WO2021092788A1 - Method and apparatus for use in manufacturing graphene-modified fiber reinforced material - Google Patents

Method and apparatus for use in manufacturing graphene-modified fiber reinforced material Download PDF

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Publication number
WO2021092788A1
WO2021092788A1 PCT/CN2019/117976 CN2019117976W WO2021092788A1 WO 2021092788 A1 WO2021092788 A1 WO 2021092788A1 CN 2019117976 W CN2019117976 W CN 2019117976W WO 2021092788 A1 WO2021092788 A1 WO 2021092788A1
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Prior art keywords
graphene
fiber
resin
fiber bundle
fiber reinforced
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PCT/CN2019/117976
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French (fr)
Chinese (zh)
Inventor
孙建旭
梁嫄
马豪
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远景能源有限公司
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Priority to PCT/CN2019/117976 priority Critical patent/WO2021092788A1/en
Priority to CN201980042146.3A priority patent/CN113115589A/en
Publication of WO2021092788A1 publication Critical patent/WO2021092788A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
    • D06B23/14—Containers, e.g. vats
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
    • D06B23/20—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration, distillation
    • D06B23/22—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration, distillation for heating
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D06M15/51—Unsaturated polymerisable polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D1/00—Wind motors with rotation axis substantially parallel to the air flow entering the rotor 
    • F03D1/06—Rotors
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • the present invention generally relates to the field of wind power generators, and in particular, to a method for manufacturing graphene-modified fiber reinforced materials.
  • the present invention also relates to a device for manufacturing graphene-modified fiber reinforced materials.
  • the blades of a wind turbine are important components for wind turbines to capture wind energy.
  • the blades installed on the hub of the wind turbine rotate under the drive of wind energy to generate lift, which is further converted into torque through the transmission chain in the nacelle to drive the generator to generate electricity.
  • the larger the impeller formed by the blades the more wind energy can be captured. Therefore, the blades of the wind turbine have a tendency to become longer and longer, but this puts higher and higher requirements on the flapping rigidity of the blades, because the blades The longer it is, the greater the deformation. Therefore, a more efficient method is needed to increase the blade swing stiffness to avoid the risk of tower sweeping.
  • the shell generally has a sandwich panel composed of glass fiber reinforced plastic and a core material and a main bearing component—a main beam, where the main beam contributes about 90% of the overall swing rigidity.
  • the present invention provides a method and equipment for manufacturing graphene-modified fiber reinforced materials (or “materials” for short).
  • graphene can be easily introduced into This material makes the introduced graphene have the required concentration and is more evenly distributed among the fiber bundles or fiber filaments, thereby significantly improving the compressive strength of the fiber-reinforced composite material, thereby significantly improving the main bearing components of the blade (such as The strength of the main beam, etc.) reduces the sensitivity of the material strength to the manufacturing process; in addition, due to the more evenly distributed graphene, the conductivity of the material is significantly improved, thereby improving the lightning protection effect of the blade.
  • this task is solved by a method for manufacturing a graphene-modified fiber reinforced material, the method including the following steps:
  • the fiber bundle impregnated with the potting material is extruded to form the graphene-modified fiber reinforced material.
  • fiber bundle covers a bundle of multiple single fibers. Moreover, the fiber bundle may include one or more fibers.
  • the graphene is single-layer graphene or multi-layer graphene.
  • graphene may also exist in other forms, such as graphene-containing composites, graphene powder, graphene particles, and the like.
  • the method further includes the following steps:
  • the potting material is stirred in the potting tank.
  • the uniformity of graphene in the matrix can be further improved, thereby further improving the compressive strength of fibers, such as carbon fibers.
  • the volume of the glue filling tank is less than or equal to 100 liters, preferably less than or equal to 50 liters.
  • the fiber bundle includes one or more of the following: carbon fiber, glass fiber, aramid fiber, boron fiber, basalt fiber, and ultra-high modulus polyethylene fiber.
  • carbon fiber glass fiber
  • aramid fiber boron fiber
  • basalt fiber basalt fiber
  • ultra-high modulus polyethylene fiber under the teaching of the present invention, other fiber bundles can be used as needed in other embodiments.
  • the matrix includes one or more of the following: thermosetting epoxy resin, vinyl resin, unsaturated polyester resin, phenol resin, and thermoplastic resin.
  • thermosetting epoxy resin vinyl resin
  • unsaturated polyester resin unsaturated polyester resin
  • phenol resin unsaturated polyester resin
  • thermoplastic resin thermoplastic resin
  • other substrates can be used as needed, as long as the substrate can be coated on the fiber bundle to form the desired material.
  • the matrix is a resin.
  • thermoplastic resin includes one or more of the following: polypropylene resin, polyethylene resin, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile-butadiene resin Ethylene-styrene resin, polyamide resin, polyether ether ketone resin, and polyphenylene sulfide resin.
  • polypropylene resin polyethylene resin
  • polyvinyl chloride resin polystyrene resin
  • polyacrylonitrile-butadiene resin Ethylene-styrene resin
  • polyamide resin polyamide resin
  • polyether ether ketone resin polyphenylene sulfide resin
  • the graphene is a nanomaterial made of graphene.
  • the nanomaterial may have a desired shape, such as a spherical shape, a powder shape, a flake shape, and so on.
  • a desired shape such as a spherical shape, a powder shape, a flake shape, and so on.
  • the aforementioned task is solved by a device for manufacturing graphene-modified fiber reinforced materials, the device including:
  • a creel having a reel for winding the fiber bundle, wherein the reel is configured to rotate to convey the fiber bundle when the fiber bundle is pulled;
  • a pulling device which is configured to directly or indirectly pull the fiber bundle so that the fiber bundle is in a pulling state
  • An injection molding box having a glue tank for accommodating a potting material and a first adding device for adding graphene, wherein the injection box is configured to allow fiber bundles in a pulled state to pass through the glue tank, Enabling the infusion material to be coated on the fiber bundle, wherein the infusion material includes a matrix and graphene;
  • a forming device configured to extrude the fiber bundle coated with a potting material to form a graphene-modified fiber reinforced material.
  • the injection box further includes a second adding device for adding the matrix.
  • the matrix can be dynamically and automatically added to the injection box to ensure sufficient filling material.
  • the amount of matrix remaining in the injection box can be detected by a liquid level detection device, and automatically added when it is lower than the threshold, or The matrix can be added in real time according to the rate of matrix consumption.
  • a plurality of matrix injection directions can be set to form a vortex, so as to achieve sufficient mixing of the matrix and graphene.
  • the device further includes:
  • a heater configured to heat the formed graphene-modified fiber reinforced material
  • the curing chamber is configured to cure the heated graphene-modified fiber reinforced material.
  • a cutting device can also be provided to cut the material into a desired shape.
  • the device further includes a fiber bundle shaping frame, which is arranged between the creel and the injection box for adjusting the relative position between the fiber bundles.
  • a fiber bundle shaping frame which is arranged between the creel and the injection box for adjusting the relative position between the fiber bundles.
  • the relative position between the fiber bundles can be adjusted.
  • the fiber bundles can be evenly spaced, so that the resin layer thickness can be filled between the fiber bundles, thereby filling approximately the same graphene between them, thereby improving the properties of the material, such as compressive strength And conductivity.
  • the volume of the glue pot is less than or equal to 100 liters, preferably less than or equal to 50 liters.
  • the injection box further has a stirring device, and the stirring device is configured to uniformly distribute the graphene in the matrix.
  • the uniformity of graphene in the matrix can be further improved, thereby further improving the compressive strength of fibers, such as carbon fibers.
  • the present invention also relates to a graphene-modified fiber reinforced material, which is manufactured using the method according to the present invention.
  • the present invention also relates to a main beam for a wind turbine blade, which has the graphene-modified fiber reinforced material according to the present invention.
  • the present invention has at least the following beneficial effects: (1) By adding graphene between fiber bundles, especially carbon fiber fiber bundles, the interface performance between the fiber and the resin can be significantly improved, thereby improving the compressive strength of the composite material after molding, and at the same time Significantly improve the electrical conductivity of the material, thereby improving the lightning protection ability of the blade; (2) By dynamically adding graphene directly to the potting tank, it can significantly promote the uniform distribution of graphene among the fiber bundles, thereby ensuring uniformity This is based on the inventor’s insight as follows: The inventor found through research that an important reason why the strength of the main beam material is sensitive to the manufacturing process is that it is difficult for the existing mixing process to make the reinforcing particles (such as the present invention) The graphene used is uniformly distributed in the resin, and the uneven distribution of the reinforcing particles in the resin will cause the strength of the main beam material, especially the compressive strength, to change significantly (for example, the strength of the lower concentration of the reinforcing particles is also higher.
  • the graphene fed at a uniform speed can be evenly coated on the fiber bundles when distributed, or without stirring, which can ensure the required concentration and concentration of graphene compared with fully stirring in a large container in advance. Improve the uniformity of mixing and simplify the mixing process, which can improve the uniform distribution of graphene between fiber bundles, thereby increasing the compressive strength of the fiber bundles and reducing the sensitivity of the material to the process. At the same time, it also increases unexpectedly.
  • the conductivity of the material can be evenly coated on the fiber bundles when distributed, or without stirring, which can ensure the required concentration and concentration of graphene compared with fully stirring in a large container in advance.
  • Figure 1 shows a schematic diagram of an apparatus for manufacturing graphene-modified fiber reinforced materials according to the present invention
  • Figure 2 shows a cross-sectional view of a graphene-modified fiber reinforced material according to the present invention
  • Figure 3 shows a cross-sectional view of the main beam according to the present invention
  • Figure 4 shows a cross-sectional view of a fan blade according to the present invention.
