WO2012057762A1 - Exfoliation of graphene by multilayer coextrusion - Google Patents

Exfoliation of graphene by multilayer coextrusion Download PDF

Info

Publication number
WO2012057762A1
WO2012057762A1 PCT/US2010/054443 US2010054443W WO2012057762A1 WO 2012057762 A1 WO2012057762 A1 WO 2012057762A1 US 2010054443 W US2010054443 W US 2010054443W WO 2012057762 A1 WO2012057762 A1 WO 2012057762A1
Authority
WO
WIPO (PCT)
Prior art keywords
processing material
graphite
processing
graphene
substrate
Prior art date
Application number
PCT/US2010/054443
Other languages
English (en)
French (fr)
Inventor
Carlos A. Cruz
Original Assignee
Empire Technology Development Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Empire Technology Development Llc filed Critical Empire Technology Development Llc
Priority to PCT/US2010/054443 priority Critical patent/WO2012057762A1/en
Priority to CN201080069797.0A priority patent/CN103180244B/zh
Priority to US13/002,080 priority patent/US8679290B2/en
Publication of WO2012057762A1 publication Critical patent/WO2012057762A1/en
Priority to US14/176,362 priority patent/US9573312B2/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/23Articles comprising two or more components, e.g. co-extruded layers the components being layers with means for avoiding adhesion of the layers, e.g. for forming peelable layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/49Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
    • B29C48/495Feedblocks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50Details of extruders
    • B29C48/695Flow dividers, e.g. breaker plates
    • B29C48/70Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows
    • B29C48/71Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows for layer multiplication
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • C01B32/19Preparation by exfoliation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/194After-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04Polymers of ethylene
    • B29K2023/06PE, i.e. polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10Polymers of propylene
    • B29K2023/12PP, i.e. polypropylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B29K2025/04Polymers of styrene
    • B29K2025/06PS, i.e. polystyrene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2031/00Use of polyvinylesters or derivatives thereof as moulding material
    • B29K2031/04Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04Polymers of esters
    • B29K2033/12Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0093Other properties hydrophobic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10935Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10Inorganic particles
    • B32B2264/107Ceramic
    • B32B2264/108Carbon, e.g. graphite particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2313/00Elements other than metals
    • B32B2313/04Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/11Methods of delaminating, per se; i.e., separating at bonding face
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/11Methods of delaminating, per se; i.e., separating at bonding face
    • Y10T156/1111Using solvent during delaminating [e.g., water dissolving adhesive at bonding face during delamination, etc.]
    • Y10T156/1116Using specified organic delamination solvent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/11Methods of delaminating, per se; i.e., separating at bonding face
    • Y10T156/1168Gripping and pulling work apart during delaminating
    • Y10T156/1189Gripping and pulling work apart during delaminating with shearing during delaminating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/11Methods of delaminating, per se; i.e., separating at bonding face
    • Y10T156/1168Gripping and pulling work apart during delaminating
    • Y10T156/1195Delaminating from release surface
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/19Delaminating means
    • Y10T156/1961Severing delaminating means [e.g., chisel, etc.]
    • Y10T156/1967Cutting delaminating means
    • Y10T156/1972Shearing delaminating means

