CN112176499A - Three-dimensional fabric reinforcement, preparation method thereof and polymer-based composite material - Google Patents

Three-dimensional fabric reinforcement, preparation method thereof and polymer-based composite material Download PDF

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CN112176499A
CN112176499A CN201910603206.6A CN201910603206A CN112176499A CN 112176499 A CN112176499 A CN 112176499A CN 201910603206 A CN201910603206 A CN 201910603206A CN 112176499 A CN112176499 A CN 112176499A
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fibers
polymer
composite material
dimensional
fiber
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王绍凯
李敏
陈昭玲
顾轶卓
张佐光
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Beihang University
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Beihang University
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    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D25/00—Woven fabrics not otherwise provided for
    • D03D25/005—Three-dimensional woven fabrics
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • 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
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
    • 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
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
    • D10B2101/06—Glass
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Woven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention relates to the technical field of composite materials with heat conduction functions, in particular to a three-dimensional fabric reinforcement, a preparation method thereof and a polymer matrix composite material. The three-dimensional fabric reinforcement provided by the invention has a three-way orthogonal structure, wherein the plane is in the X direction and the Y direction, the thickness is in the Z direction, and continuous fibers are distributed in the X direction, the Y direction and the Z direction; the Z-direction fibers used in the Z direction are carbon fibers coated with a polymer layer; the carbon fibers include mesophase pitch-based carbon fibers and/or high-modal polyacrylonitrile carbon fibers. According to the invention, the polymer layer is coated on the surface of the carbon fiber, so that the toughness of the carbon fiber can be increased, the problem of easy broken filaments and fuzz in the weaving process of the high-model carbon fiber is solved, and the continuity of the carbon fiber and the efficient conversion of the heat conduction performance and the electric conduction performance when the carbon fiber is used for preparing a composite material are ensured; the three-dimensional fabric reinforcement is used as a preformed body to prepare the polymer-based composite material, and the heat conduction and the electric conductivity in the thickness direction, the interlayer performance and the like of the polymer-based composite material are obviously improved.

Description

Three-dimensional fabric reinforcement, preparation method thereof and polymer-based composite material
Technical Field
The invention relates to the technical field of composite materials with heat conduction functions, in particular to a three-dimensional fabric reinforcement, a preparation method thereof and a polymer matrix composite material.
Background
The fiber composite material has been widely applied in the fields of aerospace, traffic, electronics, fan blades and the like because of the advantages of light weight, high strength, designability, corrosion resistance, fatigue resistance, structure-function integration and the like, particularly the continuous fiber composite material is a typical representative of advanced composite materials, and the traditional fiber composite material is prepared by taking one-dimensional fabrics or two-dimensional fabrics as reinforcements through a multilayer laying method. Because the layering mode lacks effective fiber reinforcement between layers, the prepared composite material has poor heat conduction and electric conductivity in the thickness direction and poor interlayer performance.
For polymer matrix composites, the heat conduction of the matrix is mainly through lattice vibration, and the heat conductivity is very low, so the key for improving the heat conductivity of the polymer matrix composites is the number of heat conduction paths formed in the matrix and the stability of the heat conduction paths. The mode through adding filler in the base member can improve polymer matrix composite's heat conductivility to a certain extent, but the filler is mostly the graininess, and can not fully contact between the graininess filler, and heat conduction route is mixed and disorderly during heat transfer, can not reach comparatively ideal effect.
The high-heat-conductivity fiber is used as a one-dimensional high-heat-conductivity material, and the high-heat-conductivity continuous fiber penetrates through the polymer-based composite material in the thickness direction, so that the defect of filling the granular filler can be overcome, and the heat conductivity and the interlayer performance in the thickness direction are both obviously improved. The high-model carbon fiber has perfect crystal structure and high graphitization degree, so that the high-model carbon fiber has excellent electric and heat conduction performance and the like. However, the high-model carbon fiber is fragile in brittleness and easy to damage in the weaving process, and the application of the high-model carbon fiber in the high-thermal-conductivity polymer matrix composite material is limited.
Disclosure of Invention
The invention aims to provide a three-dimensional fabric reinforcement, a preparation method thereof and a polymer matrix composite material, wherein the three-dimensional fabric reinforcement provided by the invention coats a polymer layer on the surface of carbon fiber, so that the problem of easy filament breakage and fuzzing in the weaving process of high-modulus carbon fiber can be solved, and the integral heat conduction and electric conductivity of the carbon fiber are not influenced; the three-dimensional fabric reinforcement is used as a preformed body to prepare the polymer-based composite material, and the heat conduction performance, the electric conductivity performance, the interlayer performance and the like of the polymer-based composite material in the thickness direction are obviously improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a three-dimensional fabric reinforcement which has a three-dimensional orthogonal structure, wherein the plane is in an X direction and a Y direction, the thickness is in a Z direction, and continuous fibers are distributed in the X direction, the Y direction and the Z direction; the Z-direction fibers used in the Z direction are carbon fibers coated with a polymer layer; the carbon fibers include mesophase pitch-based carbon fibers and/or high-modal polyacrylonitrile carbon fibers.
