WO2014168979A1 - Utilisation de composites de polymère contenant du graphène - Google Patents

Utilisation de composites de polymère contenant du graphène Download PDF

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Publication number
WO2014168979A1
WO2014168979A1 PCT/US2014/033383 US2014033383W WO2014168979A1 WO 2014168979 A1 WO2014168979 A1 WO 2014168979A1 US 2014033383 W US2014033383 W US 2014033383W WO 2014168979 A1 WO2014168979 A1 WO 2014168979A1
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Prior art keywords
graphene sheets
weight percent
article
composition
graphite
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PCT/US2014/033383
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English (en)
Inventor
Robert Heuser
Jeffrey KACZMARCZYK
John S. Lettow
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Vorbeck Materials
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Publication of WO2014168979A1 publication Critical patent/WO2014168979A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • Articles made from polymer compositions are used in many areas. In some cases, uses are limited by temperature limitations of the of polymer compositions (for example, some compositions can have exhibit diminished physical properties at higher temperatures). In some cases, it can be useful or necessary to use polymer systems that are more costly for higher temperature applications. It may also be desirable to replace metal components with polymer compositions, but in applications require resistance to elevated temperatures, this may not be cost-effective or even possible.
  • Disclosed and claimed herein is a method of using an article, comprising heating the article to a temperature of at least about 100 °C, wherein the article comprises a composition comprising at least one polymer and graphene sheets. Further disclosed and claimed is method of using an article, wherein the article comprises a first composition comprising at least one polymer, graphene sheets, and, optionally, additional components, comprising heating the article to a temperature above which a second composition that is identical to the first composition except that it has no graphene sheets has a storage modulus that is at least about 10 percent less than the storage modulus of the second composition at 25 °C.
  • Also disclosed and claimed is a method of using an article, wherein the article comprises a first composition comprising at least one polymer, graphene sheets, and, optionally, additional components, comprising heating the article to a temperature that is at about or greater than the heat deflection temperature of a second composition that is identical to the first composition except that it has no graphene sheets.
  • the composites are formed into articles that are used at elevated temperatures.
  • the articles may be part of a larger apparatus. Some or all of the larger apparatus can be exposed to elevated temperatures during use.
  • use is meant the use of the article in practical manner.
  • the mere act of performing analytical/laboratory testing of properties of the composite material or articles made therefrom at elevated temperatures is not considered to be a use, for example.
  • the article is exposed to elevated temperatures for a consecutive time of at least about 1 second, or at least about 30 seconds, or at least about 1 minute, or at least about 5 minutes, or at least about 10 minutes, or at least about 30 minutes, or at least about 1 hours, or at least about 5 hours, or at least about 10 hours, or at least about 1 day, or at least about 5 days, or at least about 10 days, or at least about 30 days, or at least about 100 days, or at least about 1 year, or at least about 3 years, or at least about 5 years.
  • the elevated temperatures can be at least about 100 °C, or at least about 125 °C, or at least about 150 °C, or at least about 160 °C, or least about 170 °C, or at least about 180 °C, or at least about 190 °C, or at least about 200 °C, or at least about 220 °C, or at least about 240 °C, or at least about 260 °C, or at least about 280 °C, or at least about 300 °C, or at least about 320 °C, or at least about 340 °C, or at least about 360 °C, or at least about 380 °C, or at least about 400 °C, or at least about 420 °C, or at least about 440 °C, or at least about 460 °C, or at least about 480 °C, or at least about 500 °C, or at least about 520 °C, or at least about 540 °C, or at least about 560 °C,
  • the article is used at a temperature above which the corresponding unfilled composition has a storage modulus that is at least about 10 percent less than the storage modulus it has at 25 °C, or at least about 20 percent less than the storage modulus it has at 25 °C, or at least about 30 percent less than the storage modulus it has at 25 °C, or at least about 40 percent less than the storage modulus it has at 25 °C, or at least about 50 percent less than the storage modulus it has at 25 °C, or at least about 60 percent less than the storage modulus it has at 25 °C.
  • Storage modulus can be measured using a dynamic mechanical analyzer. For example, it can be measured using a multifrequency strain method with a tension clamp.
  • the article is used at a temperature that is at about the heat deflection temperature of the unfilled composition, or at least 5 °C above, or at least about 10 °C above, or at least about 15 °C above, or at least about 20 °C above, or at least about 25 °C above, or at least about 30 °C above, or at least about 40 °C above, or at least about 50 °C above, or at least about 60 °C above, or at least about 70 °C above, or at least about 80 °C above, or at least about 90 °C above, or at least about 100 °C above, or at least about 120 °C above, or at least about 140 °C above, or at least about 160 °C above, or at least about 180 °C above, or at least about 200 °C above, or at least about 220 °C above, or at least about 240 °C above, or at least about 260 °C above, or at least about 280 °C above, or at least about
  • the polymers can be thermosets, thermoplastics, non-melt processible polymers, rubbers, elastomers, thermoplastic elastomers, polymer alloys, copolymers (where the term “copolymers” refers to polymers derived from two or more monomers), etc.