Definitions

  • the present disclosure generally pertains to production of graphene from graphite and, more particularly, to exfoliation of graphene from graphite using multilayer coextrusion.
  • graphite may be dispersed within a first processing material, and the first processing material and a second processing material may be co-extruded through a plurality of series coupled layer multiplication dies to exfoliate graphene from the graphite.
  • the graphene may be separated from the resulting multi-layered material.
  • graphite flake and/or expanded graphite may be dispersed within the first processing material.
  • Some example apparatuses may include multilayer co-extrusion devices comprising a plurality of series coupled layer multiplication dies.
  • Some example multilayer co-extrusion apparatuses may be configured to exfoliate graphene by co-extrusion of a first processing material and a second processing material through the plurality of series coupled layer multiplication dies to produce a resulting material including a plurality of alternating layers of the first processing material and the second processing material, where the first processing material may comprise a first graphite material dispersed in a first substrate and the second processing material may comprise a second substrate material.
  • Some example methods may include dispersing a first graphite material in a first substrate material to form a first processing material. Some example methods may further include exfoliating graphene from the first graphite material by co-extrusion of the first processing material and a second processing material through one or more layer multiplication dies to yield a resulting material including individual layers of the first processing material interposed between individual layers of the second processing material, the second processing material comprising a second substrate material. Some example methods may also further include separating the graphene from the first substrate material and the second substrate material.
  • Some example methods may include mixing a multi-sheet substance comprising a plurality of stacked sheets with a first substrate material to form a first processing material. Some example methods may further include delaminating one or more sheets from the multi-sheet substance by application of shear stress to the first processing material. Some example methods may also further include separating the one or more delaminated sheets from the first substrate material.
  • FIG. 1 is a block diagram illustrating an example device for producing graphene
  • FIG. 2 is a block diagram illustrating an example device for producing graphene
  • FIG. 3 is a flow chart illustrating an method of producing graphene from graphite.
  • FIG. 4 is a flow chart illustrating an example method of delaminating a multi- sheet substance; all in accordance with at least some examples of the present disclosure.
  • This disclosure is drawn, inter alia, to exfoliating graphene from graphite.
  • shear stresses caused by multilayer coextrusion of two processing materials, at least one of which may contain graphite dispersed therein, may be used to exfoliate graphene from the graphite.
  • graphite may be described as a layered structure in which an individual layer may be called graphene.
  • Graphene may be described as a flat monolayer of carbon atoms tightly packed into a two-dimensional honeycomb lattice.
  • Graphene may be considered to be a basic building block for other graphitic materials.
  • the present disclosure contemplates that a single layer of graphene was first isolated in 2004 using a so-called peeling method, which used cellophane adhesive tape to successively remove layers from a graphite flake. Although the flakes present on the tape may be much thicker than one layer, a single sheet may be delaminated when the tape is lifted away from the graphite flake. The peeling method may require a great deal of patience, and locating a single layer may be difficult.
  • Example methods according to the present disclosure may utilize shear forces produced by multilayer coextrusion of processing materials (e.g., one or more organic polymers such as polyethylene, polypropylene, polyethylene oxide, polystyrene, or other similar polymers and/or one or more waxes such as polyethylene wax, and/or similar substances) to exfoliate graphene from graphite.
  • processing materials e.g., one or more organic polymers such as polyethylene, polypropylene, polyethylene oxide, polystyrene, or other similar polymers and/or one or more waxes such as polyethylene wax, and/or similar substances.
  • FIG. 1 is a block diagram illustrating an example device for producing graphene in accordance with at least some examples described herein.
  • Extruders 112, 114 may be configured to supply a first processing material 106 and a second processing material 108, respectively, to a feed block 113.
  • Feed block 113 may be configured to supply first processing material 106 and second processing material 108 to a plurality of series coupled layer multiplication dies 116, 118, 120, 122.
  • various thermal controllers, heating devices and/or even cooling devices can be readily adapted for use as a suitable means of precise temperature control.
  • An example method of producing graphene from graphite may comprise dispersing a first graphite material 102 in a first substrate material 104 to form first processing material 106.
  • First processing material 106 and second processing material 108 (which may comprise a second substrate material 110) may be co-extruded, such as using extruders 112, 114 and/or feed block 113, through series coupled layer multiplication dies 116, 118, 120, 122 to produce a resulting material 124 comprising a plurality of alternating layers of first processing material 106 and second processing material 108.
  • first processing material 106 and/or second processing material 108 may exfoliate at least some graphene 126 from first graphite material 102; thus, resulting material 124 may comprise graphene 126.