Preferably, the volume fraction of the X-direction fibers and the Y-direction fibers in the three-dimensional fabric reinforcement body is 35-45% independently, and the volume fraction of the Z-direction fibers is 15-30%.
Preferably, the specification of the carbon fiber is 1-24K.
Preferably, the polymer used for the polymer layer includes polyvinyl alcohol, polyurethane, polyacrylonitrile or polyphenylene sulfide resin.
Preferably, the thickness of the polymer layer is 0.1-0.5 mm.
Preferably, the preparation method of the Z-direction fiber comprises the following steps:
and coating the mixed material containing the polymer and the organic solvent used by the polymer layer on the surface of the carbon fiber, and removing the organic solvent to form the polymer layer on the surface of the carbon fiber to obtain the Z-direction fiber.
Preferably, the X-direction fibers used in the X direction and the Y-direction fibers used in the Y direction independently comprise one or more of carbon fibers, basalt fibers, glass fibers and aramid fibers; the specification of the X-direction fiber and the specification of the Y-direction fiber are 1-24K independently.
Preferably, the number of layers of the three-dimensional fabric reinforcement is 2-5, the thickness of a single layer is 1-5 mm, and the interlayer spacing is 5-10 mm.
The invention provides a preparation method of the three-dimensional fabric reinforcement body in the technical scheme, which comprises the following steps:
providing X-direction fibers for the X-direction, Y-direction fibers for the Y-direction, and Z-direction fibers for the Z-direction;
and weaving the X-direction fibers and the Y-direction fibers to form orthogonal layers, and simultaneously penetrating the Z-direction fibers through the thickness directions of a plurality of orthogonal layers to obtain the three-dimensional fabric reinforcement.
The invention provides a polymer matrix composite material, and the three-dimensional fabric reinforcement body prepared by the preparation method of the technical scheme or the three-dimensional fabric reinforcement body prepared by the preparation method of the technical scheme is a preformed body.
The invention provides a three-dimensional fabric reinforcement which has a three-dimensional orthogonal structure, wherein the plane is in an X direction and a Y direction, the thickness is in a Z direction, and continuous fibers are distributed in the X direction, the Y direction and the Z direction; a Z-direction fiber used in the Z directionThe fibers are carbon fibers coated with a polymer layer; the carbon fibers include mesophase pitch-based carbon fibers and/or high-modal polyacrylonitrile carbon fibers. In the invention, the mesophase pitch-based carbon fiber and the high-model polyacrylonitrile carbon fiber are high-model carbon fibers, have high heat conductivity and high electrical conductivity, and have the heat conductivity coefficient of more than 100 W.m-1·K-1The conductivity is more than 100S/cm; the polymer layer is coated on the surface of the carbon fiber, so that the toughness of the carbon fiber can be improved, and the problem of easy broken yarn fuzzing in the weaving process of the high-model carbon fiber is solved; the three-dimensional fabric reinforcement is used as a preformed body to prepare the polymer-based composite material, and the heat conduction performance, the electric conductivity performance, the interlayer performance and the like of the polymer-based composite material in the thickness direction are obviously improved. Experimental results in the examples show that the conductivity of the polymer matrix composite material provided by the invention can reach 54S/m at most, and the interlaminar shear strength can reach 92.6 MPa.
Drawings
FIG. 1 is a schematic structural view of a three-dimensional textile reinforcement;
FIG. 2 is a schematic cross-sectional view of a three-dimensional textile reinforcement;
FIG. 3 is a flow chart of a process for coating the surface of carbon fibers by dipping;
FIG. 4 is a flow chart of a process for coating the surface of carbon fibers by spraying;
FIG. 5 is a schematic diagram of a three-dimensional textile reinforcement in a polymer-matrix composite.
Detailed Description
In the present invention, the X direction, the Y direction and the Z direction described below only indicate relative positional relationships of fibers, and are not particularly limited.