  • the polymers can be crosslinked, vulcanized, or otherwise cured.
  • polymers examples include polyolefins, such as polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density
  • polyethylene ultrahigh molecular weight polyethylene, polypropylene, olefin polymers and copolymers, ethylene/propylene copolymers (EPR), ethylene/propylene/diene monomer copolymers (EPDM); olefin and styrene copolymers; polystyrene (including high impact polystyrene); styrene/butadiene rubbers (SBR);
  • SEBS styrene/ethylene/butadiene/styrene copolymers
  • SEBS isobutylene/maleic anhydride copolymers
  • ethylene/acrylic acid copolymers acrylonitrile/butadiene/styrene
  • ABS styrene/acrylonitrile polymers
  • SAN styrene/maleic anhydride copolymers
  • PE/ABS polyvinyl pyrrolidone
  • polyvinyl pyrrolidone vinyl acetate/vinyl pyrrolidone copolymers
  • polyvinyl acetate polyvinyl acetate
  • ethylene/vinyl acetate copolymers EVA
  • polyvinyl alcohols PVOH
  • ethylene/vinyl alcohol copolymers EVOH
  • polyvinyl butyral PVB
  • polyvinyl formal polycarbonates
  • PC polycarbonate/acrylonitrile butadiene styrene copolymers
  • PC/ABS polyamides; polyesters; liquid crystalline polymers (LCPs); poly(lactic acid) (PLA); poly(phenylene oxide) (PPO); PPO-polyamide alloys; polysulphones (PSU); polysulfides; poly(phenylene sulfide); polyetherketone (PEK); polyetheretherketone (PEEK); cross-linked
  • fluoropolymers such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene polymers (FEP), polyvinyl fluoride), poly(vinylidene fluoride), vinylidene
  • PEVE perfluoro(ethyl vinyl ether)
  • PPVE perfluoro(propyl vinyl ether)
  • CTFE chlorotrifluoroethylene
  • alkyl vinyl ethers etc.
  • polysiloxanes e.g., (polydimethylenesiloxane, dimethylsiloxane/vinylmethylsiloxane copolymers, vinyldimethylsiloxane terminated poly(dimethylsiloxane), etc.
  • polysiloxanes e.g., (polydimethylenesiloxane, dimethylsiloxane/vinylmethylsiloxane copolymers, vinyldimethylsiloxane terminate
  • polyamides include, but are not limited to, aliphatic polyamides (such as polyamide 4,6; polyamide 6,6; polyamide 6; polyamide 1 1 ; polyamide 12;
  • poly(dodecamethylene terephthalamide) (polyamide 12,T), poly(decamethylene terephthalamide) (polyamide 10,T), poly(nonamethylene terephthalamide) (polyamide 9,T), the polyamide of hexamethylene terephthalamide and hexamethylene adipamide, the polyamide of hexamethyleneterephthalamide, and 2- methylpentamethyleneterephthalamide), etc.
  • the polyamides can be polymers and copolymers (i.e., polyamides having at least two different repeat units) having melting points between about 120 and 255 °C including aliphatic copolyamides having a melting point of about 230 °C or less, aliphatic copolyamides having a melting point of about 210 °C or less, aliphatic copolyamides having a melting point of about 200 °C or less, aliphatic copolyamides having a melting point of about 180 °C or less, etc. Examples of these include those sold under the trade names Macromelt by Henkel and Versamid by Cognis.
  • Examples include polymers derived from one or more acrylates, methacrylates, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylates, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl (meth)acrylate, acrylonitrile, and the like.
  • the polymers can comprise repeat units derived from other monomers such as olefins (e.g. ethylene, propylene, etc.), vinyl acetates, vinyl alcohols, vinyl pyrrolidones, etc. They can include partially neutralized acrylate polymers and copolymers (such as ionomer resins).