  • Fig. 5 shows a flow chart of a method for manufacturing a graphene-modified fiber reinforced material according to the present invention.
  • the quantifiers "one” and “one” do not exclude the scenario of multiple elements.
  • the number of the steps of each method of the present invention does not limit the execution order of the method steps. Unless otherwise specified, the method steps can be performed in a different order.
  • the present invention is based on the inventor’s insight as follows:
  • the strength of the existing main beam material, especially the compressive strength, is sensitive to the manufacturing process. An important reason is that in the manufacturing process of the existing main beam material, the pouring material is very large.
  • the mixing is carried out in the container, and since the amount of reinforcing particles added in the large container is much smaller than the amount of resin, the distribution of the reinforcing particles in the resin is greatly dependent on the mixing process, and even if the mixing is for a long time It is still not necessarily evenly mixed, which results in a large change in the strength of the manufactured material; the inventor found through research that by dynamically adding graphene directly to the potting tank, the graphene can be significantly promoted between the fiber bundles.
  • Fig. 1 shows a schematic diagram of an apparatus 100 for manufacturing a graphene-modified fiber reinforced material according to the present invention.
  • the apparatus 100 for manufacturing graphene-modified fiber reinforced materials includes the following components (some of which are optional):
  • the creel 101 has a reel 102 for winding the fiber bundle.
  • the creel 101 has 12 reels 102. In other embodiments, other numbers of reels may be provided.
  • the creel 101 can be placed vertically or horizontally, and the reel 102 is arranged with its rotation axis perpendicular to the plane where the creel 101 is located.
  • the reel 102 is configured to rotate with the fiber bundles 103a, 103b being pulled to convey the fiber bundles 103a, 103b.
  • the spool 102 carries two different fiber bundles 103a and 103b. In other embodiments, more kinds or one kind of fiber bundles may be provided.
  • Different fiber bundles 103a and 103b can be distinguished in terms of their composition, thickness, or other parameters, for example.
  • the fiber bundles 103a and 103b include or are carbon fiber bundles, thereby improving the tensile strength and conductivity of the material. Improved electrical conductivity is beneficial to the lightning protection of the blade, because when lightning strikes the blade, the current can be grounded through the conductive material on the blade, thereby avoiding arcs or sparks.
  • a pulling device (not shown), which is configured to directly or indirectly pull the fiber bundles 103a, 103b to put the fiber bundles in a pulling state.
  • the pulling device may pull the fiber bundles 103a, 103b at the finished material 111 or other locations.
  • the pulling force may be so large that the fiber bundles 103a, 103b can be straightened and the reel 102 can be rotated at a desired speed to convey the fiber bundles 103a, 103b at the desired speed.
  • the pulling device may be, for example, a stepping motor, which pulls and drives the fiber bundles 103a, 103b to advance through a belt.
  • Optional fiber bundle shaping frame 104 which is arranged between the creel and the injection box for adjusting the relative position between the fiber bundles.
  • the relative position between the fiber bundles 103a and 103b or between the individual fibers of the fiber bundles 103a and 103b can be adjusted.
  • the fiber bundles can be evenly spaced, so that the resin layer thickness can be filled between the fiber bundles, thereby filling approximately the same graphene between them, thereby improving the properties of the material, such as compressive strength And conductivity.
  • the injection box 105 which has a glue tank (not shown) for containing the infusion material and a first adding device for adding graphene, wherein the injection box is configured to allow the fiber bundle in a pulled state to pass through Through the glue pot, the infusion material is coated on the fiber bundles 103a, 103b, wherein the infusion material includes resin 106 and graphene 107.
  • the graphene 107 may be a single-layer graphene or a multi-layer graphene.
  • the graphene 107 may also exist in other forms, such as graphene-containing composites, graphene powder, graphene particles, graphene nanomaterials, graphene solutions, and so on.
  • the graphene 107 is dynamically added into the injection box 105 by the first adding device, and the resin 106 is dynamically added into the injection box 105 by the second adding device.
  • the first and second addition devices are, for example, conveying pipes with electric pumps.
  • the numbers 106 and graphene 107 can be dynamically and automatically added to the injection box 105 to ensure sufficient filling material.
  • the amount of resin remaining in the injection box 105 can be detected by a liquid level detection device, and the resin can be automatically added when it is below a threshold, or the resin can be added in real time according to the resin consumption rate.
  • multiple resin conveying pipes with different input directions can be set to make the output resin form a vortex, so as to realize the full mixing of the resin and the graphene.
  • the fiber bundles 103a and 103b pass through the glue tank in the injection box 105 at a uniform speed, so that each fiber bundle can be sufficiently coated with the potting material, that is, the mixture of resin and graphene.
  • graphene 107 can be added at a uniform speed (that is, the same amount of graphene 107 is added per unit time, and the addition speed can be determined according to the required concentration of graphene 107 in the resin 106), so that the graphene 107 input at a uniform speed can be Coat evenly on the fiber bundle.
  • the graphene addition position is preferably close to the position where the fiber bundle contacts the potting material, so that the added graphene can be coated on the fiber bundle immediately.
  • the volume of the glue tank is less than or equal to 100 liters, preferably less than or equal to 50 liters, for example, 40 liters, 30 liters, and so on.
  • a forming device 109 configured to press the fiber bundles 103a, 103b coated with the potting material to form the graphene-modified fiber reinforced material 111.
  • the molding device 109 is, for example, a mold.
  • Optional heater 109 which is configured to heat the formed graphene-modified fiber reinforced material 111. Through the extrusion, the resin 106 and the graphene 107 will be more deeply filled between the fiber bundles 103a and 103b.
  • Optional curing chamber (not shown), which is configured to cure the heated graphene-modified fiber reinforced material.
  • the curing chamber is optional because curing can also be performed outside of the equipment.
  • FIG. 2 shows a cross-sectional view of the graphene-modified fiber reinforced material 111 according to the present invention.
  • the method and equipment manufacturing material 111 has better strength, especially compressive strength, and better conductivity, thereby providing better material quality and lightning protection capabilities.
  • Fig. 3 shows a cross-sectional view of the main beam 300 according to the present invention.
  • the main beam 300 includes two upper and lower layers of materials 111 according to the present invention, and a multilayer extruded plate 301 is arranged between the two layers of materials 111.
  • the pressing plate 301 is laid in two layers in the chord direction and four layers in the thickness direction.
  • other layers of extruded plates 301 may be laid in the two directions, or other layers of materials 111 may be arranged.
  • the strength, especially the compressive strength of the main beam 300 can be improved.
  • the material 111 has higher conductivity, so that the main beam 300 has higher conductivity, thereby improving the lightning protection capability of the blade.
  • Fig. 4 shows a cross-sectional view of a fan blade 400 according to the present invention.
  • the blade 400 includes a leading edge 401 and a trailing edge 405, as well as a pressure surface (PS surface) 402 and a suction surface (SS surface) 404.
  • the blade 400 also includes a main beam 300 as its main bearing structure, and also includes a web 403 for supporting the main beam 300.
  • the strength and conductivity of the main beam 300 can be significantly improved, thereby increasing the strength and conductivity of the entire blade 400.
  • FIG. 5 shows a process 500 of a method for manufacturing a graphene-modified fiber reinforced material according to the present invention.
  • the fiber bundle may include one or more fiber bundles.
  • step 504 the fiber bundle is pulled.
  • step 506 graphene is added to the potting tank so that the graphene and the matrix in the potting tank together form a potting material.
  • the addition is on-site and dynamic addition, which can increase the uniformity of graphene in the resin and simplify the addition and stirring procedures.
  • graphene 107 can be added at a uniform speed (that is, the same amount of graphene 107 is added per unit time, and the addition speed can be determined according to the required concentration of graphene 107 in the resin 106), so that the required concentration of graphene is guaranteed and
  • the graphene 107 fed at a constant speed can be uniformly coated on the fiber bundle.
  • the graphene addition position is preferably close to the position where the fiber bundle contacts the potting material, so that the added graphene can be coated on the fiber bundle immediately.
  • step 508 the fiber bundle in a stretched state is infiltrated into the potting material in the potting tank.
  • the fiber bundle can be pulled through the glue tank so that the infusion material in the glue tank is automatically and evenly applied to the fiber bundle, especially each fiber in the fiber bundle.
  • step 510 the fiber bundle impregnated with the potting material is extruded to form the graphene-modified fiber reinforced material.
  • the present invention has at least the following beneficial effects: (1) By adding graphene between fiber bundles, especially carbon fiber fiber bundles, the interface performance between the fiber and the resin can be significantly improved, thereby improving the compressive strength of the composite material after molding, and at the same time Significantly improve the electrical conductivity of the material, thereby improving the lightning protection ability of the blade; (2) By dynamically adding graphene directly to the potting tank, it can significantly promote the uniform distribution of graphene among the fiber bundles, thereby ensuring uniformity This is based on the inventor’s insight as follows: The inventor found through research that an important reason why the strength of the main beam material is sensitive to the manufacturing process is that it is difficult for the existing mixing process to make the reinforcing particles (such as the present invention) The graphene used is uniformly distributed in the resin, and the uneven distribution of the reinforcing particles in the resin will cause the strength of the main beam material, especially the compressive strength, to change significantly (for example, the strength of the lower concentration of the reinforcing particles is also higher.
  • the inventors unexpectedly found that compared with pre-mixing graphene and resin in a large container (such as a 2 ton capacity) , Dynamically adding graphene to a small-capacity glue tank (the capacity is generally less than 100L, preferably less than or equal to 50L), which will ensure the concentration of graphene in the resin and greatly improve the uniformity of graphene distribution in the resin and at the same time Simplify the mixing process.