The invention provides a three-dimensional fabric reinforcement (figure 1 is a structural schematic diagram of the three-dimensional fabric reinforcement; figure 2 is a section schematic diagram of the three-dimensional fabric reinforcement), which has a three-way orthogonal structure, wherein the plane is an X direction and a Y direction, the thickness is the Z direction, and continuous fibers are distributed in the X direction, the Y direction and the Z direction; the Z-direction fibers used in the Z direction are carbon fibers coated with a polymer layer; the carbon fibers include mesophase pitch-based carbon fibers and/or high-modal polyacrylonitrile carbon fibers.
In the present invention, the high-modal polyacrylonitrile carbon fiber is preferably a high-modal polyacrylonitrile carbon fiber M55J or M40J. In the invention, the mesophase pitch-based carbon fiber and the high-model polyacrylonitrile carbon fiber are high-model carbon fibers, have high heat conductivity and high electrical conductivity, and have the heat conductivity coefficient of more than 100 W.m-1·K-1The conductivity is more than 100S/cm, so that the polymer matrix composite material taking the three-dimensional fabric reinforcement as the preformed body can have high conductivity and high heat conductivity in the Z direction; the polymer layer is coated on the surface of the carbon fiber, so that the toughness of the carbon fiber can be improved, the problem that the high-model carbon fiber is easy to break and fluff in the weaving process can be solved, and meanwhile, the continuity of the carbon fiber and the efficient conversion of the heat conduction performance and the electric conduction performance in the preparation of the composite material can be guaranteed.
In the invention, the volume fractions of the X-direction fibers and the Y-direction fibers in the three-dimensional fabric reinforcement body are preferably 35-45% independently, and more preferably 35-40%; wherein, the volume fractions of the X-direction fiber and the Y-direction fiber can be the same or different, and when the volume fractions of the X-direction fiber and the Y-direction fiber are different, the difference of the volume fractions of the X-direction fiber and the Y-direction fiber is preferably less than or equal to 5%. In the invention, the volume fraction of the Z-direction fibers in the three-dimensional fabric reinforcement is preferably 15-30%, and more preferably 15-20%.
In the invention, the specification of the carbon fiber in the Z-direction fiber is preferably 1-24K, and more preferably 3-6K; the diameter of the carbon fiber is preferably 5-11 μm, and more preferably 7-9 μm.
In the present invention, the polymer used for the polymer layer in the Z-direction fibers preferably includes polyvinyl alcohol, polyurethane, polyacrylonitrile or polyphenylene sulfide resin. The source of the polymer in the present invention is not particularly limited, and it can be prepared by a commercially available method known to those skilled in the art or a preparation method known to those skilled in the art. In the present invention, the thickness of the polymer layer is preferably 0.1 to 0.5mm, and more preferably 0.2 to 0.4 mm. According to the invention, the proper polymer is selected and the thickness of the polymer layer is controlled, so that the phenomena of carbon fiber bending, matrix damage, composite material mechanical property reduction and the like caused by residual stress generated in the preparation process are reduced, and the high-model carbon fiber has strong toughness and cannot influence the whole heat conduction and electric conductivity.
In the present invention, the method for preparing the Z-direction fiber preferably includes the steps of:
and coating the mixed material containing the polymer and the organic solvent used by the polymer layer on the surface of the carbon fiber, and removing the organic solvent to form the polymer layer on the surface of the carbon fiber to obtain the Z-direction fiber.
The present invention preferably provides a mixture comprising the polymer used for the polymer layer and an organic solvent. In the present invention, the mixture may be obtained by directly mixing the polymer and the organic solvent, or other chemical substances such as a plasticizer may be added according to the characteristics of the polymer, which is not particularly limited in the present invention. In the invention, the mass fraction of the polymer in the mixed material is preferably 5-25%, and more preferably 5-20%; according to the invention, the proper organic solvent is preferably selected according to the specific type of the polymer, and the proper proportion relationship between the organic solvent and the polymer is selected. In the embodiment of the present invention, specifically:
when the polymer is polyacrylonitrile, dimethyl sulfoxide is preferably used as a solvent, and the polyacrylonitrile and the dimethyl sulfoxide are mixed to prepare a polyacrylonitrile solution (namely a mixed material); the mass fraction of polyacrylonitrile in the polyacrylonitrile solution is preferably 10-20%;
when the polymer is polyvinyl alcohol, preferably adding polyvinyl alcohol particles into warm water at the temperature of 25-35 ℃, stirring at the rotating speed of 200-300 r/min for 1-2 hours, raising the temperature to 90-95 ℃ after the polyvinyl alcohol particles fully absorb water and swell, and continuously stirring for 3-4 hours; cooling to room temperature, adding ethanol, and continuously stirring for 1-2 h to obtain a polyvinyl alcohol solution (namely a mixed material); the mass fraction of polyvinyl alcohol in the polyvinyl alcohol solution is preferably 4-7%, and the volume ratio of water to ethanol in the polyvinyl alcohol solution is preferably 1: (0.8 to 1.2);
when the polymer is polyphenylene sulfide resin, the polyphenylene sulfide resin and industrial alcohol are preferably mixed, and then ball-milled until the particle size is less than 120 μm to obtain a suspension (i.e. a mixed material), wherein the mass fraction of the polyphenylene sulfide resin in the suspension is preferably 20-25%.