  • Graphene 126 may be separated from resulting material 124, such as by at least partially dissolving first substrate material 104 and/or second substrate material 110 in a solvent 128 (e.g., water and/or an organic solvent).
  • second processing material 108 may comprise a second graphite material 130, which may be dispersed in second substrate material 110.
  • the present disclosure contemplates that coextruded multilayers with numbers of layers ranging from tens of layers to thousands of layers may be made using layer multiplication dies.
  • FIG. 2 is block diagram illustrating an example device for producing graphene; in accordance with at least some examples described herein.
  • Feed block 113 may be configured to supply first processing material 106 and second processing material 108 to a plurality of series coupled layer multiplication dies 116, 118, 120 to produce resulting material 124 comprising a plurality of alternating layers of first processing material 106 and second processing material 108.
  • resulting material 124 may be at least partially immersed in a solvent bath 128A and/or may be subjected to a solvent spray 128B to separate the graphene.
  • resulting material 124 may be utilized for further applications without separating the graphene.
  • resulting material 124 (including the graphene) may be utilized as a concentrate that may be let down into a selected matrix.
  • the two layer material may be forced through layer multiplication die 116, which may split the two layer material into two parts (each including the two layers from material 102 and material 110), and the individual parts may be compressed, rotated, stretched, and/or stacked together with other individual parts.
  • a fourth layer multiplication die e.g., layer multiplication die 122 shown in FIG. 1
  • one or more of the layer multiplication dies 116, 118, 120, 122 may be substantially the same as one another. In some other example embodiments, one or more of the layer multiplication dies 116, 118, 120, 122 may be different than one another.
  • the individual layers of the resulting material may be about twenty (20) ⁇ thick.
  • the resulting material may comprise about four-thousand and ninety-six (4096) layers, where each of the individual layers of the resulting material may be about one -hundred and fifty six (156) nm thick.
  • Further increasing the number of series-coupled layer multiplication dies e.g., about 18 series couple layer multiplication dies may produce about 524,288 layers
  • feed block 113 may be configured to produce other numbers of layers (e.g., four layers) and/or layer multiplication dies 116, 118, 120, 122 may be configured to triple or quadruple the number of layers, for example.
  • first graphite material 102 and/or second graphite material 130 may comprise graphite flake and/or expanded graphite.
  • first processing material 106 may be formed by blending first graphite material 102 (e.g., a powder) and first substrate material 104 (e.g., a powder) and/or feeding the blend into extruder 112 (which may be a single and/or a twin extruder).
  • Second processing material 108 may be formed in a similar manner using extruder 114.
  • first processing material 106 may be produced by mixing first substrate material 104 and first graphite material 102 together.
  • powdered first substrate material 104 and powdered first graphite material 102 may be combined and stirred, which may disperse first graphite material 102 in first substrate material 104.
  • first processing material 106 may be extruded and/or pelletized prior to being supplied to extruder 112.
  • first substrate material 104 and first graphite material 102 may be heated (e.g., by heating elements and/or due to friction in an extruder) during mixing and/or during extrusion, which may at least partially melt first substrate material 104.
  • second processing material 108 may be produced by mixing second substrate material 110 and second graphite material 130 together.
  • second processing material 108 may be extruded and/or pelletized prior to being supplied to extruder 114
  • second substrate material 110 and second graphite material 130 may be heated (e.g., by heating elements and/or due to friction in an extruder) during mixing and/or during extrusion, which may at least partially melt second substrate material 110.
  • first substrate material 104 and/or second substrate material 110 may have substantially the same composition and/or substantially similar properties.
  • first substrate material and/or second substrate material may both be at least partially soluble in the same solvent.
  • first substrate material 104 and/or second substrate material 110 may comprise non-polar (hydrophobic) materials.
  • non-polar materials may include paraffin wax materials, with or without the addition of a high molecular weight polyolefin, which may improve processing.
  • Such materials may be useful for cold extrusion (e.g., about 25 to about 40 °C).
  • first substrate material 104 and/or second substrate material 1 10 may comprise polar (hydrophilic) materials.
  • such hydrophilic materials may include polyethylene oxide (PEO), which may be useful for low temperature extrusion (e.g., about 40 to about 60 °C).
  • first substrate material 104 and/or second substrate material 110 may have substantially different compositions and/or properties.
  • first substrate material may comprise one or more hydrophobic polymers and/or second substrate material may comprise one or more hydrophilic polymers.
  • one of first substrate material 104 and/or second substrate material 110 may comprise a hydrophobic material (e.g., polyethylene/paraffin wax blends, polystyrene, poly (4-methyl pentene) (P4MP).
  • the other of first substrate material 104 and/or second substrate material 110 may comprise a hydrophilic material (e.g., polyethylene oxide), polyvinyl acetate, styrene acrylonitrile (SAN), poly (methyl