  • a large container such as a 2 ton capacity

Abstract

The present invention relates to a method for use in manufacturing a graphene-modified fiber reinforced material, comprising the following steps: providing a fiber bundle; stretching the fiber bundle; adding graphene to an adhesive injection tank to allow the graphene and a matrix in the adhesive injection tank to form an injection material; wetting the fiber bundle in a stretched state with the injection material in the adhesive injection tank; and extruding the fiber bundle coated with the injection material to form the graphene-modified fiber reinforced material. The present invention also relates to an apparatus for use in manufacturing the graphene-modified fiber reinforced material. The present invention ensures the concentration and even distribution of the graphene being introduced, thus significantly increasing the compression strength of the fiber bundle, thereby significantly increasing the strength of the material and a main force-bearing component of a blade, and reducing the sensitivity of material strength with respect to the manufacturing process. In addition, owing to the evenly distributed graphene, the electrical conductivity of the material is significantly increased, thus increasing a lightening protection effect of the blade.

Description

一种用于制造石墨烯改性纤维增强材料的方法及设备Method and equipment for manufacturing graphene modified fiber reinforced material 技术领域Technical field
本发明总的来说涉及风力发电机领域，具体而言，涉及一种用于制造石墨烯改性纤维增强材料的方法。此外，本发明还涉及一种用于制造石墨烯改性纤维增强材料的设备。The present invention generally relates to the field of wind power generators, and in particular, to a method for manufacturing graphene-modified fiber reinforced materials. In addition, the present invention also relates to a device for manufacturing graphene-modified fiber reinforced materials.
背景技术Background technique
近年来，随着各国对环境的重视度提高，清洁能源领域呈现出快速发展的趋势。清洁能源作为一种新型能源，与传统化石燃料相比具有分布广泛、可再生、环境污染小等优点。作为清洁能源的代表，风力发电机的应用日益增长。In recent years, as countries pay more attention to the environment, the field of clean energy has shown a trend of rapid development. As a new type of energy, clean energy has the advantages of being widely distributed, renewable, and less environmentally polluting compared with traditional fossil fuels. As a representative of clean energy, the application of wind turbines is increasing day by day.
风力发电机的叶片是风力发电机捕捉风能的重要组件，其中安装在风机轮毂上的叶片在风能驱动下旋转以产生升力，通过机舱内的传动链进一步转化为转矩带动发电机发电。在相同情况下，叶片构成的叶轮越大，则能够捕捉的风能越多，因此风机的叶片有越来越长的趋势，但是这对叶片的挥舞刚度提出了越来越高的要求，因为叶片越长则变形越大，因此需要更高效的方法提升叶片挥舞刚度以避免扫塔风险。目前大多数叶片由两片壳体构成，所述壳体分为压力面和吸力面壳体。所述壳体一般具有由玻璃钢和芯材组成的夹层板和主承力部件——主梁，其中主梁贡献了整体挥舞刚度的约90％。The blades of a wind turbine are important components for wind turbines to capture wind energy. The blades installed on the hub of the wind turbine rotate under the drive of wind energy to generate lift, which is further converted into torque through the transmission chain in the nacelle to drive the generator to generate electricity. Under the same circumstances, the larger the impeller formed by the blades, the more wind energy can be captured. Therefore, the blades of the wind turbine have a tendency to become longer and longer, but this puts higher and higher requirements on the flapping rigidity of the blades, because the blades The longer it is, the greater the deformation. Therefore, a more efficient method is needed to increase the blade swing stiffness to avoid the risk of tower sweeping. At present, most blades are composed of two-piece shells, which are divided into pressure surface and suction surface shells. The shell generally has a sandwich panel composed of glass fiber reinforced plastic and a core material and a main bearing component—a main beam, where the main beam contributes about 90% of the overall swing rigidity.
为了提高主梁挥舞刚度，已经将碳纤维复合材料引入主梁。与碳纤维预浸料、碳纤维织物灌注相比，碳纤维拉挤工艺以其优异的性价比、稳定的工艺和质量控制，越来越多地应用于叶片行业。由于碳纤维复合材料的压缩强度远低于拉伸强度，因此提高压缩强度将有利于更高效地利用材料。然而，目前采用碳纤维的主梁的强度对制造工艺较为敏感、即主梁强度会因制造工艺的差异或公差而在较大范围内波动。而且鉴于叶片有日益加长的趋势，主梁的强度仍有进一步提升的必要。In order to improve the swing stiffness of the main beam, carbon fiber composite materials have been introduced into the main beam. Compared with carbon fiber prepreg and carbon fiber fabric infusion, the carbon fiber pultrusion process is increasingly used in the blade industry due to its excellent cost performance, stable process and quality control. Since the compressive strength of carbon fiber composites is much lower than the tensile strength, increasing the compressive strength will help to use the material more efficiently. However, the strength of the main beam currently using carbon fiber is more sensitive to the manufacturing process, that is, the strength of the main beam will fluctuate in a relatively large range due to differences or tolerances in the manufacturing process. Moreover, in view of the growing trend of blades, the strength of the main beam still needs to be further improved.
发明内容Summary of the invention
从现有技术出发，本发明提供了一种用于制造石墨烯改性纤维增强 材料(或简称“材料”)的方法及设备，通过该方法和/或该设备，可以方便地将石墨烯引入该材料并且使所引入的石墨烯具有所需浓度且更均匀地分布在各纤维束或纤维丝之间，从而显著地提高纤维增强复合材料的压缩强度，从而明显提高叶片主承力部件(如主梁等)的强度并减少材料强度对制造工艺的敏感性；此外，由于更均匀分布的石墨烯，该材料的导电性得到显著提高，从而改善叶片的避雷效果。Starting from the prior art, the present invention provides a method and equipment for manufacturing graphene-modified fiber reinforced materials (or “materials” for short). Through the method and/or the equipment, graphene can be easily introduced into This material makes the introduced graphene have the required concentration and is more evenly distributed among the fiber bundles or fiber filaments, thereby significantly improving the compressive strength of the fiber-reinforced composite material, thereby significantly improving the main bearing components of the blade (such as The strength of the main beam, etc.) reduces the sensitivity of the material strength to the manufacturing process; in addition, due to the more evenly distributed graphene, the conductivity of the material is significantly improved, thereby improving the lightning protection effect of the blade.
在本发明的第一方面，该任务通过一种用于制造石墨烯改性纤维增强材料的方法来解决，该方法包括下列步骤：In the first aspect of the present invention, this task is solved by a method for manufacturing a graphene-modified fiber reinforced material, the method including the following steps:
提供纤维束；Provide fiber bundles;
牵拉所述纤维束；Pulling the fiber bundle;
将石墨烯添加到灌胶槽以便使石墨烯与所述灌胶槽中的基质一起形成灌注材料；Adding graphene to the glue pot so that the graphene and the matrix in the glue pot together form a potting material;
在灌胶槽中将处于牵拉状态的纤维束浸润到灌注材料中；以及Infiltrate the stretched fiber bundle into the potting material in the potting tank; and
挤压浸润有灌注材料的纤维束以形成石墨烯改性纤维增强材料。The fiber bundle impregnated with the potting material is extruded to form the graphene-modified fiber reinforced material.
在此应当指出，在本发明中，术语“纤维束”涵盖了多个单根纤维的聚束。而且所述纤维束可以包含一种或多种纤维。It should be pointed out here that in the present invention, the term "fiber bundle" covers a bundle of multiple single fibers. Moreover, the fiber bundle may include one or more fibers.
在本发明的一个扩展方案中规定，所述石墨烯为单层石墨烯或多层石墨烯。另外，石墨烯也可以以其它形式存在、例如包含石墨烯的复合物、石墨烯粉末、石墨烯微粒等等。In an extended solution of the present invention, it is provided that the graphene is single-layer graphene or multi-layer graphene. In addition, graphene may also exist in other forms, such as graphene-containing composites, graphene powder, graphene particles, and the like.
在本发明的一个优选方案中规定，该方法还包括下列步骤：In a preferred solution of the present invention, it is stipulated that the method further includes the following steps:
在灌胶槽中对所述灌注材料进行搅拌。The potting material is stirred in the potting tank.
通过该优选方案，可以进一步提高石墨烯在基质中的均匀度，从而进一步提高纤维、如碳纤维的压缩强度。Through this preferred solution, the uniformity of graphene in the matrix can be further improved, thereby further improving the compressive strength of fibers, such as carbon fibers.
在本发明的另一优选方案中规定，所述灌胶槽的体积小于等于100升、优选小于等于50升。通过设置容量较小的灌胶槽，可以提高石墨烯的分布均匀度，从而进一步提高纤维、如碳纤维的压缩强度。In another preferred solution of the present invention, it is provided that the volume of the glue filling tank is less than or equal to 100 liters, preferably less than or equal to 50 liters. By setting a small-capacity glue tank, the distribution uniformity of graphene can be improved, thereby further improving the compressive strength of fibers, such as carbon fibers.
在本发明的一个扩展方案中规定，所述纤维束包括下列各项中的一个或多个：碳纤维、玻璃纤维、芳纶纤维、硼纤维、玄武岩纤维、以及超高模量聚乙烯纤维。在本发明的教导下，在其它实施例中可以根据需要采用其它纤维束。In an extended solution of the present invention, it is provided that the fiber bundle includes one or more of the following: carbon fiber, glass fiber, aramid fiber, boron fiber, basalt fiber, and ultra-high modulus polyethylene fiber. Under the teaching of the present invention, other fiber bundles can be used as needed in other embodiments.