After the mixed material is obtained, the mixed material is preferably coated on the surface of the carbon fiber, and a polymer layer is formed on the surface of the carbon fiber after the organic solvent is removed, so that the Z-direction fiber is obtained. The coating method of the present invention is not particularly limited, and a coating method known to those skilled in the art may be used according to the solubility of the polymer and the melting temperature, and the dipping method or the spraying method is preferably used in the present invention. The specific operation mode of the dipping method or the spraying method is not particularly limited, and a polymer layer with uniform thickness meeting the requirement can be obtained. The method and the conditions for removing the organic solvent are not specially limited, so that the formed polymer layer has high toughness and stability, and the problems of cracking, easy aging and the like are avoided. In the embodiment of the invention, a flow chart of coating the surface of the carbon fiber by using an impregnation method is shown in fig. 3, specifically, the mixed material is placed in an impregnation tank to impregnate the fiber, and then a drying furnace (the temperature is preferably 75-80 ℃) is used for volatilizing a solvent; the flow chart of coating the surface of the carbon fiber by using the spraying method is shown in fig. 4, and specifically, the mixed material is placed in a spray gun, spraying is carried out in a spraying chamber, and then the solvent is volatilized by a drying furnace (the temperature is preferably 75-80 ℃). In the invention, in the coating process, the speed of the take-up roller is preferably controlled to be 0.1-0.2 m/min. In addition, in the present invention, in order to obtain a polymer layer having a uniform thickness, coating may be performed several times according to actual needs, specifically, coating the next layer when one layer of coating is dry, which may provide a large adhesion between the coating layers.
In the present invention, the X-direction fibers used in the X direction and the Y-direction fibers used in the Y direction preferably independently include one or more of carbon fibers, basalt fibers, glass fibers, and aramid fibers, more preferably independently carbon fibers, basalt fibers, glass fibers, or aramid fibers, and further preferably carbon fibers. In the invention, the carbon fiber in the X-direction fiber and the Y-direction fiber can be a high-model carbon fiber (such as mesophase pitch-based carbon fiber or high-model polyacrylonitrile carbon fiber), and can also be a non-high-model carbon fiber (such as high-strength polyacrylonitrile carbon fiber T300, T700 or T800); when the carbon fibers in the X-direction fibers and the Y-direction fibers are high-model carbon fibers, the surface of the high-model carbon fibers is preferably coated with a polymer layer; the selectable range of the polymers used for the polymer layers in the X-direction fibers and the Y-direction fibers is preferably consistent with the selectable range of the polymers used for the polymer layers in the Z-direction fibers, and the details are not repeated herein; the preparation method of the polymer layer in the X-direction fibers and the Y-direction fibers is preferably consistent with that of the polymer layer in the Z-direction fibers, and is not described in detail herein. In the invention, the specifications of the X-direction fibers and the Y-direction fibers are preferably 1-24K independently, and more preferably 3-6K; the diameters of the X-direction fibers and the Y-direction fibers are preferably 5-11 μm independently, and more preferably 7-9 μm independently.
In the invention, the number of layers of the three-dimensional fabric reinforcement (wherein, the orthogonal layer formed by the X-direction fibers and the Y-direction fibers is taken as one layer) is preferably 2-5 layers, and more preferably 3-4 layers; the thickness of the single layer is preferably 1-5 mm, and more preferably 2-4 mm; the interlayer spacing is preferably 5-10 mm, and more preferably 6-9 mm; the orthogonal layers are connected through Z-direction fibers, and the interlayer spacing specifically refers to the length of the Z-direction fibers between the adjacent orthogonal layers.
The invention provides a preparation method of the three-dimensional fabric reinforcement body in the technical scheme, which comprises the following steps:
providing X-direction fibers for the X-direction, Y-direction fibers for the Y-direction, and Z-direction fibers for the Z-direction;
and weaving the X-direction fibers and the Y-direction fibers to form orthogonal layers, and simultaneously penetrating the Z-direction fibers through the thickness directions of a plurality of orthogonal layers to obtain the three-dimensional fabric reinforcement.