  • PMMA methacrylate
  • polylactic acid polylactic acid
  • blends of these and/or other polymers PMMA
  • first processing material 106 and/or second processing material 108 may comprise graphene. More specifically, in some example embodiments including first substrate material 104 and second substrate material 110 having substantially the same composition and/or substantially similar properties, one or both of first processing material 106 and/or second processing material 108 may include graphene. Similarly, in some example embodiments including first substrate material 104 and second substrate material 110 having substantially different compositions and/or properties, one or both of first processing material 106 and/or second processing material 108 may include graphene.
  • extrusion operations may be conducted at low temperatures (for example and without limitation, cold extrusion and low temperature extrusion discussed above), which may contribute to increased shear stresses within the processing material(s), which may increase the exfoliation of graphene from graphite.
  • extrusion operations may be conducted at or near about the lowest practicable extrusion temperatures for the substrate and/or processing material(s).
  • graphene produced as described herein may be useful in the area of polymer composites, such as where higher strength via high aspect ratio reinforcements may be advantageous.
  • graphene may be used in polyvinyl chloride (PVC) siding, which may increase the heat deflection temperature of the siding such that it may better withstand hot weather-related deformations.
  • PVC polyvinyl chloride
  • poly(lactic acid) a very much appreciated biopolymer, may be utilized in connection with graphene to improve its performance despite its relatively low softening temperature.
  • graphene may be used in automotive and/or other transportation-related applications, where some under-the-hood conditions may benefit from high mechanical strength and heat resistance.
  • the two-dimensional geometry of graphene may provide an extremely low percolation threshold of about 0.1%, which may enhance their electrical conductivity and/or the strength of the matrix.
  • graphene may be used to provide electrically conductive polymers for textile applications.
  • graphene may provide long-lasting antistatic properties.
  • graphene may be useful in some electronics-related applications.
  • the present disclosure contemplates that processes described herein may be used to produce substances besides graphene.
  • multilayer coextrusion processes described herein may be useful for delaminating multi-sheet substances comprising a plurality of stacked sheets.
  • the present disclosure contemplates that mica may be delaminated into its constituent sheets using multilayer coextrusion processes described herein.
  • FIG. 3 is a flow chart illustrating an example method 400 of producing graphene from graphite in accordance with at least some examples described herein.
  • Method 400 may include one or more operations, functions or actions as illustrated by one or more of blocks 402, 404, and/or 406.
  • Block 402 may include dispersing a first graphite material in a first substrate material to form a first processing material.
  • Block 402 may be followed by block 404.
  • Block 404 may include exfoliating graphene from the first graphite material by co-extrusion of the first processing material and a second processing material through one or more layer multiplication dies to yield a resulting material including individual layers of the first processing material interposed between individual layers of the second processing material, the second processing material comprising a second substrate material.
  • block 404 may be followed by block 406.
  • Block 406 may include separating the graphene from the first substrate material and the second substrate material.
  • FIG. 4 is a flow chart illustrating an example method 500 of delaminating a multi-sheet substance in accordance with at least some examples described herein.
  • Method 500 may include one or more operations, functions or actions as illustrated by one or more of blocks 502, 504 and/or 506.
  • Block 502 may include mixing a multi-sheet substance comprising a plurality of stacked sheets with a first substrate material to form a first processing material.
  • Block 502 may be followed by block 504.
  • Block 504 may include delaminating one or more sheets from the multi-sheet substance by application of shear stress to the first processing material.
  • Block 504 may be follow by block 506.
  • Block 506 may include separating the one or more delaminated sheets from the first substrate material.
  • any two components so associated may also be viewed as being “operably connected”, or “operably coupled”, to each other to achieve the desired functionality, and any two components capable of being so associated may also be viewed as being “operably couplable”, to each other to achieve the desired functionality.
  • operably couplable include but are not limited to physically mateable and/or physically interacting components and/or wirelessly interactable and/or wirelessly interacting components and/or logically interacting and/or logically interactable components.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/US2010/054443 2010-10-28 2010-10-28 Exfoliation of graphene by multilayer coextrusion WO2012057762A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/US2010/054443 WO2012057762A1 (en) 2010-10-28 2010-10-28 Exfoliation of graphene by multilayer coextrusion
CN201080069797.0A CN103180244B (zh) 2010-10-28 2010-10-28 石墨烯通过多层共挤出的剥离
US13/002,080 US8679290B2 (en) 2010-10-28 2010-10-28 Exfoliation of graphene by multilayer coextrusion
US14/176,362 US9573312B2 (en) 2010-10-28 2014-02-10 Exfoliation of graphene by multilayer coextrusion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2010/054443 WO2012057762A1 (en) 2010-10-28 2010-10-28 Exfoliation of graphene by multilayer coextrusion