在本发明的另一扩展方案中规定，所述基质包括下列各项中的一个或多个：热固性环氧树脂、乙烯基树脂、不饱和聚酯树脂、酚醛树脂、 以及热塑性树脂。在本发明的教导下，在其它实施例中可以根据需要采用其它基质，只要所述基质能够涂敷到纤维束上以形成所期望的材料。在一个优选方案中，所述基质为树脂。In another extension of the present invention, it is provided that the matrix includes one or more of the following: thermosetting epoxy resin, vinyl resin, unsaturated polyester resin, phenol resin, and thermoplastic resin. Under the teaching of the present invention, in other embodiments, other substrates can be used as needed, as long as the substrate can be coated on the fiber bundle to form the desired material. In a preferred embodiment, the matrix is a resin.
在本发明的又一扩展方案中规定，所述热塑性树脂包括下列各项中的一个或多个：聚丙烯树脂、聚乙烯树脂、聚氯乙烯树脂、聚苯乙烯树脂、聚丙烯腈-丁二烯-苯乙烯树脂、聚酰胺树脂、聚醚醚酮树脂、以及聚苯硫醚树脂。在本发明的教导下，在其它实施例中可以根据需要采用其它树脂作为基质。In another extension of the present invention, it is provided that the thermoplastic resin includes one or more of the following: polypropylene resin, polyethylene resin, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile-butadiene resin Ethylene-styrene resin, polyamide resin, polyether ether ketone resin, and polyphenylene sulfide resin. Under the teaching of the present invention, other resins can be used as the matrix as needed in other embodiments.
在本发明的一个优选方案中规定，所述石墨烯是由石墨烯制成的纳米材料。该纳米材料可以具有所期望的形状、如球形、粉末状、片状等等。通过采用由石墨烯制成的具有特定形状的纳米材料，可以制造具有不同物理特性、如不同压缩强度的材料。In a preferred embodiment of the present invention, it is specified that the graphene is a nanomaterial made of graphene. The nanomaterial may have a desired shape, such as a spherical shape, a powder shape, a flake shape, and so on. By using nanomaterials with specific shapes made of graphene, materials with different physical properties, such as different compressive strengths, can be manufactured.
在本发明的第二方面，前述任务通过一种用于制造石墨烯改性纤维增强材料的设备来解决，该设备包括：In the second aspect of the present invention, the aforementioned task is solved by a device for manufacturing graphene-modified fiber reinforced materials, the device including:
纱架，其具有用于缠绕纤维束的卷轴，其中所述卷轴被配置为在纤维束被牵拉的情况下旋转以输送纤维束；A creel having a reel for winding the fiber bundle, wherein the reel is configured to rotate to convey the fiber bundle when the fiber bundle is pulled;
牵拉装置，其被配置为直接或间接地牵拉纤维束以使纤维束处于牵拉状态；A pulling device, which is configured to directly or indirectly pull the fiber bundle so that the fiber bundle is in a pulling state;
注塑盒，其具有用于容纳灌注材料的灌胶槽以及用于添加石墨烯的第一添加装置，其中所述注塑盒被配置为允许处于牵拉状态的纤维束穿过所述灌胶槽，使得所述灌注材料被涂敷到所述纤维束上，其中所述灌注材料包含基质和石墨烯；以及An injection molding box having a glue tank for accommodating a potting material and a first adding device for adding graphene, wherein the injection box is configured to allow fiber bundles in a pulled state to pass through the glue tank, Enabling the infusion material to be coated on the fiber bundle, wherein the infusion material includes a matrix and graphene; and
成形装置，其被配置为对涂敷有灌注材料的纤维束进行挤压以形成石墨烯改性纤维增强材料。A forming device configured to extrude the fiber bundle coated with a potting material to form a graphene-modified fiber reinforced material.
在本发明的一个优选方案中规定，注塑盒还包括用于添加基质的第二添加装置。通过该优选方案，可以向注塑盒中动态地自动添加基质，从而保证充足的灌注材料，例如可以通过液面检测装置来检测注塑盒中剩余的基质的量，在低于阈值时自动添加，或者可以根据基质消耗速度实时地添加基质。在添加过程中可以通过设置多个基质注入方向以形成涡流，从而实现基质与石墨烯的充分混合。In a preferred embodiment of the present invention, it is provided that the injection box further includes a second adding device for adding the matrix. Through this preferred solution, the matrix can be dynamically and automatically added to the injection box to ensure sufficient filling material. For example, the amount of matrix remaining in the injection box can be detected by a liquid level detection device, and automatically added when it is lower than the threshold, or The matrix can be added in real time according to the rate of matrix consumption. During the addition process, a plurality of matrix injection directions can be set to form a vortex, so as to achieve sufficient mixing of the matrix and graphene.
在本发明的一个扩展方案中规定，该设备还包括：In an extended solution of the present invention, it is provided that the device further includes:
加热器，其被配置为对所形成的石墨烯改性纤维增强材料进行加 热；和/或A heater configured to heat the formed graphene-modified fiber reinforced material; and/or
固化室，其被配置为使经加热的石墨烯改性纤维增强材料固化。The curing chamber is configured to cure the heated graphene-modified fiber reinforced material.
通过该扩展方案，可以实现材料的加热和固化，从而实现加工的完全自动化。此外，还可以设置切割设备以将材料切割成所期望的形状。Through this expansion scheme, heating and curing of materials can be realized, thereby realizing complete automation of processing. In addition, a cutting device can also be provided to cut the material into a desired shape.
在本发明的一个优选方案中规定，该设备还包括纤维束整形架，所述纤维束整形架布置在纱架与注塑盒之间以用于调整纤维束之间的相对位置。通过采用整形架，可以实现纤维束之间的相对位置的调整。例如，可以使各纤维束均匀地间隔开，使得能够在各纤维束之间填充基本相同的树脂层厚，由此在它们之间填充大致相同的石墨烯，从而提高材料的性能、如压缩强度和导电性。In a preferred solution of the present invention, it is provided that the device further includes a fiber bundle shaping frame, which is arranged between the creel and the injection box for adjusting the relative position between the fiber bundles. By adopting the shaping frame, the relative position between the fiber bundles can be adjusted. For example, the fiber bundles can be evenly spaced, so that the resin layer thickness can be filled between the fiber bundles, thereby filling approximately the same graphene between them, thereby improving the properties of the material, such as compressive strength And conductivity.
在本发明的另一扩展方案中规定，所述灌胶槽的体积小于等于100升、优选小于等于50升。通过设置容量较小的灌胶槽，可以提高石墨烯的分布均匀度，从而进一步提高纤维、如碳纤维的压缩强度。In another extended solution of the present invention, it is provided that the volume of the glue pot is less than or equal to 100 liters, preferably less than or equal to 50 liters. By setting a small-capacity glue tank, the distribution uniformity of graphene can be improved, thereby further improving the compressive strength of fibers, such as carbon fibers.
在本发明的又一优选方案中规定，所述注塑盒还具有搅拌装置，所述搅拌装置被配置为使石墨烯均匀地分布在基质中。通过该优选方案，可以进一步提高石墨烯在基质中的均匀度，从而进一步提高纤维、如碳纤维的压缩强度。In yet another preferred solution of the present invention, it is provided that the injection box further has a stirring device, and the stirring device is configured to uniformly distribute the graphene in the matrix. Through this preferred solution, the uniformity of graphene in the matrix can be further improved, thereby further improving the compressive strength of fibers, such as carbon fibers.
此外，本发明还涉及一种石墨烯改性纤维增强材料，该材料是使用根据本发明的方法制造的。In addition, the present invention also relates to a graphene-modified fiber reinforced material, which is manufactured using the method according to the present invention.
另外，本发明还涉及一种用于风力发电机叶片的主梁，其具有根据本发明的石墨烯改性纤维增强材料。In addition, the present invention also relates to a main beam for a wind turbine blade, which has the graphene-modified fiber reinforced material according to the present invention.