In the invention, the Z-direction fibers are used as binding yarns of a three-dimensional fabric reinforcement body, so that the connection among multiple layers of orthogonal layers can be realized; in practical use, the number of layers of the orthogonal layers can be determined according to the thickness of the required three-dimensional fabric reinforcement, then binder yarns (namely Z-direction fibers) among the multiple layers of orthogonal layers are cut off, and the three-dimensional fabric reinforcement with the required thickness can be obtained by compacting.
The invention provides a polymer matrix composite material, wherein the three-dimensional fabric reinforcement body prepared by the preparation method of the technical scheme or the three-dimensional fabric reinforcement body prepared by the preparation method of the technical scheme is a preformed body. In the invention, the resin matrix system used by the polymer matrix composite material comprises a resin material and a diluent, and a curing agent or a catalyst can be added according to actual needs; the invention has no special limitation on the types and the proportion relation of the resin material, the diluent, the curing agent and the catalyst, and can adopt the technical scheme which is well known by the technical personnel in the field. In the present invention, the resin material preferably includes an epoxy resin, a cyanate resin, a phenolic resin, or a bismaleimide resin, more preferably an epoxy resin or a cyanate resin, and the epoxy resin is preferably epoxy resin E51; the viscosity of the resin material is preferably lower than 0.5 pas, and more preferably 0.2-0.3 pas; the diluent preferably comprises polyethylene glycol diglycidyl ether (PEGDGE), butyl glycidyl ether (BGE, reactive diluent 501), or dibutyl phthalate; the curing agent preferably comprises triethylene tetramine or phthalic anhydride; the catalyst preferably comprises triethylamine. In the present invention, the molar ratio of the resin material and the diluent is preferably 100: (5-30), more preferably 100: (10-25); the mass ratio of the resin material to the curing agent is preferably 100: (10 to 80), more preferably 100: (10-60); the mass ratio of the resin material to the catalyst is preferably 100: (3-5). The preparation method of the resin matrix system is not specially limited, and all the components are directly stirred and uniformly mixed.
The preparation method of the polymer-based composite material is not particularly limited in the present invention, and a preparation method well known to those skilled in the art may be used. The three-dimensional fabric reinforcement is preferably laid in a mould, a Resin Transfer Molding (RTM) process is adopted at room temperature, and an injection machine is used for injecting the resin matrix system; after the injection is finished, putting the mixture into an oven for curing; and (4) demolding and polishing to obtain the polymer matrix composite.
In the present invention, the volume ratio of the resin matrix system to the three-dimensional textile reinforcement is preferably 4: (5-7), more preferably 4: 6.
in the invention, in the injection process, the injection pressure is preferably 0.5-1.5 MPa, and more preferably 0.6-1.0 MPa.
In the invention, the curing temperature is preferably 90-250 ℃, and the time is preferably 6-20 h; in the embodiment of the invention, the curing temperature and time are selected according to the composition of the resin matrix system, when the adopted resin material is epoxy resin, the curing is preferably performed at 90-100 ℃ for 3-4 h, and then the curing is continuously performed at 120-130 ℃ for 3-4 h; when the adopted resin material is cyanate ester resin, the cyanate ester resin is preferably cured at 145-155 ℃ for 4-5 hours, and then is continuously cured at 180-185 ℃ for 2-3 hours, at 200-205 ℃ for 2-3 hours, at 220-225 ℃ for 2-3 hours, and at 240-245 ℃ for 4-5 hours.
According to the invention, the upper surface and the lower surface of the composite material obtained after demolding are preferably ground by using sand paper, the specifications of the sand paper are preferably 400 meshes, 800 meshes, 1000 meshes and 2000 meshes in sequence until the end part of the Z-direction fiber (shown in figure 5) is directly exposed, the upper surface and the lower surface of the composite material are parallel, the thickness direction is vertical to the horizontal plane, and the Z-direction fiber is generally kept in a vertical continuous state, so that the Z direction presents a vertical continuous passage and penetrates through the whole polymer matrix composite material.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a Z-direction fiber, comprising the following steps:
using dimethyl sulfoxide as a solvent to prepare 15 wt% of polyacrylonitrile solution, coating the polyacrylonitrile solution on the surface of mesophase pitch-based carbon fiber (with the specification of 3K and the diameter of 9 mu m) by an impregnation method, volatilizing the solvent by a drying furnace (with the temperature of 80 ℃), and forming a polyacrylonitrile layer (with the thickness of 0.2mm as Z-direction fiber) on the surface of the mesophase pitch-based carbon fiber.