  • polyesters include, but are not limited to, poly(butylene
  • PBT poly(ethylene terephthalate)
  • PET poly(1 ,3-propylene
  • PPT poly(ethylene naphthalate)
  • PEN poly(cyclohexanedimethanol terephthalate)
  • rubbers and elastomers examples include styrene/butadiene copolymers (SBR), styrene/ethylene/butadiene/styrene copolymer (SEBS), polyisoprene,
  • EPR ethylene/propylene copolymers
  • EPM ethylene/propylene/monomer copolymers
  • EPDM ethylene/propylene/diene monomer copolymers
  • CSM polyethylene
  • CM chlorinated polyethylene
  • EVM ethylene/vinyl acetate copolymers
  • butyl rubber natural rubber, polybutadiene (Buna CB), chloroprene rubber (CR), halogenated butyl rubber, bromobutyl rubber, chlorobutyl rubber, nitrile rubber
  • copolyetheresters such as polysiloxanes (e.g., (polydimethylenesiloxane, dimethylsiloxane/vinylmethylsiloxane copolymers, vinyldimethylsiloxane terminated poly(dimethylsiloxane), etc.), fluorosilicone rubber, fluoromethyl silicone rubber (FMQ), fluorovinyl silicone rubbers (FVMQ), phenylmethyl silicone rubbers (PMQ), vinyl silicone rubbers, etc.), fluoropolymers (such as
  • FFKM perfluorocarbon rubbers
  • FKM fluoronated hydrocarbon rubbers
  • FEP fluorinated ethylene propylene polymers
  • polyvinyl fluoride poly(vinylidene fluoride)
  • vinylidene fluoride/hexafluoropropylene copolymers VF2/HFP
  • vinylidene fluoride/ hexafluoropropylene/tetrafluoroethylene VF2/HFP/TFE copolymers
  • vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymers VF2/HPF/TFE
  • vinylidene fluoride/tetrafluoroethylene/propylene VF2/TFE/P
  • perfluoroelastomers such as tetrafluoroethylene perfluor
  • PEVE perfluoro(ethyl vinyl ether)
  • PPVE perfluoro(propyl vinyl ether)
  • the polymers, graphene sheets, and other components, if used, can be formed into the composite compositions using any suitable means, including melt processing (using, for example, one or more of single or twin-screw extruders, blenders, kneaders, mixers, Brabender mixers, Banbury mixers, roller mills (such as two-roll mills, three-roll mill), etc.), solution/dispersion processing/blending, via thermosetting lay-ups, etc.
  • melt processing using, for example, one or more of single or twin-screw extruders, blenders, kneaders, mixers, Brabender mixers, Banbury mixers, roller mills (such as two-roll mills, three-roll mill), etc.
  • solution/dispersion processing/blending via thermosetting lay-ups, etc.
  • graphene sheets can be added to monomer or oligomers that are then in-situ polymerized to form the polymers.
  • the graphene sheets (and/or other components) can be added to a polymer matrix that is then cross-linked, vulcanized, or otherwise cured.
  • Graphene sheets can be blended with rubbers and other elastomers in a mixer and the rubber or elastomer blends later crosslinked.
  • the graphene sheets can be added to the polymer as dry powder, in a solvent dispersion, suspension, or paste, or the like.
  • Articles can be formed from the composite compositions using any suitable method, including compression molding, extrusion, ram extrusion, injection molding, extrusion, co-extrusion, rotational molding, blow molding, injection blow molding, flexible molding, thermoforming, vacuum forming, casting, solution casting, centrifugal casting, overmolding, reaction injection molding, vacuum assisted resin transfer molding, spinning, printing, spraying, sputtering, coating, roll-to-roll processing, laminating, etc.
  • Thermoset compositions can be formed by mixing resin precursors with graphene sheets and, optionally, other additives in a mold and curing to form the article.
  • compositions can contain electrically conductive components, such as metals (including metal alloys), conductive metal oxides, conductive carbons, polymers, metal-coated materials, etc. These components can take a variety of forms, including particles, powders, flakes, foils, needles, etc.
  • electrically conductive components such as metals (including metal alloys), conductive metal oxides, conductive carbons, polymers, metal-coated materials, etc. These components can take a variety of forms, including particles, powders, flakes, foils, needles, etc.
  • metals include, but are not limited to zinc, aluminum, nickel, silver, copper, tin, iron, gold, brass, bronze, platinum, palladium, lead, steel, rhodium, titanium, tungsten, magnesium, colloidal metals, etc.
  • metal oxides include antimony tin oxide and indium tin oxide and materials such as fillers coated with metal oxides.
  • Metal and metal-oxide coated materials include, but are not limited to metal coated carbon and graphite fibers, metal coated glass fibers, metal coated glass beads, metal coated ceramic materials (such as beads), etc. These materials can be coated with a variety of metals, including nickel.