本发明至少具有如下有益效果：(1)通过在纤维束、尤其是碳纤纤维束之间添加石墨烯，可以显著地提高纤维和树脂的界面性能，从而提高成型后复合材料的压缩强度，并同时显著提高材料的导电性，由此提高叶片防雷能力；(2)通过动态地将石墨烯直接添加到灌胶槽，可以显著地促进石墨烯在纤维束之间的均匀分布，从而保证均匀一致的压缩强度和导电性，这基于本发明人的如下洞察：本发明人通过研究发现，主梁材料的强度对制造工艺敏感的一个重要原因在于，现有搅拌工艺难以使增强颗粒(如本发明使用的石墨烯)均匀地分布在树脂中，而增强颗粒在树脂中的分布不均匀又会导致主梁材料的强度、尤其是压缩强度显著变化(例如增强颗粒浓度较低之处的强度也较低)，从而导致主梁材料的强度非常依赖于增强颗粒的均匀搅拌过程；同时，本发明人令人 意想不到地发现，与在大容器(如2吨容量)中预先混合石墨烯和树脂相比，动态地向小容量的灌胶槽(其容量一般小于100L、优选小于等于50L)中添加石墨烯，可以保证所引入的石墨烯在树脂中的浓度并且将极大地提高石墨烯在树脂中的分布均匀性并同时简化搅拌过程，这是因为在向小容量的灌胶槽中实时、动态地添加石墨烯时，通过添加石墨烯的初始流动速度或者稍加搅拌就可以实现石墨烯较均匀的分布，或者在不搅拌的情况下，匀速地输入的石墨烯即可均匀地被涂敷到纤维束上，这与预先在大容器中充分搅拌相比，既能保证石墨烯的所需浓度且提高搅拌均匀度，又简化了搅拌流程，由此可以提高石墨烯在纤维束之间的均匀分布，进而提高纤维束的压缩强度并降低了材料对工艺的敏感性，同时还令人意想不到地提高了材料的导电性。The present invention has at least the following beneficial effects: (1) By adding graphene between fiber bundles, especially carbon fiber fiber bundles, the interface performance between the fiber and the resin can be significantly improved, thereby improving the compressive strength of the composite material after molding, and at the same time Significantly improve the electrical conductivity of the material, thereby improving the lightning protection ability of the blade; (2) By dynamically adding graphene directly to the potting tank, it can significantly promote the uniform distribution of graphene among the fiber bundles, thereby ensuring uniformity This is based on the inventor’s insight as follows: The inventor found through research that an important reason why the strength of the main beam material is sensitive to the manufacturing process is that it is difficult for the existing mixing process to make the reinforcing particles (such as the present invention) The graphene used is uniformly distributed in the resin, and the uneven distribution of the reinforcing particles in the resin will cause the strength of the main beam material, especially the compressive strength, to change significantly (for example, the strength of the lower concentration of the reinforcing particles is also higher. Low), resulting in that the strength of the main beam material is very dependent on the uniform stirring process of the reinforcing particles; at the same time, the inventors unexpectedly found that compared with pre-mixing graphene and resin in a large container (such as a 2 ton capacity) , Dynamically add graphene to a small capacity glue tank (its capacity is generally less than 100L, preferably less than or equal to 50L), which can ensure the concentration of the introduced graphene in the resin and greatly improve the graphene in the resin Distribution uniformity and simplification of the stirring process at the same time, this is because when adding graphene to a small-capacity glue tank in real time and dynamically, by adding the initial flow rate of the graphene or a little stirring, the graphene can be more uniform. The graphene fed at a uniform speed can be evenly coated on the fiber bundles when distributed, or without stirring, which can ensure the required concentration and concentration of graphene compared with fully stirring in a large container in advance. Improve the uniformity of mixing and simplify the mixing process, which can improve the uniform distribution of graphene between fiber bundles, thereby increasing the compressive strength of the fiber bundles and reducing the sensitivity of the material to the process. At the same time, it also increases unexpectedly. The conductivity of the material.
附图说明Description of the drawings
下面结合具体实施方式参考附图进一步阐述本发明。The present invention will be further explained below with reference to the drawings in combination with specific embodiments.
图1示出了根据本发明的用于制造石墨烯改性纤维增强材料的设备的示意图；Figure 1 shows a schematic diagram of an apparatus for manufacturing graphene-modified fiber reinforced materials according to the present invention;
图2示出了根据本发明的石墨烯改性纤维增强材料的横截面图；Figure 2 shows a cross-sectional view of a graphene-modified fiber reinforced material according to the present invention;
图3示出了根据本发明的主梁的截面图；Figure 3 shows a cross-sectional view of the main beam according to the present invention;
图4示出了根据本发明的风机叶片的截面图；以及Figure 4 shows a cross-sectional view of a fan blade according to the present invention; and
图5示出了根据本发明的用于制造石墨烯改性纤维增强材料的方法的流程。Fig. 5 shows a flow chart of a method for manufacturing a graphene-modified fiber reinforced material according to the present invention.
具体实施方式Detailed ways
应当指出，各附图中的各组件可能为了图解说明而被夸大地示出，而不一定是比例正确的。在各附图中，给相同或功能相同的组件配备了相同的附图标记。It should be noted that the components in the drawings may be shown exaggeratedly for illustration purposes, and not necessarily in correct proportions. In the drawings, the same reference numerals are assigned to the same or the same components.
在本发明中，除非特别指出，“布置在…上”、“布置在…上方”以及“布置在…之上”并未排除二者之间存在中间物的情况。此外，“布置在…上或上方”仅仅表示两个部件之间的相对位置关系，而在一定情况下、如在颠倒产品方向后，也可以转换为“布置在…下或下方”，反之亦然。In the present invention, unless otherwise specified, "arranged on", "arranged on" and "arranged on" do not exclude the presence of intermediates between the two. In addition, "arranged on or above" only means the relative positional relationship between the two components, and under certain circumstances, such as inverting the product direction, it can also be converted to "arranged under or below", and vice versa. Of course.
在本发明中，各实施例仅仅旨在说明本发明的方案，而不应被理解 为限制性的。In the present invention, each embodiment is only intended to illustrate the solution of the present invention, and should not be construed as restrictive.
在本发明中，除非特别指出，量词“一个”、“一”并未排除多个元素的场景。In the present invention, unless otherwise specified, the quantifiers "one" and "one" do not exclude the scenario of multiple elements.
在此还应当指出，在本发明的实施例中，为清楚、简单起见，可能示出了仅仅一部分部件或组件，但是本领域的普通技术人员能够理解，在本发明的教导下，可根据具体场景需要添加所需的部件或组件。It should also be pointed out here that in the embodiments of the present invention, for clarity and simplicity, only a part of the parts or components may be shown, but those of ordinary skill in the art can understand that under the teaching of the present invention, the The scene needs to add required parts or components.
在此还应当指出，在本发明的范围内，“相同”、“相等”、“等于”等措辞并不意味着二者数值绝对相等，而是允许一定的合理误差，也就是说，所述措辞也涵盖了“基本上相同”、“基本上相等”、“基本上等于”。以此类推，在本发明中，表方向的术语“垂直于”、“平行于”等等同样涵盖了“基本上垂直于”、“基本上平行于”的含义。It should also be pointed out here that within the scope of the present invention, the terms "same", "equal", "equal to" and other terms do not mean that the values of the two are absolutely equal, but allow certain reasonable errors, that is, the The wording also covers "substantially the same", "substantially equal", and "substantially equal". By analogy, in the present invention, the terms "perpendicular to", "parallel to" and the like in the direction of the table also cover the meanings of "substantially perpendicular to" and "substantially parallel to".
另外，本发明的各方法的步骤的编号并未限定所述方法步骤的执行顺序。除非特别指出，各方法步骤可以以不同顺序执行。In addition, the number of the steps of each method of the present invention does not limit the execution order of the method steps. Unless otherwise specified, the method steps can be performed in a different order.
本发明基于发明人的如下洞察：现有的主梁材料的强度、尤其是压缩强度之所以对制造过程敏感，一个重要原因是，在现有主梁材料的制造过程中，灌注材料是在大容器中进行搅拌的，而由于在大容器中添加的增强颗粒的量与树脂的量相比少得多，这导致增强颗粒在树脂中的分布极大地依赖于搅拌过程，且即使混合较长时间仍然不一定混合均匀，因此导致所制造的材料的强度变化较大；本发明人通过研究发现，通过动态地将石墨烯直接添加到灌胶槽，可以显著地促进石墨烯在纤维束之间的均匀分布，由此进一步提高压缩强度并意想不到地提高了材料导电性，这基于本发明人的如下洞察；这是因为，与在大容器(如2吨容量)中预先混合石墨烯和树脂相比，动态地向小容量的灌胶槽(其容量一般小于100L、优选小于等于50L)中直接添加石墨烯，将保证石墨烯在树脂中的浓度并且极大地提高石墨烯在树脂中的分布均匀性并同时简化搅拌过程，这是因为在向小容量的灌胶槽中实时、动态地添加石墨烯时，通过添加石墨烯的初始流动速度或者稍加搅拌就可以实现石墨烯较均匀的分布，或者在不搅拌的情况下，匀速地输入的石墨烯即可均匀地被涂敷到纤维束上，这与预先在大容器中充分搅拌相比，既能保证石墨烯的所需浓度且提高搅拌均匀度，又简化了搅拌流程，由此可以提高石墨烯在纤维束之间的均匀分布，进而提高纤维束的压缩强度和材料的导电能力。The present invention is based on the inventor’s insight as follows: The strength of the existing main beam material, especially the compressive strength, is sensitive to the manufacturing process. An important reason is that in the manufacturing process of the existing main beam material, the pouring material is very large. The mixing is carried out in the container, and since the amount of reinforcing particles added in the large container is much smaller than the amount of resin, the distribution of the reinforcing particles in the resin is greatly dependent on the mixing process, and even if the mixing is for a long time It is still not necessarily evenly mixed, which results in a large change in the strength of the manufactured material; the inventor found through research that by dynamically adding graphene directly to the potting tank, the graphene can be significantly promoted between the fiber bundles. Uniform distribution, thereby further improving the compressive strength and unexpectedly improving the conductivity of the material, which is based on the following insights of the present inventor; this is because it is combined with the pre-mixing of graphene and resin in a large container (such as a 2 ton capacity) Compared with, dynamically adding graphene directly to a small-capacity glue tank (the capacity is generally less than 100L, preferably less than or equal to 50L), which will ensure the concentration of graphene in the resin and greatly improve the uniform distribution of graphene in the resin It also simplifies the mixing process. This is because when graphene is added to a small-capacity glue tank in real time and dynamically, a more uniform distribution of graphene can be achieved by adding the initial flow rate of the graphene or a little stirring. Or without stirring, the graphene fed at a uniform speed can be evenly coated on the fiber bundle. Compared with fully stirring in a large container in advance, this can ensure the required concentration of graphene and increase the stirring. The uniformity simplifies the stirring process, which can improve the uniform distribution of graphene among the fiber bundles, thereby improving the compressive strength of the fiber bundles and the conductivity of the material.