Preparing a three-dimensional textile reinforcement comprising the steps of:
the method comprises the steps of taking high-strength polyacrylonitrile carbon fibers T300 (the specification is 6K, the diameter is 7 microns) as X-direction fibers and Y-direction fibers, weaving the X-direction fibers and the Y-direction fibers to form orthogonal layers, and enabling the Z-direction fibers to penetrate through the thickness direction of two layers of the orthogonal layers to obtain the three-dimensional fabric reinforcement body with the three-way orthogonal structure, wherein the thickness of a single-layer orthogonal layer is 2mm, the interlayer spacing is 6mm, the volume fraction of the Z-direction fibers in the three-dimensional fabric reinforcement body is 15%, the volume fraction of the X-direction fibers is 42%, and the volume fraction of the Y-direction fibers is 43%.
Preparing a polymer matrix composite comprising the steps of:
according to the molar ratio of the epoxy resin E51 to polyethylene glycol diglycidyl ether (PEGDGE) diluent of 100: 10, uniformly mixing, adding 10% of triethylene tetramine curing agent by mass of epoxy resin E51, and uniformly stirring to obtain a resin matrix system;
laying the three-dimensional fabric reinforcement in a mold, adopting an RTM (resin transfer molding) process at room temperature, and injecting the resin matrix system by using an injection machine, wherein the volume ratio of the resin matrix system to the three-dimensional fabric reinforcement is 4: 6, the injection pressure is 0.6 MPa; after the injection is finished, putting the mixture into an oven to be cured for 3h at 90 ℃, and then continuing to cure for 3.5h at 120 ℃; and (3) obtaining a composite material after demolding, then polishing the upper surface and the lower surface of the composite material, wherein the specifications of the selected sand paper are 400 meshes, 800 meshes, 1000 meshes and 2000 meshes in sequence until the end part of the Z-direction fiber is directly exposed, the upper surface and the lower surface of the composite material are parallel, the thickness direction of the composite material is vertical to the horizontal plane, and the Z-direction fiber is generally kept in a vertical continuous state, so that a vertical continuous passage is formed in the Z direction.
Example 2
Preparing a Z-direction fiber, comprising the following steps:
adding polyvinyl alcohol particles into warm water at 25 ℃, stirring for 1.5h at the rotating speed of 200r/min, raising the temperature to 90 ℃ after the polyvinyl alcohol particles fully absorb water and swell, and continuously stirring for 3 h; cooling to room temperature, adding ethanol, and continuously stirring for 1h to obtain a polyvinyl alcohol solution (the mass fraction of polyvinyl alcohol is 5%, and the volume ratio of water to ethanol is 1: 1); the surface of the mesophase pitch-based carbon fiber (specification 3K, diameter 9 μm) was coated with the polyvinyl alcohol solution by an impregnation method, and the solvent was volatilized by a drying oven (temperature 75 ℃), so that a polyvinyl alcohol layer (thickness 0.5mm, as a Z-direction fiber) was formed on the surface of the mesophase pitch-based carbon fiber.
Preparing a three-dimensional textile reinforcement comprising the steps of:
the method comprises the steps of taking high-strength polyacrylonitrile carbon fibers T800 (the specification is 6K, the diameter is 5 microns) as X-direction fibers and Y-direction fibers, weaving the X-direction fibers and the Y-direction fibers to form orthogonal layers, and enabling the Z-direction fibers to penetrate through the thickness direction of the three orthogonal layers to obtain the three-dimensional fabric reinforcement body with the three-way orthogonal structure, wherein the thickness of the single-layer orthogonal layers is 4mm, the interlayer spacing is 8mm, the volume fraction of the Z-direction fibers in the three-dimensional fabric reinforcement body is 20%, the volume fraction of the X-direction fibers is 40%, and the volume fraction of the Y-direction fibers is 40%.
Preparing a polymer matrix composite comprising the steps of:
according to the molar ratio of the epoxy resin E51 to polyethylene glycol diglycidyl ether (PEGDGE) diluent of 100: 10, uniformly mixing, adding a phthalic anhydride curing agent accounting for 60 percent of the mass of the epoxy resin E51, and uniformly stirring to obtain a resin matrix system;
laying the three-dimensional fabric reinforcement in a mold, adopting an RTM (resin transfer molding) process at room temperature, and injecting the resin matrix system by using an injection machine, wherein the volume ratio of the resin matrix system to the three-dimensional fabric reinforcement is 4: 6, the injection pressure is 0.8 MPa; after the injection is finished, putting the mixture into an oven to be cured for 3h at 90 ℃, and then continuing to cure for 3.5h at 120 ℃; and (3) obtaining a composite material after demolding, then polishing the upper surface and the lower surface of the composite material, wherein the specifications of the selected sand paper are 400 meshes, 800 meshes, 1000 meshes and 2000 meshes in sequence until the end part of the Z-direction fiber is directly exposed, the upper surface and the lower surface of the composite material are parallel, the thickness direction of the composite material is vertical to the horizontal plane, and the Z-direction fiber is generally kept in a vertical continuous state, so that a vertical continuous passage is formed in the Z direction.
