CN110799592A - Carbon nanotube fiber composite material and preparation method thereof - Google Patents
Carbon nanotube fiber composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110799592A CN110799592A CN201980001641.XA CN201980001641A CN110799592A CN 110799592 A CN110799592 A CN 110799592A CN 201980001641 A CN201980001641 A CN 201980001641A CN 110799592 A CN110799592 A CN 110799592A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- nanotube fiber
- fiber fabric
- thermosetting resin
- fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 317
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 312
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 312
- 239000000835 fiber Substances 0.000 title claims abstract description 272
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004744 fabric Substances 0.000 claims abstract description 213
- 229920005989 resin Polymers 0.000 claims abstract description 127
- 239000011347 resin Substances 0.000 claims abstract description 127
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 126
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims description 31
- 229920000647 polyepoxide Polymers 0.000 claims description 31
- 239000002238 carbon nanotube film Substances 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000009941 weaving Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 9
- 239000000805 composite resin Substances 0.000 claims description 8
- 238000001721 transfer moulding Methods 0.000 claims description 7
- 239000007849 furan resin Substances 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
- D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
-
- 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
- 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
- D10B2101/122—Nanocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a preparation method of a carbon nanotube fiber composite material, which comprises the following steps: mixing the carbon nanotube fiber fabric with a thermosetting resin solution to prepare the carbon nanotube fiber fabric soaked with the thermosetting resin solution; and curing the carbon nanotube fiber fabric soaked with the thermosetting resin solution to obtain the carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite material. The method adopts the carbon nanotube fiber fabric as the reinforcement, avoids the problem that carbon nanotube powder is agglomerated in thermosetting resin, and plays the reinforcement role of the carbon nanotube to the maximum extent, so that the carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite material prepared by the preparation method has good mechanical property. The carbon nano tube fiber composite material prepared by the preparation method comprises the following steps: the fiber fabric is formed by compounding a carbon nanotube fiber fabric and a thermosetting resin.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a carbon nanotube fiber composite material and a preparation method thereof.
Background
The carbon nano tube has unique structure and excellent mechanical property, is an ideal reinforcing material for the composite material, and can greatly improve the strength and toughness of the polymer-based composite material due to the super-strong mechanical property and thermal stability of the carbon nano tube. In recent years, the research on carbon nanotube/polymer composite materials has become a new hot spot for the application research of carbon nanotubes. At present, carbon nanotubes are mainly dispersed in a polymer matrix in a powder form, the mechanical properties of the carbon nanotubes are still to be further improved, the carbon nanotube/epoxy resin composite material is prepared by a blending method such as Allaoui, Schadler, Breton and the like, and the addition of the carbon nanotubes can improve the mechanical properties of the matrix, but the problem of the dispersibility of the carbon nanotubes cannot be well solved, so that the mechanical properties of the composite material are not greatly improved or even reduced.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to obtain a preparation method of a carbon nanotube fiber composite material and the carbon nanotube fiber composite material prepared by the preparation method, so as to further improve the mechanical property of the carbon nanotube/polymer carbon nanotube fiber composite material.
Means for solving the problems
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a carbon nanotube fiber composite material, which comprises the following steps:
preparing a carbon nanotube fiber fabric;
obtaining a thermosetting resin solution, and mixing the carbon nanotube fiber fabric with the thermosetting resin solution to prepare the carbon nanotube fiber fabric soaked with the thermosetting resin solution;
and curing the carbon nanotube fiber fabric soaked with the thermosetting resin solution to obtain the carbon nanotube fiber fabric/thermosetting resin composite material.
Preferably, in the step of mixing the carbon nanotube fiber fabric with the thermosetting resin solution, the carbon nanotube fiber fabric is immersed in the thermosetting resin solution until the carbon nanotube fiber fabric is completely soaked by the thermosetting resin solution.