  • curing and crosslinking agents examples include radical initiators such as radical polymerization initiators, radical sources, etc., including organic and inorganic compounds. Coagents and crosslinking promoters may be used as well. Examples include organic and inorganic peroxides (such as hydrogen peroxide, dialkyl peroxides, hydroperoxides, peracids, diacyl peroxides, peroxy esters, ketone peroxides,
  • hydrocarbon peroxides organometallic peroxides, organic polyoxides, organic polyoxides, dialkyl trioxides, hydrotrioxides, tetroxides, alkali metal peroxides (such as lithium peroxide), etc.), azo compounds, polyphenylhydrocarbons, substituted
  • peroxides include, but are not limited to dibenzoyl peroxide, dicumyl peroxide, acetone peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, fe/f-butyl peroxide, ie f-butyl peracetate, di-fe/f-amyl peroxide, ie f-butyl hydroperoxide, cumene hydroperoxide, 1 ,3-b/ ' s-(ie f-butylperoxy-1 -propyl) benzene, b/ ' s-(ie f-butylperoxy) valerate, b/ ' s-(2,4-dichlorobenzoyl) peroxide, etc.
  • azo compounds examples include azobisisobutylonitrile (AIBN); 1 ,1 '- azobis(cyclohexanecarbonitrile) (ABCN); 2,2'-azobis(2-methylbutyronitrile); 2,2'- azobis(2-methylpropionitrile); 2,2'-azobis(2-methylpropionitrile); /V-ie f-butyl-/V-(2-methyl- 1 -phenylpropyl)-0-(1-phenylethyl)hydroxylamine, etc.
  • AIBN azobisisobutylonitrile
  • ABCN 1 ,1 '- azobis(cyclohexanecarbonitrile)
  • 2,2'-azobis(2-methylbutyronitrile) 2,2'-azobis(2-methylpropionitrile)
  • 2,2'-azobis(2-methylpropionitrile) 2,2'-azobis(2-methylpropionitrile)
  • Graphite is made up of many layers of graphene, which are one-atom thick sheets of carbon atoms arranged in a hexagonal lattice.
  • the graphene sheets are graphite sheets preferably having one or more layers of graphene having a surface area of from about 100 to about 2630 m 2 /g.
  • the graphene sheets primarily, almost completely, or completely comprise fully exfoliated single sheets of graphite (these are approximately ⁇ 1 nm thick and are often referred to as "graphene"), while in other embodiments, at least a portion of the graphene sheets can comprise partially exfoliated graphite sheets, in which two or more sheets of graphite have not been exfoliated from each other.
  • the graphene sheets can comprise mixtures of fully and partially exfoliated graphite sheets.
  • Graphene sheets are distinct from carbon nanotubes.
  • Graphene sheets can have a "platy" (e.g. two-dimensional) structure and do not have the needle-like form of carbon nanotubes.
  • the two longest dimensions of the graphene sheets can each be at least about 10 times greater, or at least about 50 times greater, or at least about 100 times greater, or at least about 1000 times greater, or at least about 5000 times greater, or at least about 10,000 times greater than the shortest dimension (i.e. thickness) of the sheets.
  • Graphene sheets are distinct from expanded, exfoliated, vermicular, etc. graphite, which has a layered or stacked structure in which the layers are not separated from each other.
  • Graphene sheets may be made using any suitable method. For example, they may be obtained from graphite, graphite oxide, expandable graphite, expanded graphite, etc.. They may be obtained by the physical exfoliation of graphite, by for example, peeling, grinding, milling, graphene sheets. They made be made by sonication of precursors such as graphite. They may be made by opening carbon nanotubes. They may be made from inorganic precursors, such as silicon carbide. They may be made by chemical vapor deposition (such as by reacting a methane and hydrogen on a metal surface). They may be made by epitaxial growth on substrates such as silicon carbide and metal substrates and by growth from metal-carbon melts.
  • They made by made They may be may by the reduction of an alcohol, such ethanol, with a metal (such as an alkali metal like sodium) and the subsequent pyrolysis of the alkoxide product (such a method is reported in Nature Nanotechnology (2009), 4, 30-33). They may be made from small molecule precursors such as carbon dioxide, alcohols (such as ethanol, methanol, etc.), alkoxides (such as ethoxides, methoxides, etc., including sodium, potassium, and other alkoxides). They may be made by the exfoliation of graphite in dispersions or exfoliation of graphite oxide in dispersions and the subsequently reducing the exfoliated graphite oxide.
  • Graphene sheets can be made from graphite oxide (also known as graphitic acid or graphene oxide). Graphite can be treated with oxidizing and/or intercalating agents and exfoliated. Graphite can also be treated with intercalating agents and
  • Graphene sheets can be formed by ultrasonically exfoliating suspensions of graphite and/or graphite oxide in a liquid (which can contain surfactants and/or intercalants). Exfoliated graphite oxide dispersions or suspensions can be subsequently reduced to graphene sheets. Graphene sheets can also be formed by mechanical treatment (such as grinding or milling) to exfoliate graphite or graphite oxide (which would subsequently be reduced to graphene sheets).
  • Reduction of graphite oxide to graphene can be by means of chemical reduction and can be carried out on graphite oxide in a dry form, in a dispersion, etc.