下面结合具体实施例和附图进一步阐述本发明。The present invention will be further described below in conjunction with specific embodiments and drawings.
图1示出了根据本发明的用于制造石墨烯改性纤维增强材料的设备100的示意图。Fig. 1 shows a schematic diagram of an apparatus 100 for manufacturing a graphene-modified fiber reinforced material according to the present invention.
如图1所示，根据本发明的用于制造石墨烯改性纤维增强材料(或简称“材料”)的设备100包括下列部件(其中一些部件是可选的)：As shown in Figure 1, the apparatus 100 for manufacturing graphene-modified fiber reinforced materials (or simply "materials") according to the present invention includes the following components (some of which are optional):
·纱架101，其具有用于缠绕纤维束的卷轴102。在本实施例中，纱架101具有12个卷轴102，在其它实施例中，可以设置其它数目的卷轴。纱架101可以竖直或水平放置，并且卷轴102被布置为其转轴垂直于纱架101所在的平面。卷轴102被配置为在纤维束103a、103b被牵拉的情况下旋转以输送纤维束103a、103b。在本实施例中，卷轴102承载有两种不同的纤维束103a、103b，在其它实施例中，也可以设置更多种或一种纤维束。不同的纤维束103a、103b例如可以在其成分、粗细度、或其它参数方面相区别。在一个优选的实施例中，纤维束103a、103b包括或者是碳纤维束，由此可以提高材料的拉伸强度和导电性。提高导电性有利于叶片的防雷，因为闪电在击中叶片时，电流可以通过叶片上的导电材料接地，从而避免产生电弧或火花。· The creel 101 has a reel 102 for winding the fiber bundle. In this embodiment, the creel 101 has 12 reels 102. In other embodiments, other numbers of reels may be provided. The creel 101 can be placed vertically or horizontally, and the reel 102 is arranged with its rotation axis perpendicular to the plane where the creel 101 is located. The reel 102 is configured to rotate with the fiber bundles 103a, 103b being pulled to convey the fiber bundles 103a, 103b. In this embodiment, the spool 102 carries two different fiber bundles 103a and 103b. In other embodiments, more kinds or one kind of fiber bundles may be provided. Different fiber bundles 103a and 103b can be distinguished in terms of their composition, thickness, or other parameters, for example. In a preferred embodiment, the fiber bundles 103a and 103b include or are carbon fiber bundles, thereby improving the tensile strength and conductivity of the material. Improved electrical conductivity is beneficial to the lightning protection of the blade, because when lightning strikes the blade, the current can be grounded through the conductive material on the blade, thereby avoiding arcs or sparks.
·牵拉装置(未示出)，其被配置为直接或间接地牵拉纤维束103a、103b以使纤维束处于牵拉状态。例如，牵拉装置可以在成品材料111或其它位置处牵拉纤维束103a、103b。在此，牵拉力可以大得以至于能够使纤维束103a、103b被拉直并且使卷轴102以所期望的速度转动以便以所期望的速度输送纤维束103a、103b。牵拉装置例如可以是步进电机，其通过皮带牵拉并带动纤维束103a、103b前进。A pulling device (not shown), which is configured to directly or indirectly pull the fiber bundles 103a, 103b to put the fiber bundles in a pulling state. For example, the pulling device may pull the fiber bundles 103a, 103b at the finished material 111 or other locations. Here, the pulling force may be so large that the fiber bundles 103a, 103b can be straightened and the reel 102 can be rotated at a desired speed to convey the fiber bundles 103a, 103b at the desired speed. The pulling device may be, for example, a stepping motor, which pulls and drives the fiber bundles 103a, 103b to advance through a belt.
·可选的纤维束整形架104，所述纤维束整形架布置在纱架与注塑盒之间以用于调整纤维束之间的相对位置。通过采用整形架104，可以实现纤维束103a、103b之间或纤维束103a、103b的单根纤维之间的相对位置的调整。例如，可以使各纤维束均匀地间隔开，使得能够在各纤维束之间填充基本相同的树脂层厚，由此在它们之间填充大致相同的石墨烯，从而提高材料的性能、如压缩强度和导电性。Optional fiber bundle shaping frame 104, which is arranged between the creel and the injection box for adjusting the relative position between the fiber bundles. By using the shaping frame 104, the relative position between the fiber bundles 103a and 103b or between the individual fibers of the fiber bundles 103a and 103b can be adjusted. For example, the fiber bundles can be evenly spaced, so that the resin layer thickness can be filled between the fiber bundles, thereby filling approximately the same graphene between them, thereby improving the properties of the material, such as compressive strength And conductivity.
·注塑盒105，其具有用于容纳灌注材料的灌胶槽(未示出)以及用于添加石墨烯的第一添加装置，其中所述注塑盒被配置为允许处于牵拉状态的纤维束穿过所述灌胶槽，使得所述灌注材料被涂敷到所述纤维束103a、103b上，其中所述灌注材料包含树脂106和石墨烯107。石墨烯 107可以为单层石墨烯或多层石墨烯。石墨烯107也可以以其它形式存在、例如包含石墨烯的复合物、石墨烯粉末、石墨烯微粒、石墨烯纳米材料、石墨烯溶液等等。在此，石墨烯107通过第一添加装置被动态地添加到注塑盒105中，并且树脂106通过第二添加装置被动态地添加到注塑盒105中。第一和第二添加装置例如是带有电泵的输送管道。通过第一和第二添加装置，可以向注塑盒105中动态地自动添加数字106和石墨烯107，从而保证充足的灌注材料。例如可以通过液面检测装置来检测注塑盒105中剩余的树脂的量，在低于阈值时自动添加树脂，或者可以根据树脂消耗速度实时地添加树脂。在添加过程中可以通过设置多个具有不同输入方向的树脂输送管道以使得所输出的树脂形成涡流，从而实现树脂与石墨烯的充分混合。在本实施例中，纤维束103a、103b以匀速通过注塑盒105中的灌胶槽，使得每个纤维束都能被充分地涂敷灌注材料、即树脂与石墨烯的混合物。例如，可以匀速地添加石墨烯107(即单位时间内添加相同量的石墨烯107，添加速度可以根据石墨烯107在树脂106中的所需浓度来确定)，使得匀速输入的石墨烯107可以被均匀地涂敷到纤维束上。在这种情况下，石墨烯的添加位置优选地接近纤维束接触灌注材料的位置，使得添加的石墨烯能够即时地被涂敷到纤维束上。灌胶槽的体积小于等于100升、优选小于等于50升、例如为40升、30升等等。通过设置容量较小的灌胶槽并且动态添加石墨烯，可以提高石墨烯的分布均匀度，从而进一步提高纤维、如碳纤维的压缩强度。这是因为，与在大容器(如2吨容量)中预先混合石墨烯和树脂相比，动态地向小容量的灌胶槽(其容量一般小于100L、优选小于等于50L)中直接添加石墨烯，将保证石墨烯在树脂中的浓度并且极大地提高石墨烯在树脂中的分布均匀性并同时简化搅拌过程，这是因为在向小容量的灌胶槽中实时、动态地添加石墨烯时，通过添加石墨烯的初始流动速度或者稍加搅拌就可以实现石墨烯较均匀的分布，或者在不搅拌的情况下，匀速地输入的石墨烯即可均匀地被涂敷到纤维束上，这与预先在大容器中充分搅拌相比，既能保证石墨烯的所需浓度且提高搅拌均匀度，又简化了搅拌流程，由此可以提高石墨烯在纤维束之间的均匀分布，进而提高纤维束的压缩强度和材料的导电能力。· The injection box 105, which has a glue tank (not shown) for containing the infusion material and a first adding device for adding graphene, wherein the injection box is configured to allow the fiber bundle in a pulled state to pass through Through the glue pot, the infusion material is coated on the fiber bundles 103a, 103b, wherein the infusion material includes resin 106 and graphene 107. The graphene 107 may be a single-layer graphene or a multi-layer graphene. The graphene 107 may also exist in other forms, such as graphene-containing composites, graphene powder, graphene particles, graphene nanomaterials, graphene solutions, and so on. Here, the graphene 107 is dynamically added into the injection box 105 by the first adding device, and the resin 106 is dynamically added into the injection box 105 by the second adding device. The first and second addition devices are, for example, conveying pipes with electric pumps. Through the first and second adding devices, the numbers 106 and graphene 107 can be dynamically and automatically added to the injection box 105 to ensure sufficient filling material. For example, the amount of resin remaining in the injection box 105 can be detected by a liquid level detection device, and the resin can be automatically added when it is below a threshold, or the resin can be added in real time according to the resin consumption rate. During the addition process, multiple resin conveying pipes with different input directions can be set to make the output resin form a vortex, so as to realize the full mixing of the resin and the graphene. In this embodiment, the fiber bundles 103a and 103b pass through the glue tank in the injection box 105 at a uniform speed, so that each fiber bundle can be sufficiently coated with the potting material, that is, the mixture of resin and graphene. For example, graphene 107 can be added at a uniform speed (that is, the same amount of graphene 107 is added per unit time, and the addition speed can be determined according to the required concentration of graphene 107 in the resin 106), so that the graphene 107 input at a uniform speed can be Coat evenly on the fiber bundle. In this case, the graphene addition position is preferably close to the position where the fiber bundle contacts the potting material, so that the added graphene can be coated on the fiber bundle immediately. The volume of the glue tank is less than or equal to 100 liters, preferably less than or equal to 50 liters, for example, 40 liters, 30 liters, and so on. By setting a small-capacity glue tank and dynamically adding graphene, the distribution uniformity of graphene can be improved, thereby further improving the compressive strength of fibers, such as carbon fibers. This is because, compared with pre-mixing graphene and resin in a large container (such as 2 tons capacity), graphene is directly added to a small-capacity glue tank (the capacity is generally less than 100L, preferably less than or equal to 50L). , It will ensure the concentration of graphene in the resin and greatly improve the uniformity of graphene distribution in the resin while simplifying the mixing process. This is because when graphene is added to a small-capacity glue tank in real time and dynamically, The graphene can be distributed more uniformly by adding the initial flow rate of the graphene or stirring slightly, or without stirring, the graphene fed at a uniform speed can be evenly coated on the fiber bundle, which is the same as Fully stirring in a large container in advance can not only ensure the required concentration of graphene and improve the uniformity of stirring, but also simplify the stirring process, which can improve the uniform distribution of graphene among the fiber bundles, thereby increasing the fiber bundles. The compressive strength and conductivity of the material.