Example 3
Preparing X-direction fibers, Y-direction fibers and Z-direction fibers, comprising the following steps:
polyphenylene sulfide resin and industrial alcohol are mixed according to the mass ratio of 1: 4, pouring the mixture into a ball milling cylinder, ball milling the mixture until the granularity is less than 120 mu m, filling the obtained suspension into a spray gun, spraying the suspension on the surface of the mesophase pitch-based carbon fiber (the specification is 3K, the diameter is 9 mu m), and drying the suspension by a drying furnace (the temperature is 75 ℃) to volatilize the solvent; repeating the above spraying-drying operation to form a polyphenylene sulfide resin layer (thickness of about 0.05mm per spraying and total thickness of 0.4mm as Z-direction fiber) on the surface of the mesophase pitch-based carbon fiber;
a polyphenylene sulfide resin layer (about 0.05mm in thickness and 0.4mm in total thickness as X-direction fibers and Y-direction fibers) was formed on the surface of a high-modulus polyacrylonitrile carbon fiber M55J (6K in gauge, 5 μ M in diameter) in the above-described manner.
Preparing a three-dimensional textile reinforcement comprising the steps of:
and weaving the X-direction fibers and the Y-direction fibers to form an orthogonal layer, and simultaneously enabling the Z-direction fibers to penetrate through the thickness direction of two layers of the orthogonal layer to obtain the three-dimensional fabric reinforcement with a three-way orthogonal structure, wherein the thickness of a single-layer orthogonal layer is 4mm, the interlayer spacing is 8mm, the volume fraction of the Z-direction fibers in the three-dimensional fabric reinforcement is 15%, the volume fraction of the X-direction fibers is 43%, and the volume fraction of the Y-direction fibers is 42%.
Preparing a polymer matrix composite comprising the steps of:
heating and melting cyanate ester resin at 120 ℃, adding catalyst triethylamine, uniformly stirring, heating to 150 ℃ for reaction for 2 hours, then cooling to 115 ℃, adding diluent dibutyl phthalate, uniformly stirring, and reacting for 30 minutes to obtain a resin matrix system; wherein the mass ratio of the cyanate ester resin to the diluent to the catalyst is 20: 5: 1;
laying the three-dimensional fabric reinforcement in a mold, adopting an RTM (resin transfer molding) process at room temperature, and injecting the resin matrix system by using an injection machine, wherein the volume ratio of the resin matrix system to the three-dimensional fabric reinforcement is 4: 6, the injection pressure is 1 MPa; after the injection is finished, putting the mixture into an oven to be cured for 4h at 150 ℃, and then continuing to cure for 2h at 180 ℃, 2h at 200 ℃, 2h at 220 ℃ and 4h at 240 ℃ in sequence; and (3) obtaining a composite material after demolding, then polishing the upper surface and the lower surface of the composite material, wherein the specifications of the selected sand paper are 400 meshes, 800 meshes, 1000 meshes and 2000 meshes in sequence until the end part of the Z-direction fiber is directly exposed, the upper surface and the lower surface of the composite material are parallel, the thickness direction of the composite material is vertical to the horizontal plane, and the Z-direction fiber is generally kept in a vertical continuous state, so that a vertical continuous passage is formed in the Z direction.
Comparative example 1
Preparing a laminated composite comprising the steps of:
preparing X-direction fibers and Y-direction fibers according to the method of example 1, and weaving the X-direction fibers and the Y-direction fibers to form an orthogonal layer;
a resin matrix system was prepared according to the method of example 1;
the orthogonal plies were laid in a mould, two plies were laid, and then a laminated composite was prepared according to the method of example 1 with the orthogonal plies as a preform.