  • useful chemical reducing agents include, but are not limited to, hydrazines (such as hydrazine, ⁇ /,/V-dimethylhydrazine, etc.), sodium borohydride, citric acid, hydroquinone, isocyanates (such as phenyl isocyanate), hydrogen, hydrogen plasma, etc.
  • a dispersion or suspension of exfoliated graphite oxide in a carrier can be made using any suitable method (such as ultrasonication and/or mechanical grinding or milling) and reduced to graphene sheets.
  • Graphite oxide can be produced by any method known in the art, such as by a process that involves oxidation of graphite using one or more chemical oxidizing agents and, optionally, intercalating agents such as sulfuric acid.
  • oxidizing agents include nitric acid, nitrates (such as sodium and potassium nitrates), perchlorates, potassium chlorate, sodium chlorate, chromic acid, potassium chromate, sodium chromate, potassium dichromate, sodium dichromate, hydrogen peroxide, sodium and potassium permanganates, phosphoric acid (H 3 P0 4 ), phosphorus pentoxide, bisulfites, etc.
  • Preferred oxidants include KCI0 4 ; HN0 3 and KCI0 3 ; KMn0 4 and/or NaMn0 4 ;
  • graphene sheets One example of a method for the preparation of graphene sheets is to oxidize graphite to graphite oxide, which is then thermally exfoliated to form graphene sheets (also known as thermally exfoliated graphite oxide), as described in US 2007/0092432, the disclosure of which is hereby incorporated herein by reference.
  • the thusly formed graphene sheets can display little or no signature corresponding to graphite or graphite oxide in their X-ray diffraction pattern.
  • the graphene sheets preferably have a surface area of at least about 100 m 2 /g to, or of at least about 200 m 2 /g, or of at least about 300 m 2 /g, or of least about 350 m 2 /g, or of least about 400 m 2 /g, or of least about 500 m 2 /g, or of least about 600 m 2 /g., or of least about 700 m 2 /g, or of least about 800 m 2 /g, or of least about 900 m 2 /g, or of least about 700 m 2 /g.
  • the surface area can be about 400 to about 1 100 m 2 /g.
  • the theoretical maximum surface area can be calculated to be 2630 m 2 /g.
  • the graphene sheets can have number average aspect ratios of about 100 to about 100,000, or of about 100 to about 50,000, or of about 100 to about 25,000, or of about 100 to about 10,000 (where "aspect ratio" is defined as the ratio of the longest dimension of the sheet to the shortest).
  • Surface area can be measured using either the nitrogen adsorption/BET method at 77 K or a methylene blue (MB) dye method in liquid solution.
  • MB methylene blue
  • the difference between the amount of MB that was initially added and the amount present in solution as determined by UV-vis spectrophotometry is assumed to be the amount of MB that has been adsorbed onto the surface of the graphene sheets.
  • the surface area of the graphene sheets are then calculated using a value of 2.54 m 2 of surface covered per one mg of MB adsorbed.
  • the graphene sheets can be functionalized with, for example, oxygen-containing functional groups (including, for example, hydroxyl, carboxyl, and epoxy groups) and typically have an overall carbon to oxygen molar ratio (C/O ratio), as determined by bulk elemental analysis, of at least about 1 :1 , or more preferably, at least about 3:2.
  • oxygen-containing functional groups including, for example, hydroxyl, carboxyl, and epoxy groups
  • C/O ratio carbon to oxygen molar ratio
  • Examples of carbon to oxygen ratios include about 3:2 to about 85:15; about 3:2 to about 20:1 ; about 3:2 to about 30:1 ; about 3:2 to about 40:1 ; about 3:2 to about 60:1 ; about 3:2 to about 80:1 ; about 3:2 to about 100:1 ; about 3:2 to about 200:1 ; about 3:2 to about 500:1 ; about 3:2 to about 1000:1 ; about 3:2 to greater than 1000:1 ; about 10:1 to about 30:1 ; about 80:1 to about 100:1 ; about 20:1 to about 100:1 ; about 20:1 to about 500:1 ; about 20:1 to about 1000:1 ; about 50:1 to about 300:1 ; about 50:1 to about 500:1 ; and about 50:1 to about 1000:1.
  • the carbon to oxygen ratio is at least about 10:1 , or at least about 15:1 , or at least about 20:1 , or at least about 35:1 , or at least about 50: 1 , or at least about 75: 1 , or at least about 100: 1 , or at least about 200:1 , or at least about 300:1 , or at least about 400:1 , or at least 500:1 , or at least about 750:1 , or at least about 1000:1 ; or at least about 1500:1 , or at least about 2000:1 .
  • the carbon to oxygen ratio also includes all values and subvalues between these ranges.