Preferably, in the step of preparing the carbon nanotube fiber fabric impregnated with the thermosetting resin solution, a vacuum assisted resin transfer molding method is adopted, so that the thermosetting resin solution completely impregnates the carbon nanotube fiber fabric.
Preferably, in the step of curing the carbon nanotube fabric impregnated with the thermosetting resin, the carbon nanotube fabric impregnated with the thermosetting resin is heated and cured at a preset temperature, and the carbon nanotube fabric impregnated with the thermosetting resin is pressurized and shaped to have a flat surface.
Preferably, the carbon nanotube fiber fabric is a plain weave fabric, a twill weave fabric or a satin weave fabric.
Preferably, the warp and weft density of the carbon nanotube fiber fabric is 5-40 bundles/square centimeter.
Preferably, the gram weight of the carbon nanotube fiber fabric is 50-400g/m2。
Preferably, the carbon nanotube fiber fabric comprises warp and weft, the warp and/or the weft are a plurality of carbon nanotube fiber bundles, and the extending direction of the warp is the length direction of the carbon nanotube fiber fabric.
Preferably, the preparation method of the carbon nanotube fiber fabric comprises the following steps:
obtaining a carbon nanotube array, pulling out a carbon nanotube film from the carbon nanotube array, and twisting the carbon nanotube film to obtain a carbon nanotube fiber;
carrying out doubling treatment on a plurality of carbon nanotube fiber yarns to obtain carbon nanotube fiber bundles;
and weaving a plurality of carbon nano tube fiber bundles into cloth to obtain the carbon nano tube fiber fabric.
Preferably, the thermosetting resin solution includes: thermosetting resin and a curing agent, wherein the weight ratio of the thermosetting resin to the curing agent is 100 (30-50).
Preferably, the thermosetting resin is at least one of an epoxy resin, a phenolic resin, an unsaturated polyester resin, a formaldehyde resin and a furan resin.
The invention also provides a carbon nanotube fiber composite material, which is a fiber fabric formed by compounding the carbon nanotube fiber fabric and the thermosetting resin.
Preferably, the thermosetting resin is coated on the surface of the carbon nanotube fiber fabric, and the thermosetting resin is filled in the gaps of the carbon nanotube fiber fabric.
Preferably, the carbon nanotube fiber fabric is a plain weave fabric, a twill weave fabric or a satin weave fabric.
Preferably, the warp and weft density of the carbon nanotube fiber fabric is 5-40 bundles/square centimeter.
Preferably, the gram weight of the carbon nanotube fiber fabric is 50-400g/m2。
Preferably, the carbon nanotube fiber fabric comprises warp and weft, the warp and/or the weft are carbon nanotube fiber bundles, and the extending direction of the warp is the length direction of the carbon nanotube fiber fabric.
Preferably, the thermosetting resin is at least one of an epoxy resin, a phenolic resin, an unsaturated polyester resin, a formaldehyde resin and a furan resin.
Effects of the invention
The preparation method of the carbon nanotube fiber composite material, which is provided by the invention, mixes the carbon nanotube fiber fabric with the thermosetting resin solution, and cures the mixture to realize the compounding between the carbon nanotube fiber fabric and the thermosetting resin. Different from the prior art, the carbon nanotube fiber fabric is used as the reinforcement, so that the problem of agglomeration of carbon nanotube powder in thermosetting resin is solved, the reinforcement effect of the carbon nanotube is exerted to the maximum extent, and the carbon nanotube fiber fabric/thermosetting resin composite material prepared by the preparation method has good mechanical property, is simple and convenient, and is easy for large-scale mass production.
The carbon nanotube fiber composite material obtained by the invention comprises the following components: the carbon nanotube fiber fabric is used as a reinforcement, has good mechanical properties, and can be widely applied to the fields of aerospace, automobiles, wind power generation, sports equipment and the like.