Test example
The performance of the composite materials prepared in examples 1 to 3 and comparative example 1 was tested, specifically as follows:
(1) according to the formula λ ═ α · CpRho is calculated to obtain the Z-direction heat conductivity coefficient of the composite material, and the formula is shown in the specification
Lambda is the thermal conductivity of the composite material in the Z direction, W/(m.K);
alpha-thermal diffusion coefficient in Z-direction of composite material, mm2/s；
Cp-specific heat capacity of the composite, J/(g · K);
rho-bulk Density of composite, g/cm3。
Wherein, α: obtained by adopting a laser flash method (specifically obtained by testing according to the GB/T22588-;
Cp: using DSC function in STA, according to ASTME1269 standard method, comparing the measured results of the standard sample with known specific heat and the sample to be measured with unknown specific heat, calculating to obtain the specific heat of the sample to be measured;
ρ: the body density of the composite material cut into fixed size is tested by a drainage method after the composite material is centrifuged by using distilled water as a solvent, and the body density can be calculated by the following formula: ρ ═ m0·ρWater (W)/(m0-m1) Wherein m is0Mass of the laminate in air, m1The corresponding mass was found to be averaged after the laminate was completely immersed.
(2) The Z-direction conductivity of the composite was measured using a dual electrical measurement four-probe tester (four-probe, guangzhou, inc. RTS-9).
(3) The interlaminar shear strength performance of the composite material is tested by an INSTRON3382 electronic universal tester according to the ASTM D2344-06 standard, and the test speed is constant at 1 mm/min. The interlaminar shear strength of the composite material is calculated by the formula tau being 3. F/(4. b. h), wherein
Tau-interlaminar shear strength of the composite, MPa;
f-maximum load present in the test, N;
b-sample width, mm;
h-specimen thickness, mm.
And 5 effective data are taken from each group of samples, and the average value is calculated to be used as the interlaminar shear strength of the composite material.
TABLE 1 results of performance testing of composites prepared in examples 1-3 and comparative example 1
Figure BDA0002119885060000121
As can be seen from table 1, after high-modulus carbon fibers (specifically mesophase pitch-based fibers) are woven in the Z direction, the composite material is prepared by using the obtained three-dimensional fabric reinforcement as a preform, and compared with a laminated composite material, the composite material provided by the invention has greatly improved Z-direction heat conduction, electric conduction and interlayer shear strength.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A three-dimensional fabric reinforcement has a three-dimensional orthogonal structure, wherein the plane is an X direction and a Y direction, the thickness is a Z direction, and continuous fibers are distributed in the X direction, the Y direction and the Z direction; the Z-direction fibers used in the Z direction are carbon fibers coated with a polymer layer; the carbon fibers include mesophase pitch-based carbon fibers and/or high-modal polyacrylonitrile carbon fibers.
2. The three-dimensional textile reinforcement according to claim 1, wherein the volume fraction of the fibers in the X-direction and the Y-direction in the three-dimensional textile reinforcement is 35 to 45% independently, and the volume fraction of the fibers in the Z-direction is 15 to 30%.
3. The three-dimensional fabric reinforcement according to claim 1, wherein the carbon fibers have a gauge of 1-24K.
4. The three-dimensional textile reinforcement according to claim 1, wherein the polymer used in the polymer layer comprises polyvinyl alcohol, polyurethane, polyacrylonitrile or polyphenylene sulfide resin.
5. The three-dimensional textile reinforcement according to claim 1, wherein the polymer layer has a thickness of 0.1 to 0.5 mm.
6. The three-dimensional textile reinforcement according to any one of claims 1 to 5, wherein the Z-direction fibers are prepared by a method comprising the following steps:
and coating the mixed material containing the polymer and the organic solvent used by the polymer layer on the surface of the carbon fiber, and removing the organic solvent to form the polymer layer on the surface of the carbon fiber to obtain the Z-direction fiber.
7. The three-dimensional textile reinforcement according to claim 1, wherein the X-direction used X-direction fibers and the Y-direction used Y-direction fibers independently comprise one or more of carbon fibers, basalt fibers, glass fibers, and aramid fibers; the specification of the X-direction fiber and the specification of the Y-direction fiber are 1-24K independently.
8. The three-dimensional textile reinforcement according to claim 1, wherein the number of layers of the three-dimensional textile reinforcement is 2-5, the thickness of a single layer is 1-5 mm, and the interlayer spacing is 5-10 mm.
9. A method for preparing the three-dimensional fabric reinforcement of any one of claims 1 to 8, comprising the steps of:
providing X-direction fibers for the X-direction, Y-direction fibers for the Y-direction, and Z-direction fibers for the Z-direction;
and weaving the X-direction fibers and the Y-direction fibers to form orthogonal layers, and simultaneously penetrating the Z-direction fibers through the thickness directions of a plurality of orthogonal layers to obtain the three-dimensional fabric reinforcement.
10. A polymer matrix composite material, characterized in that the three-dimensional textile reinforcement according to any one of claims 1 to 8 or the three-dimensional textile reinforcement prepared by the preparation method according to claim 9 is a preform.
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