  • the graphene sheets can contain atomic scale kinks. These kinks can be caused by the presence of lattice defects in, or by chemical functionalization of the two- dimensional hexagonal lattice structure of the graphite basal plane.
  • compositions can further comprise graphite (including natural, Kish, and synthetic, annealed, pyrolytic, highly oriented pyrolytic, etc. graphites).
  • the ratio by weight of graphite to graphene sheets can be from about 2:98 to about 98:2, or from about 5:95 to about 95:5, or from about 10:90 to about 90:10, or from about 20:80 to about 80:20, or from about 30:70 to 70:30, or from about 40:60 to about 90:10, or from about 50:50 to about 85:15, or from about 60:40 to about 85:15, or from about 70:30 to about 85:15.
  • the graphene sheets can comprise two or more graphene powders having different particle size distributions and/or morphologies.
  • the graphite can also comprise two or more graphite powders having different particle size distributions and/or morphologies.
  • the graphene sheets (and/or graphite, if present) can be combined with one or more solvents in the form of a paste, dispersion, suspension that can be combined with the polymer when the composition or article is formed. Some of all of the solvent can be removed from the composition or article during or after processing.
  • Suitable materials for use as grinding media include metals, carbon steel, stainless steel, ceramics, stabilized ceramic media (such as cerium yttrium stabilized zirconium oxide), PTFE, glass, tungsten carbide, etc. Methods such as these can be used to change the particle size and/or morphology of the graphene sheets (and/or graphite, if present).
  • stabilized ceramic media such as cerium yttrium stabilized zirconium oxide
  • PTFE ttrium stabilized zirconium oxide
  • glass glass
  • tungsten carbide etc.
  • solvents include water, distilled or synthetic isoparaffinic
  • hydrocarbons such Isopar® and Norpar® (both manufactured by Exxon) and Dowanol® (manufactured by Dow)
  • citrus terpenes and mixtures containing citrus terpenes such as Purogen, Electron, and Positron (all manufactured by Ecolink)
  • terpenes and terpene alcohols including terpineols, including alpha-terpineol
  • limonene aliphatic petroleum distillates
  • alcohols such as methanol, ethanol, n-propanol, / ' -propanol, n-butanol, / ' - butanol, sec-butanol, ie f-butanol, pentanols, i-amyl alcohol, hexanols, heptanols, octanols, diacetone alcohol, butyl glycol, etc.), ketones (such as acetone, methyl
  • Solvents can be low- or non-VOC solvents, non-hazardous air pollution solvents, and non-halogenated solvents.
  • the articles are useful in many environments where they will be used at elevated temperatures.
  • the articles can be used to replace metal components in many applications (including hoses, seals, gaskets, etc.).
  • the articles can be used in environments where they are exposed to hot air and other gases, steams, hot water and other fluids, fuels, lubricants, coolants, hot materials, etc.
  • the articles can be components of pumps, such as vacuum pumps, diaphragm pumps, impeller pumps, piston pumps, positive displacement pumps, etc. They can be components of or serve as pump heads, vanes, float balls, piping, tubing, hoses, seals, connectors, valves, belts, apparel, etc.
  • the articles can be used as engine and motor components, such as gaskets, belts, tubes and hoses, engine or motor mounts, etc.
  • the articles can be used in batteries and other energy capture and storage devices, such as high temperature flow batteries (such as in flow loops and salt baths), solar energy systems (e.g. photovoltaic and thermal collection systems (such as heaters)), geothermal power systems, wind power systems, nuclear power systems, etc.
  • high temperature flow batteries such as in flow loops and salt baths
  • solar energy systems e.g. photovoltaic and thermal collection systems (such as heaters)
  • geothermal power systems e.g. photovoltaic and thermal collection systems (such as heaters)
  • wind power systems such as in wind power systems, nuclear power systems, etc.
  • the articles can be used in applications where fire retardancy and/or drip suppression are important.
  • the articles can be used as components in weapons systems such as firearms (including small firearms, artillery, etc.), projectile launch tubes (such as torpedo launch tubes). They can be used in explosives and pyrotechnics (including fireworks) systems, etc.
  • the articles can be used in apparel and personal protective equipment for high temperature uses, when exposure to high temperatures is possible, etc. such as that used by industrial workers, welders, construction works, chemical plant workers, foundry workers, emergency personnel (such as firefighters, first responders, rescue workers, hazmat workers, etc.), military personnel, electrical workers, etc.
  • Example include, but are not limited to boots, shoes, and other footwear, gaiters, overboots, spats, chaps, coats, jackets, pants, belts, shirts, undergarments, hoods, visors, glasses, goggles, chin guards, gloves, mittens, smocks, aprons, bibs, overalls, coveralls, hats, hard hats, helmets, respirators, gas masks, blankets, fire curtains, breathing air (such as tanks, such as oxygen tanks) equipment (such as tubing, face masks, etc.), harnesses and lanyards, space suits, etc.