Drawings
Fig. 1 is an appearance of a carbon nanotube fiber fabric prepared in example 1;
fig. 2 is an appearance of the carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite prepared in example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A preparation method of a carbon nanotube fiber composite material comprises the following steps:
s01, preparing a carbon nanotube fiber fabric; obtaining a thermosetting resin solution, and mixing the carbon nanotube fiber fabric with the thermosetting resin solution to prepare the carbon nanotube fiber fabric soaked with the thermosetting resin solution;
s02, curing the carbon nanotube fiber fabric soaked with the thermosetting resin solution to obtain the carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite material.
According to the preparation method of the carbon nanotube fiber composite material, the carbon nanotube fiber fabric and the thermosetting resin solution are mixed and cured, and the carbon nanotube fiber fabric and the thermosetting resin are compounded. Different from the prior art, the carbon nanotube fiber fabric is used as the reinforcement, so that the problem of agglomeration of carbon nanotube powder in thermosetting resin is solved, the reinforcement effect of the carbon nanotube is exerted to the maximum extent, and the carbon nanotube fiber fabric/thermosetting resin composite material prepared by the preparation method has good mechanical property, is simple and convenient, and is easy for large-scale mass production.
Specifically, in step S01, the carbon nanotube fiber fabric is used as a reinforcement of the carbon nanotube fiber composite material, so that the problem of agglomeration of the powdered carbon nanotubes dispersed in the thermosetting resin in the prior art is avoided, and the reinforcement of the carbon nanotubes is exerted to the maximum extent, so that the carbon nanotube fiber fabric/thermosetting resin composite material prepared by the preparation method of the present invention has good mechanical properties.
The carbon nanotube fiber fabric can be of a single-layer structure, and can also be of a composite layer structure with two or more layers, and can be flexibly adjusted according to the specific actual conditions of the carbon nanotube fiber composite material. In some embodiments, the carbon nanotube fiber fabric has a single-layer structure, and the thickness of the single-layer structure is about the diameter of one carbon nanotube fiber bundle. As an embodiment, the carbon nanotube fiber fabric includes warp and weft, the warp and/or the weft are carbon nanotube fiber bundles, and the extending direction of the warp is the length direction of the carbon nanotube fiber fabric. As another embodiment, the carbon nanotube fiber fabric is a plain weave fabric, a twill fabric or a satin weave fabric, preferably a plain weave fabric, the plain weave fabric has good operability and stability, and has a large number of weave interlacing points and yarn buckling points, so that the fabric is firm, wear-resistant, stiff and flat, and the plain weave fabric has the best weave fastness and wear resistance among the three fabrics under the conditions of the same thickness and density of the warp and weft yarns. In some embodiments, the carbon nanotube fiber fabric has a warp and weft density of 5 to 40 bundles/square centimeter; in other embodiments of the present invention, the substrate may be,the gram weight of the carbon nano tube fiber fabric is 50-400g/m2. The carbon nanotube fiber fabric with the warp and weft density and the gram weight has good mechanical property, good hardness and flexibility, and is easy to be soaked by the thermosetting resin.
Furthermore, the carbon nanotube fiber fabric is mainly obtained by weaving a plurality of carbon nanotube fiber bundles, and meanwhile, the carbon nanotube fiber bundles are obtained by doubling a plurality of carbon nanotube fiber yarns. In some embodiments, the method for preparing the carbon nanotube fiber fabric comprises the following steps:
s011, obtaining a carbon nanotube array, pulling out a carbon nanotube film from the carbon nanotube array, and twisting the carbon nanotube film to obtain a carbon nanotube fiber;
s012, carrying out doubling treatment on a plurality of carbon nanotube fibers to obtain carbon nanotube fiber bundles;
s013, weaving a plurality of carbon nanotube fiber bundles into cloth, and obtaining the carbon nanotube fiber fabric.
More specifically, in step S011, the preparation of the carbon nanotube array may refer to the conventional operations in the art, and in some embodiments, the preparation method of the carbon nanotube array comprises: depositing a catalyst layer on the substrate, placing the substrate in a chemical vapor deposition reaction furnace, introducing protective gas, heating to 500-900 ℃, introducing carbon source gas, and reacting for about 20min, thereby generating a uniformly-grown carbon nanotube array on the substrate.