·成形装置109，其被配置为对涂敷有灌注材料的纤维束103a、103b进行挤压以形成石墨烯改性纤维增强材料111。成型装置109例如为模 具。A forming device 109 configured to press the fiber bundles 103a, 103b coated with the potting material to form the graphene-modified fiber reinforced material 111. The molding device 109 is, for example, a mold.
·可选的加热器109，其被配置为对所形成的石墨烯改性纤维增强材料111进行加热。通过所述挤压，树脂106和石墨烯107将更加深入地填充到纤维束103a、103b之间。 Optional heater 109, which is configured to heat the formed graphene-modified fiber reinforced material 111. Through the extrusion, the resin 106 and the graphene 107 will be more deeply filled between the fiber bundles 103a and 103b.
·可选的固化室(未示出)，其被配置为使经加热的石墨烯改性纤维增强材料固化。固化室是可选的，因为固化也可以在设备之外进行。• Optional curing chamber (not shown), which is configured to cure the heated graphene-modified fiber reinforced material. The curing chamber is optional because curing can also be performed outside of the equipment.
图2示出了根据本发明的石墨烯改性纤维增强材料111的横截面图。FIG. 2 shows a cross-sectional view of the graphene-modified fiber reinforced material 111 according to the present invention.
如图2所示，在材料111中，分布有两种纤维束103a、103b，在其它实施例中，更少或更多种类的纤维束也是可设想的。在纤维束103a、103b之间填充有石墨烯107与树脂106的混合物，其中石墨烯107均匀地分布在所述混合物中。由此，根据本发明的方法和设备制造材料111具有较好的强度、尤其是压缩强度以及较好的导电性，由此提供更好的材料质量和防雷能力。As shown in Fig. 2, in the material 111, two types of fiber bundles 103a and 103b are distributed. In other embodiments, fewer or more types of fiber bundles are also conceivable. A mixture of graphene 107 and resin 106 is filled between the fiber bundles 103a and 103b, wherein the graphene 107 is uniformly distributed in the mixture. Therefore, the method and equipment manufacturing material 111 according to the present invention has better strength, especially compressive strength, and better conductivity, thereby providing better material quality and lightning protection capabilities.
图3示出了根据本发明的主梁300的截面图。Fig. 3 shows a cross-sectional view of the main beam 300 according to the present invention.
如图3所示，主梁300包括上下两层根据本发明的材料111，并且在两层材料111之间布置有多层挤压板301。在此，挤压板301沿弦向铺设两层并且沿厚度方向铺设四层。在其它实施例中，可以在所述两个方向上铺设其它层数的挤压板301，也可以布置其它层数的材料111。从图3中可以得知，通过采用根据本发明的材料111，可以提高主梁300的强度、尤其是压缩强度。此外，由于纤维束之间的更均匀分布的石墨烯，材料111具有更高的导电性，使得主梁300具有更高的导电性，从而提高叶片的防雷能力。As shown in FIG. 3, the main beam 300 includes two upper and lower layers of materials 111 according to the present invention, and a multilayer extruded plate 301 is arranged between the two layers of materials 111. Here, the pressing plate 301 is laid in two layers in the chord direction and four layers in the thickness direction. In other embodiments, other layers of extruded plates 301 may be laid in the two directions, or other layers of materials 111 may be arranged. It can be seen from FIG. 3 that by using the material 111 according to the present invention, the strength, especially the compressive strength of the main beam 300 can be improved. In addition, due to the more evenly distributed graphene between the fiber bundles, the material 111 has higher conductivity, so that the main beam 300 has higher conductivity, thereby improving the lightning protection capability of the blade.
图4示出了根据本发明的风机叶片400的截面图。Fig. 4 shows a cross-sectional view of a fan blade 400 according to the present invention.
如图4所示，叶片400包括前缘401和尾缘405、以及压力面(PS面)402和吸力面(SS面)404。叶片400还包括主梁300作为其主承力结构，并且还包括用于支撑主梁300的腹板403。在此，通过采用具有材料111的主梁300，可以显著提高主梁300的强度和导电性，由此提高整个叶片400的强度和导电性。As shown in FIG. 4, the blade 400 includes a leading edge 401 and a trailing edge 405, as well as a pressure surface (PS surface) 402 and a suction surface (SS surface) 404. The blade 400 also includes a main beam 300 as its main bearing structure, and also includes a web 403 for supporting the main beam 300. Here, by using the main beam 300 with the material 111, the strength and conductivity of the main beam 300 can be significantly improved, thereby increasing the strength and conductivity of the entire blade 400.
图5示出了根据本发明的用于制造石墨烯改性纤维增强材料的方法的流程500。FIG. 5 shows a process 500 of a method for manufacturing a graphene-modified fiber reinforced material according to the present invention.
在步骤502提供纤维束。纤维束可以包括一种或多种纤维束。In step 502, a fiber bundle is provided. The fiber bundle may include one or more fiber bundles.
在步骤504，牵拉所述纤维束。In step 504, the fiber bundle is pulled.
在步骤506，将石墨烯添加到灌胶槽以便使石墨烯与所述灌胶槽中的基质一起形成灌注材料。该添加为现场、动态添加，由此可增加石墨烯在树脂中的均匀性并简化添加和搅拌工序。例如，可以匀速地添加石墨烯107(即单位时间内添加相同量的石墨烯107，添加速度可以根据石墨烯107在树脂106中的所需浓度来确定)，使得保证石墨烯的所需浓度且匀速输入的石墨烯107可以被均匀地涂敷到纤维束上。在这种情况下，石墨烯的添加位置优选地接近纤维束接触灌注材料的位置，使得添加的石墨烯能够即时地被涂敷到纤维束上。In step 506, graphene is added to the potting tank so that the graphene and the matrix in the potting tank together form a potting material. The addition is on-site and dynamic addition, which can increase the uniformity of graphene in the resin and simplify the addition and stirring procedures. For example, graphene 107 can be added at a uniform speed (that is, the same amount of graphene 107 is added per unit time, and the addition speed can be determined according to the required concentration of graphene 107 in the resin 106), so that the required concentration of graphene is guaranteed and The graphene 107 fed at a constant speed can be uniformly coated on the fiber bundle. In this case, the graphene addition position is preferably close to the position where the fiber bundle contacts the potting material, so that the added graphene can be coated on the fiber bundle immediately.
在步骤508，在灌胶槽中将处于牵拉状态的纤维束浸润到灌注材料中。例如，可以将纤维束牵拉经过灌胶槽，使得灌胶槽中的灌注材料自动、均匀地涂敷到纤维束上、尤其是纤维束中的每根纤维上。In step 508, the fiber bundle in a stretched state is infiltrated into the potting material in the potting tank. For example, the fiber bundle can be pulled through the glue tank so that the infusion material in the glue tank is automatically and evenly applied to the fiber bundle, especially each fiber in the fiber bundle.
在步骤510，挤压浸润有灌注材料的纤维束以形成石墨烯改性纤维增强材料。In step 510, the fiber bundle impregnated with the potting material is extruded to form the graphene-modified fiber reinforced material.