  • air such as tanks, such as oxygen tanks
  • harnesses and lanyards such as tubing, face masks, etc.
  • the articles can be used as components of conveyer systems, such as belts, rollers, drive rollers, etc. These include conveyer systems that transport materials, ore and finished metal products, food products, etc. They include conveyer systems that transport items to and from ovens, furnaces, kilns, boilers, dryers, and other high temperature sources. Examples of conveyer systems include those used in metal processing and smelting, chemical processing, fuel (e.g. coal, etc.) transport and feeding, assembly and production lines (such as those used to make automobiles and other vehicles), casting (such as metal casting), packaging, waste handling and recycling, etc.
  • conveyer systems include those used in metal processing and smelting, chemical processing, fuel (e.g. coal, etc.) transport and feeding, assembly and production lines (such as those used to make automobiles and other vehicles), casting (such as metal casting), packaging, waste handling and recycling, etc.
  • the articles can offer an increased coefficient of friction that can reduce belt wear.
  • the articles can be used as comments of high temperature printing systems (e.g. laser printing, digital printing, flexographic printing, gravure printing, etc., such as fusers, belts, gears, etc.
  • high temperature printing systems e.g. laser printing, digital printing, flexographic printing, gravure printing, etc., such as fusers, belts, gears, etc.
  • the articles can be used in aerospace, aviation, space exploration, etc.
  • Examples include aircraft, airplanes, helicopters, rockets, satellites, booster engines, re-entry vehicles, balloons (including weather balloons, weather balloons), airships, blimps, dirigibles, drones, space shuttles, space stations,
  • interplanetary and intergalactic exploration devices and vehicles etc.
  • the articles can be used in automotive applications, such as engine mounts, belts, timing belts, drive belts, transmission belts, seals, gaskets, boots (e.g. constant velocity boots), body panels, heaters, tubing, coolant system components, etc.
  • the articles can be used for cooking and baking (e.g., heat resistant cookware and bakeware) and laboratory equipment.
  • the coating has conductivities of at least about 0.001 S/m, of at least about 0.01 S/m, of at least about 0.1 S/m, of at least about 1 S/m, of at least about 10 S/m, of at least about 100 S/m, or at least about 1000 S/m, or at least about 10,000 S/m, or at least about 20,000 S/m, or at least about 30,000 S/m, or at least about 40,000 S/m, or at least about 50,000 S/m, or at least about 60,000 S/m, or at least about 75,000 S/m, or at least about 10 5 S/m, or at least about 10 6 S/m.
  • the surface resistivity of the composite composition can be no greater than about 10 megaQ/square/mil, or no greater than about 1 mega ⁇ /square/mil, or no greater than about 500 kiloQ/square/mil, or no greater than about 200
  • kiloQ/square/mil or no greater than about 100 kiloQ/square/mil, or no greater than about 50kiloQ/square/mil, or no greater than about 25 kiloQ/square/mil, or no greater than about 10 kiloQ/square/mil, or no greater than about 5 kilo ⁇ /square/mil, or no greater than about 1000 ⁇ /square/mil, or no greater than about 700 ⁇ /square/mil, or no greater than about 500 ⁇ /square/mil, or no greater than about 350 ⁇ /square/mil, or no greater than about 200 ⁇ /square/mil, or no greater than about 200 ⁇ /square/mil, or no greater than about 150 ⁇ /square/mil, or no greater than about 100 ⁇ /square/mil, or no greater than about 75 ⁇ /square/mil, or no greater than about 50 ⁇ /square/mil, or no greater than about 30 ⁇ /square/mil, or no greater than about

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé d'utilisation d'un article comprenant le chauffage de l'article à une température d'au moins environ 150°C, l'article comprenant une composition incluant au moins un polymère et des feuilles de graphène. L'invention concerne également un procédé d'utilisation d'un article, l'article comprenant une première composition incluant au moins un polymère, des feuilles de graphène et éventuellement des composants additionnels, ledit procédé comprenant le chauffage de l'article à une température au-dessus de laquelle une seconde composition qui est identique à la première composition excepté qu'elle ne contient pas de feuilles de graphène, présente un module de conservation qui est d'au moins environ 10 pour cent inférieur au module de conservation de la seconde composition à 25°C, ou le chauffage de l'article à une température qui est environ égale, ou supérieure à la température de déformation à chaud d'une seconde composition qui est identique à la première composition excepté qu'elle ne contient pas de feuilles de graphène.