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US13/002,080 A-371-Of-International US8679290B2 (en) 2010-10-28 2010-10-28 Exfoliation of graphene by multilayer coextrusion
US14/176,362 Division US9573312B2 (en) 2010-10-28 2014-02-10 Exfoliation of graphene by multilayer coextrusion

Publications (1)

Publication Number Publication Date
WO2012057762A1 true WO2012057762A1 (en) 2012-05-03

Family

ID=45994232

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/054443 WO2012057762A1 (en) 2010-10-28 2010-10-28 Exfoliation of graphene by multilayer coextrusion

Country Status (3)

Country Link
US (2) US8679290B2 (und)
CN (1) CN103180244B (und)
WO (1) WO2012057762A1 (und)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105540574A (zh) * 2016-01-28 2016-05-04 成都新柯力化工科技有限公司 一种利用对喷式气流粉碎机制备石墨烯微片的方法
CN112645311A (zh) * 2020-12-15 2021-04-13 浙江工业大学 一种以超支化聚乙烯为助剂球磨法制备石墨烯的方法

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9227354B2 (en) * 2012-05-06 2016-01-05 Extend Optronics Corp. Feedblock multiplier with thickness gradient variation, feedblock system, method, and related multilayer structure
US9061806B2 (en) * 2012-08-30 2015-06-23 Thomas & Betts International, Llc Cable ties employing a nylon/graphene composite
CN104692363B (zh) * 2013-12-04 2017-02-15 北京化工大学 一种超重力法制备石墨烯的方法
TWI500515B (zh) * 2014-03-28 2015-09-21 Yeou Fu Lin 石墨片的製備方法及其系統
CN105271247B (zh) * 2015-10-09 2017-08-01 本益新材料股份公司 高性能石英砂及其制备方法
CN105271210B (zh) * 2015-11-27 2017-04-12 成都新柯力化工科技有限公司 一种通过热塑化石墨材料制备石墨烯的方法
CN105329886B (zh) * 2015-12-08 2017-07-25 成都新柯力化工科技有限公司 一种利用振动螺杆挤出机复合剪切应力剥离制备石墨烯的方法
CN105329887A (zh) * 2015-12-08 2016-02-17 成都新柯力化工科技有限公司 一种利用晶型诱导在螺杆挤出机中制备石墨烯的方法
CN105417534B (zh) * 2015-12-28 2017-08-29 成都新柯力化工科技有限公司 一种利用螺杆机制备生物质石墨烯材料的方法
CN105417535B (zh) * 2015-12-29 2017-05-31 成都新柯力化工科技有限公司 一种通过拉伸制备石墨烯材料的方法
CN105502367B (zh) * 2015-12-31 2017-09-22 成都新柯力化工科技有限公司 一种利用胶状物拉拔制备石墨烯的方法
CN105800545B (zh) * 2016-03-18 2019-01-18 北京化工大学 一种剥离制备二维材料的方法
CN107662321A (zh) * 2016-07-27 2018-02-06 东莞前沿技术研究院 阻隔膜的制备方法、阻隔膜、囊体与浮空器
CN106542523B (zh) * 2016-10-19 2019-02-01 成都新柯力化工科技有限公司 一种螺杆挤出制备石墨烯复合材料的成套装置及应用
CN106744887A (zh) * 2017-01-16 2017-05-31 湖南大学 一种石墨烯的制备方法
DE102018218603A1 (de) * 2018-10-30 2020-04-30 Bühler AG Kontinuierliche Herstellung von Graphen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5186919A (en) * 1988-11-21 1993-02-16 Battelle Memorial Institute Method for producing thin graphite flakes with large aspect ratios