本发明至少具有如下有益效果：(1)通过在纤维束、尤其是碳纤纤维束之间添加石墨烯，可以显著地提高纤维和树脂的界面性能，从而提高成型后复合材料的压缩强度，并同时显著提高材料的导电性，由此提高叶片防雷能力；(2)通过动态地将石墨烯直接添加到灌胶槽，可以显著地促进石墨烯在纤维束之间的均匀分布，从而保证均匀一致的压缩强度和导电性，这基于本发明人的如下洞察：本发明人通过研究发现，主梁材料的强度对制造工艺敏感的一个重要原因在于，现有搅拌工艺难以使增强颗粒(如本发明使用的石墨烯)均匀地分布在树脂中，而增强颗粒在树脂中的分布不均匀又会导致主梁材料的强度、尤其是压缩强度显著变化(例如增强颗粒浓度较低之处的强度也较低)，从而导致主梁材料的强度非常依赖于增强颗粒的均匀搅拌过程；同时，本发明人令人意想不到地发现，与在大容器(如2吨容量)中预先混合石墨烯和树脂相比，动态地向小容量的灌胶槽(其容量一般小于100L、优选小于等于50L)中添加石墨烯，将保证石墨烯在树脂中浓度并且极大地提高石墨烯在树脂中的分布均匀性并同时简化搅拌过程，这是因为在向小容量的灌胶槽中实时、动态地添加石墨烯时，通过添加石墨烯的初始流动速度或者稍加搅拌就可以实现石墨烯较均匀的分布，或者在不搅拌的情况下，匀速地输入的石墨烯即可均匀地被涂敷到纤维束上，这与预先在大 容器中充分搅拌相比，既能保证石墨烯的所需浓度且提高搅拌均匀度，又简化了搅拌流程，由此可以提高石墨烯在纤维束之间的均匀分布，进而提高纤维束的压缩强度并降低了材料对工艺的敏感性，同时还令人意想不到地提高了材料的导电性。The present invention has at least the following beneficial effects: (1) By adding graphene between fiber bundles, especially carbon fiber fiber bundles, the interface performance between the fiber and the resin can be significantly improved, thereby improving the compressive strength of the composite material after molding, and at the same time Significantly improve the electrical conductivity of the material, thereby improving the lightning protection ability of the blade; (2) By dynamically adding graphene directly to the potting tank, it can significantly promote the uniform distribution of graphene among the fiber bundles, thereby ensuring uniformity This is based on the inventor’s insight as follows: The inventor found through research that an important reason why the strength of the main beam material is sensitive to the manufacturing process is that it is difficult for the existing mixing process to make the reinforcing particles (such as the present invention) The graphene used is uniformly distributed in the resin, and the uneven distribution of the reinforcing particles in the resin will cause the strength of the main beam material, especially the compressive strength, to change significantly (for example, the strength of the lower concentration of the reinforcing particles is also higher. Low), resulting in that the strength of the main beam material is very dependent on the uniform stirring process of the reinforcing particles; at the same time, the inventors unexpectedly found that compared with pre-mixing graphene and resin in a large container (such as a 2 ton capacity) , Dynamically adding graphene to a small-capacity glue tank (the capacity is generally less than 100L, preferably less than or equal to 50L), which will ensure the concentration of graphene in the resin and greatly improve the uniformity of graphene distribution in the resin and at the same time Simplify the mixing process. This is because when graphene is added to a small-capacity glue tank in real time and dynamically, a more uniform distribution of graphene can be achieved by adding the initial flow rate of the graphene or a little stirring, or when the graphene is not In the case of stirring, the graphene input at a uniform speed can be evenly coated on the fiber bundle. Compared with fully stirring in a large container in advance, this can ensure the required concentration of graphene and improve the uniformity of stirring. It also simplifies the stirring process, which can improve the uniform distribution of graphene between the fiber bundles, thereby increasing the compressive strength of the fiber bundles and reducing the sensitivity of the material to the process, while also unexpectedly improving the conductivity of the material .
虽然本发明的一些实施方式已经在本申请文件中予以了描述，但是本领域技术人员能够理解，这些实施方式仅仅是作为示例示出的。本领域技术人员在本发明的教导下可以想到众多的变型方案、替代方案和改进方案而不超出本发明的范围。所附权利要求书旨在限定本发明的范围，并由此涵盖这些权利要求本身及其等同变换的范围内的方法和结构。Although some embodiments of the present invention have been described in this application document, those skilled in the art can understand that these embodiments are only shown as examples. Under the teaching of the present invention, those skilled in the art can think of numerous variations, alternatives and improvements without going beyond the scope of the present invention. The appended claims are intended to define the scope of the present invention, and thus cover methods and structures within the scope of these claims and their equivalents.

Claims (16)

  1. 一种用于制造石墨烯改性纤维增强材料的方法，包括下列步骤：A method for manufacturing graphene modified fiber reinforced materials, including the following steps:
    提供纤维束；Provide fiber bundles;
    牵拉所述纤维束；Pulling the fiber bundle;
    将石墨烯添加到灌胶槽以便使石墨烯与所述灌胶槽中的基质一起形成灌注材料；Adding graphene to the glue pot so that the graphene and the matrix in the glue pot together form a potting material;
    在灌胶槽中将处于牵拉状态的纤维束浸润到灌注材料中；以及Infiltrate the stretched fiber bundle into the potting material in the potting tank; and
    挤压浸润有灌注材料的纤维束以形成石墨烯改性纤维增强材料。The fiber bundle impregnated with the potting material is extruded to form the graphene-modified fiber reinforced material.
  2. 根据权利要求1所述的方法，其中所述石墨烯为单层石墨烯或多层石墨烯。The method according to claim 1, wherein the graphene is single-layer graphene or multi-layer graphene.
  3. 根据权利要求1所述的方法，还包括下列步骤：The method according to claim 1, further comprising the following steps:
    在灌胶槽中对所述灌注材料进行搅拌。The potting material is stirred in the potting tank.
  4. 根据权利要求1所述的方法，其中所述灌胶槽的体积小于等于100升、优选小于等于50升。The method according to claim 1, wherein the volume of the glue tank is less than or equal to 100 liters, preferably less than or equal to 50 liters.
  5. 根据权利要求1所述的方法，其中所述纤维束包括下列各项中的一个或多个：碳纤维、玻璃纤维、芳纶纤维、硼纤维、玄武岩纤维、以及超高模量聚乙烯纤维。The method according to claim 1, wherein the fiber bundle includes one or more of the following: carbon fiber, glass fiber, aramid fiber, boron fiber, basalt fiber, and ultra-high modulus polyethylene fiber.
  6. 根据权利要求1所述的方法，其中所述基质包括下列各项中的一个或多个：热固性环氧树脂、乙烯基树脂、不饱和聚酯树脂、酚醛树脂、以及热塑性树脂。The method of claim 1, wherein the matrix includes one or more of the following: thermosetting epoxy resin, vinyl resin, unsaturated polyester resin, phenol resin, and thermoplastic resin.
  7. 根据权利要求6所述的方法，其中所述热塑性树脂包括下列各项中的一个或多个：聚丙烯树脂、聚乙烯树脂、聚氯乙烯树脂、聚苯乙烯树脂、聚丙烯腈-丁二烯-苯乙烯树脂、聚酰胺树脂、聚醚醚酮树脂、以及聚苯硫醚树脂。The method according to claim 6, wherein the thermoplastic resin comprises one or more of the following: polypropylene resin, polyethylene resin, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile-butadiene -Styrene resin, polyamide resin, polyether ether ketone resin, and polyphenylene sulfide resin.
  8. 根据权利要求1所述的方法，其中所述石墨烯是由石墨烯制成的纳米材料。The method according to claim 1, wherein the graphene is a nanomaterial made of graphene.
  9. 一种用于制造石墨烯改性纤维增强材料的设备，包括：An equipment for manufacturing graphene-modified fiber reinforced materials, including:
    纱架，其具有用于缠绕纤维束的卷轴，其中所述卷轴被配置为在纤维束被牵拉的情况下旋转以输送纤维束；A creel having a reel for winding the fiber bundle, wherein the reel is configured to rotate to convey the fiber bundle when the fiber bundle is pulled;
    牵拉装置，其被配置为直接或间接地牵拉纤维束以使纤维束处于牵拉状态；A pulling device, which is configured to directly or indirectly pull the fiber bundle so that the fiber bundle is in a pulling state;
    注塑盒，其具有用于容纳灌注材料的灌胶槽以及用于添加石墨烯的 第一添加装置，其中所述注塑盒被配置为允许处于牵拉状态的纤维束穿过所述灌胶槽，使得所述灌注材料浸润到所述纤维束上，其中所述灌注材料包含基质和石墨烯；以及An injection molding box having a glue tank for accommodating a potting material and a first adding device for adding graphene, wherein the injection box is configured to allow fiber bundles in a pulled state to pass through the glue tank, Causing the infusion material to infiltrate the fiber bundle, wherein the infusion material includes a matrix and graphene; and
    成形装置，其被配置为对涂敷有灌注材料的纤维束进行挤压以形成石墨烯改性纤维增强材料。A forming device configured to extrude the fiber bundle coated with a potting material to form a graphene-modified fiber reinforced material.
  10. 根据权利要求9所述的设备，其中注塑盒还包括用于添加基质的第二添加装置。9. The apparatus according to claim 9, wherein the injection box further comprises a second adding device for adding the matrix.
  11. 根据权利要求9所述的设备，还包括：The device according to claim 9, further comprising:
    加热器，其被配置为对所形成的石墨烯改性纤维增强材料进行加热；和/或A heater configured to heat the formed graphene-modified fiber reinforced material; and/or
    固化室，其被配置为使经加热的石墨烯改性纤维增强材料固化。The curing chamber is configured to cure the heated graphene-modified fiber reinforced material.
  12. 根据权利要求9所述的设备，还包括纤维束整形架，所述纤维束整形架布置在纱架与注塑盒之间以用于调整纤维束之间的相对位置。9. The apparatus according to claim 9, further comprising a fiber bundle shaping frame arranged between the creel and the injection box for adjusting the relative position between the fiber bundles.
  13. 根据权利要求9所述的设备，其中所述灌胶槽的体积小于等于100升、优选小于等于50升。The device according to claim 9, wherein the volume of the glue tank is less than or equal to 100 liters, preferably less than or equal to 50 liters.
  14. 根据权利要求9所述的设备，其中所述注塑盒还具有搅拌装置，所述搅拌装置被配置为使石墨烯均匀地分布在基质中。9. The apparatus according to claim 9, wherein the injection box further has a stirring device configured to uniformly distribute the graphene in the matrix.
  15. 一种使用根据权利要求1至8之一所述的方法制造的石墨烯改性纤维增强材料。A graphene-modified fiber reinforced material manufactured using the method according to any one of claims 1 to 8.
  16. 一种用于风力发电机叶片的主梁，其具有根据权利要求15所述的石墨烯改性纤维增强材料。A main beam for a wind turbine blade, which has the graphene-modified fiber reinforced material according to claim 15.
PCT/CN2019/117976 2019-11-13 2019-11-13 Method and apparatus for use in manufacturing graphene-modified fiber reinforced material WO2021092788A1 (en)

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