PCT/US2014/033383 2013-04-08 2014-04-08 Utilisation de composites de polymère contenant du graphène WO2014168979A1 (fr)

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US201361809453P 2013-04-08 2013-04-08
US61/809,453 2013-04-08

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RU2618881C1 (ru) * 2016-05-16 2017-05-11 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" ФГБОУ ВО "ТГТУ" Способ получения дисперсий углеродных наноматериалов
CN108194158A (zh) * 2017-12-19 2018-06-22 玉环捷宇机械制造有限公司 一种凸轮组件及加工工艺以及应用该凸轮组件的配气机构
US10612492B2 (en) 2017-03-16 2020-04-07 Northrop Grumman Innovation Systems, Inc. Precursor compositions for an insulation, insulated rocket motors, and related methods
WO2020174391A1 (fr) * 2019-02-25 2020-09-03 Reliance Industries Limited Composition polymère comprenant du graphène en tant qu'additif de réchauffage, procédé et utilisation de cette dernière
US11090860B2 (en) 2015-03-06 2021-08-17 Signify Holding B.V. 3D printing of graphene (oxide) composites
CN113921844A (zh) * 2021-11-15 2022-01-11 成都先进金属材料产业技术研究院股份有限公司 基于丁苯橡胶的全钒液流电池用双极板及其制备方法
CN114517013A (zh) * 2022-03-01 2022-05-20 青岛科技大学 一种阻燃输送带用滚筒摩擦助剂及其制备方法
WO2022133023A1 (fr) 2020-12-18 2022-06-23 Martinrea International US Inc. Tube de transport de carburant et de vapeur d'automobile ayant une structure monocouche ou multicouche incorporant du graphène
US20230026484A1 (en) * 2021-07-22 2023-01-26 Zhejiang Normal University Vinyl-modified nanofillers as interfacial compatibilizers and method for producing compatibilized polymer blends
US11858239B2 (en) 2021-09-22 2024-01-02 AISIN Technical Center of America, Inc. Polymer-graphene energy absorbing composite structures and methods of manufacture
CN117534938A (zh) * 2024-01-10 2024-02-09 广州简米餐具有限公司 一种用于制作抗污餐具的密胺粉及其制备方法

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11090860B2 (en) 2015-03-06 2021-08-17 Signify Holding B.V. 3D printing of graphene (oxide) composites
RU2618881C1 (ru) * 2016-05-16 2017-05-11 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" ФГБОУ ВО "ТГТУ" Способ получения дисперсий углеродных наноматериалов
US11306683B2 (en) 2017-03-16 2022-04-19 Northrop Grumman Systems Corporation Precursor compositions for an insulation and insulated rocket motors
US10612492B2 (en) 2017-03-16 2020-04-07 Northrop Grumman Innovation Systems, Inc. Precursor compositions for an insulation, insulated rocket motors, and related methods
CN108194158A (zh) * 2017-12-19 2018-06-22 玉环捷宇机械制造有限公司 一种凸轮组件及加工工艺以及应用该凸轮组件的配气机构
CN108194158B (zh) * 2017-12-19 2024-02-09 玉环捷宇机械制造有限公司 一种凸轮组件及加工工艺以及应用该凸轮组件的配气机构
WO2020174391A1 (fr) * 2019-02-25 2020-09-03 Reliance Industries Limited Composition polymère comprenant du graphène en tant qu'additif de réchauffage, procédé et utilisation de cette dernière
WO2022133023A1 (fr) 2020-12-18 2022-06-23 Martinrea International US Inc. Tube de transport de carburant et de vapeur d'automobile ayant une structure monocouche ou multicouche incorporant du graphène
US20230026484A1 (en) * 2021-07-22 2023-01-26 Zhejiang Normal University Vinyl-modified nanofillers as interfacial compatibilizers and method for producing compatibilized polymer blends
US12012502B2 (en) * 2021-07-22 2024-06-18 Zhejiang Normal University Vinyl-modified nanofillers as interfacial compatibilizers and method for producing compatibilized polymer blends
US11858239B2 (en) 2021-09-22 2024-01-02 AISIN Technical Center of America, Inc. Polymer-graphene energy absorbing composite structures and methods of manufacture
CN113921844A (zh) * 2021-11-15 2022-01-11 成都先进金属材料产业技术研究院股份有限公司 基于丁苯橡胶的全钒液流电池用双极板及其制备方法
CN114517013A (zh) * 2022-03-01 2022-05-20 青岛科技大学 一种阻燃输送带用滚筒摩擦助剂及其制备方法
CN117534938A (zh) * 2024-01-10 2024-02-09 广州简米餐具有限公司 一种用于制作抗污餐具的密胺粉及其制备方法
CN117534938B (zh) * 2024-01-10 2024-04-02 广州简米餐具有限公司 一种用于制作抗污餐具的密胺粉及其制备方法

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