic waves, anti-corrosion, and more unique properties.

[0040] In summary, our invention leads to large a number of graphene-based nanocomposite parts or articles formed for machines, robotics, airplanes, ships, and vehicles (cars, trucks, trailers, vans etc.) plus tram and trains, which have compete mechanical strength as steel, light weight as carbon fibers, much lighter than alloy of Al—Mg, and have a variety of unique properties. It has excellent mechanical properties such as strength, and adjustable properties for thermal and electrical conductivities, shielding radiations, and electromagnetic waves, anti-corrosion, and more.

[0041] Referring now to FIG. 1 showing the operational flowchart of the method of manufacturing graphene into carbon fiber according to the present invention. As shown in FIG. 1, the method of the present invention generally comprises the steps of obtaining graphene flakes or graphene oxide S10, forming the fibers via cotton-candy machine or similar setup for spinning S20, and applying a heat treatment between 200° C. to 2000° C., preferring 1800° C. S30. By altering the heat treatment applied, the qualities of the resulting carbon fiber can be manipulated and enhanced; finally graphene-based carbon fiber sheet is prepared by placing the as-prepared graphene carbon fibers in vacuum molds S40.

[0042] FIG. 2 shows the operational flowchart of the method of manufacturing graphene carbon fiber sheets to form vehicle parts or articles according to the present invention. As shown in FIG. 2, the method of the present invention generally comprises the steps of obtaining graphene carbon fiber sheet in a mold S10, forming the fiber sheet stacks via over-layering them S20, forming the parts or articles by applying vacuum in the mold, injecting resin to cure at 20 to 400° C. preferring 250° C. S30, and applying the parts or articles to the desired vehicles S40. In a preferred embodiment and curing of the present invention the heating process heats the fibers up to 400° C., preferring 250° C. in air S30.

[0043] FIG. 3 shows the operational flowchart of the method of manufacturing graphene-based nanocomposite parts or articles through additive manufacturing 3D printing according to the present invention. As shown in FIG. 3, the method of the present invention generally comprises the steps of obtaining graphene flakes or graphene oxide S10, forming the uniform suspension in solvent with small amount resin and other additives S20, applying adaptive 3D printing technology S30 via an Adaptive 3D Printer with digital control through a computer, applying a further heat treatment between 20 to 400° C., preferring 250° C. for curing S40, and applying a further heat treatment heated to 400 to 2000° C., preferring 1800° C. in inert/flow gas environment S50 which results in a further refined and crosslinking formation inside the nanocomposites.

[0044] FIG. 4 shows the operational flowchart of the method of manufacturing porous graphene nanocomposite sheets or plates according to the present invention. The method of the present invention generally comprises the steps of obtaining graphene flakes or graphite oxide S10, forming a mixture with additives, polymers and pore-forming agents S20, pouring the suspension into a mold, and applying a heat treatment 400° C. first, then to 2000° C. preferring 1800° C. in a reduction gas flow environment S30. Graphene-based porous carbon nanocomposites sheet is prepared, which has high surface area, extremely high tensile and Young's modulus. Pore sizes are in the range of 1 nm to 8 μm.

[0045] As shown in FIG. 5, the method of the present invention generally comprises the steps of applying a porous graphene carbon plate or sheet in a mold S10, forming the plate or sheet stacks via over-layer them S20, forming the parts or articles by applying vacuum in the mold, injecting resin to cure at 20° C. to 400° C. preferring 250° C. S30, and applying the parts or articles to the desired vehicles S40. In a preferred embodiment and curing of the present invention the heating process heats the fibers up to 400° C., preferring 250° C. in air S30.

[0046] FIG. 6 provides the graphene composite compound pellets and the corresponding graphene-based carbon fibers that can be used to form some intelligent machine parts as it did using PAN conventional carbon fibers. The processing of those fibers have low cost manufacturing compared to PAN carbon fibers. Only intelligent articles from this invention will be selected with its mechanical strength matching aluminum/magnesium (Al—Mg) alloys and some of the parts as the same as steels.

[0047] FIG. 7 shows the graphene gel that is formed by mixing graphene powder with epoxy. Then at low heating conditions, it is cured by heating and form a machine article with 3D molding. Similar designed articles and processing can be used for intelligent machine or vehicle parts, or liquid transportation pipes such as working in chemical plants and in the ocean to avoid corrosion. Graphene-based composites are excellent for having anti-corrosion properties while maintaining an excellent mechanical properties.

[0048] FIG. 8 shows a 3D printed trolley or wagon models. The 3D printing materials is a graphene-based ABS composite filament. This model has body size of 10 cm×4 cm×2 cm, and thickness of printing is 1 mm, but only weighs 0.5 gram. The same volume size of steel have weight about 30 grams, decreasing 80% of the conventional steel wagon weight.

[0049] FIG. 9 shows embodiments of components that are produced from this invention through the foaming agent added into graphene gel. Those graphene foams can be cut into a satisfactory shape, and, using epoxy, to make the machine articles formed after cured either by UV light or by heating.