US5468541A (en) * 1993-09-07 1995-11-21 United Microelectronics Corporation Thin film delamination test chip
EP1582572A1 (de) * 2004-04-02 2005-10-05 Henkel Kommanditgesellschaft auf Aktien Klebemittel für Fügeverbindungen
JP2008214434A (ja) * 2007-03-01 2008-09-18 Lintec Corp マーキングシート

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3801429A (en) 1969-06-06 1974-04-02 Dow Chemical Co Multilayer plastic articles
GB1313749A (en) * 1969-10-02 1973-04-18 Canadian Patents Dev Polymeric high performance composites
US5019446A (en) 1988-11-21 1991-05-28 Battelle Memorial Institute Enhancement of mechanical properties of polymers by thin flake addition and apparatus for producing such thin flakes
US4987175A (en) 1988-11-21 1991-01-22 Battelle Memorial Institute Enhancement of the mechanical properties by graphite flake addition
US5065948A (en) 1988-11-21 1991-11-19 Battelle Memorial Institute Apparatus for producing thin flakes
US5269995A (en) * 1992-10-02 1993-12-14 The Dow Chemical Company Coextrusion of multilayer articles using protective boundary layers and apparatus therefor
US6261674B1 (en) * 1998-12-28 2001-07-17 Kimberly-Clark Worldwide, Inc. Breathable microlayer polymer film and articles including same
US6808658B2 (en) * 1998-01-13 2004-10-26 3M Innovative Properties Company Method for making texture multilayer optical films
WO2003034514A2 (en) * 2001-10-12 2003-04-24 Koninklijke Philips Electronics N.V. A barrier and a method of manufacture thereof
US7303642B2 (en) * 2002-11-12 2007-12-04 Kimberly-Clark Worldwide, Inc. Methods of making responsive film with corrugated microlayers having improved properties
US7662321B2 (en) * 2005-10-26 2010-02-16 Nanotek Instruments, Inc. Nano-scaled graphene plate-reinforced composite materials and method of producing same
US8110026B2 (en) * 2006-10-06 2012-02-07 The Trustees Of Princeton University Functional graphene-polymer nanocomposites for gas barrier applications
CN101681056B (zh) * 2007-05-20 2013-03-27 3M创新有限公司 中空光循环腔型显示器背光源
CN201317092Y (zh) * 2008-11-21 2009-09-30 翁文桂 一种多层材料制备装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5186919A (en) * 1988-11-21 1993-02-16 Battelle Memorial Institute Method for producing thin graphite flakes with large aspect ratios
US5468541A (en) * 1993-09-07 1995-11-21 United Microelectronics Corporation Thin film delamination test chip
EP1582572A1 (de) * 2004-04-02 2005-10-05 Henkel Kommanditgesellschaft auf Aktien Klebemittel für Fügeverbindungen
JP2008214434A (ja) * 2007-03-01 2008-09-18 Lintec Corp マーキングシート

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105540574A (zh) * 2016-01-28 2016-05-04 成都新柯力化工科技有限公司 一种利用对喷式气流粉碎机制备石墨烯微片的方法
CN112645311A (zh) * 2020-12-15 2021-04-13 浙江工业大学 一种以超支化聚乙烯为助剂球磨法制备石墨烯的方法
CN112645311B (zh) * 2020-12-15 2022-02-11 浙江工业大学 一种以超支化聚乙烯为助剂球磨法制备石墨烯的方法

Also Published As

Publication number Publication date
US9573312B2 (en) 2017-02-21
US8679290B2 (en) 2014-03-25
CN103180244A (zh) 2013-06-26
US20140154166A1 (en) 2014-06-05
CN103180244B (zh) 2015-05-27
US20120103535A1 (en) 2012-05-03

Similar Documents

Publication Publication Date Title
US8679290B2 (en) Exfoliation of graphene by multilayer coextrusion
Yu et al. Hot-pressing induced alignment of boron nitride in polyurethane for composite films with thermal conductivity over 50 Wm− 1 K− 1
JP7575103B2 (ja) ナノグラファイトスポンジおよびその製造方法
JP5152711B2 (ja) 充填剤並びに非相溶性の樹脂若しくはエラストマーにより構成される構造体およびその製造方法若しくはその用途
EP2909028B1 (en) In situ exfoliation method to fabricate a graphene-reinforced polymer matrix composite
JP6484348B2 (ja) ホスト中でのグラフェンナノ粒子の均一な分散
CN103481393B (zh) 具有连续交替层状结构的聚合物材料及其制备方法
TWI352716B (und)
CN102837430A (zh) 一种可设计聚合物基导电复合材料的制备方法
CN103129070B (zh) 微纳多层复合介电材料及其制备方法及装置
JP7319198B2 (ja) 超臨界流体を使用してポリマー母材中に黒鉛材料を剥離し分散させる方法
Zhao et al. Fabrication of pristine graphene-based conductive polystyrene composites towards high performance and light-weight
Farahanchi et al. Extreme shear processing for exfoliating organoclay in nanocomposites with incompatible polymers
CN101217066A (zh) 层状聚合物基ptc材料及其制备方法
CN113799286A (zh) 一种分散相尺寸和维度可控的聚合物共混物制备方法
JP5167427B1 (ja) 樹脂多層成形体及びその製造方法
CN103059434A (zh) 一种高阻隔聚苯乙烯复合薄膜的制备方法
CN103333394A (zh) 一种可设计聚合物基功能膜的制备方法
CN111303521A (zh) 一种柔性高导热聚合物纳米复合膜及制备方法
CN107286607B (zh) 一种制备兼具优异水蒸气和氧气阻隔性能的交替层状生物降解高分子阻隔材料的方法
US20160090522A1 (en) Flexible heat-dissipating composite sheet including filler and low-viscosity polymerizable thermoplastic resin and cost effective mass producible method for preparing the same
EP3269544A1 (en) Organic-inorganic composite film, and multi-layer heat resistant separator material using same
CN108394078A (zh) 一种提高聚乳酸气体阻隔性的方法
CN106166880A (zh) 一种抗静电聚碳酸酯薄膜
JP6342102B2 (ja) シボ模様が形成された成形品の製造方法、及びシボ模様が形成された成形品

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 13002080

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10859077

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10859077

Country of ref document: EP

Kind code of ref document: A1