And pulling out the carbon nanotube film from the carbon nanotube array, and twisting the carbon nanotube film to prepare the carbon nanotube fiber. The carbon nanotube film drawn from the carbon nanotube array is orderly arranged, and has uniform length and diameter, so that the carbon nanotube fiber yarn obtained by twisting has better mechanical property. In some embodiments, a 0.1-20cm carbon nanotube film is pulled from the carbon nanotube array.
And twisting the carbon nanotube film to obtain the carbon nanotube fiber. Further, in the step of twisting the carbon nanotube film, the carbon nanotube film with uniform diameter and length and no defect is selected for twisting; and in the step of twisting the carbon nanotube film, twisting the carbon nanotube film according to the twist of 100-15000 tpm. In some embodiments, the twist is preferably 1200-.
In step S012, a plurality of carbon nanotube filaments are subjected to a doubling process to obtain a carbon nanotube fiber bundle. The step of doubling a plurality of carbon nanotube fiber yarns comprises the following steps: and carrying out no-twist doubling or twist doubling on the plurality of carbon nano tube fiber yarns. In some embodiments, the number of carbon nanotube fiber filaments is 50-120; in other embodiments, a plurality of the carbon nanotube fiber yarns are twisted and doubled, and the twist is 50 to 150 tpm; in still other embodiments, a plurality of the carbon nanotube fiber filaments are arranged in parallel or spirally and rotatably along the axial direction of the carbon nanotube fiber bundle.
In step S013, a plurality of the carbon nanotube fiber bundles are woven into a cloth to obtain the carbon nanotube fiber fabric. The step of weaving the plurality of carbon nanotube fiber bundles into the fabric may refer to a fabric weaving process.
Specifically, the thermosetting resin solution is used for providing thermosetting resin, so that the carbon nanotube fiber fabric is conveniently compounded with the thermosetting resin. As an embodiment, the thermosetting resin solution includes: thermosetting resin and a curing agent, wherein the weight ratio of the thermosetting resin to the curing agent is 100 (30-50). When the curing agent is more than 50 parts by taking the thermosetting resin as 100 parts, the carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite material obtained subsequently is brittle; when the curing agent is less than 30 parts, the curing is incomplete during the subsequent curing treatment. In some embodiments, the weight ratio of the thermosetting resin to the curing agent is 100:30, 100:32, 100:35, 100:37, 100:39, 100:42, 100:45, 100:46, 100:49, 100: 50. As another embodiment, the viscosity of the thermosetting resin solution is 0.1 to 0.5pa.s to ensure good fluidity of the thermosetting resin solution. In some embodiments, the viscosity of the thermosetting resin solution is 0.10, 0.15, 0.25, 0.30, 0.40, 0.50 pa.s. As yet another embodiment, the thermosetting resin is at least one of an epoxy resin, a phenolic resin, an unsaturated polyester resin, a formaldehyde resin, and a furan resin; the curing agent is selected from amine curing agents. In some embodiments, the thermosetting resin is an epoxy resin, and the epoxy resin is selected from at least one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin; the amine curing agent is selected from aliphatic amine and/or aromatic amine, wherein the aliphatic amine is preferably at least one of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and diethylamino propylamine, and the aromatic amine is preferably at least one of m-xylylenediamine, m-phenylenediamine and diaminodiphenylmethane. As still another embodiment, the thermosetting resin solution further comprises: an organic solvent for dissolving the thermosetting resin and the curing agent, the organic solvent preferably being at least one of acetone, butanone, xylene, n-butanol, and ethyl acetate.
And mixing the carbon nanotube fiber fabric with the thermosetting resin solution to ensure that the carbon nanotube fiber fabric is fully contacted with the thermosetting resin solution so as to obtain the carbon nanotube fiber fabric soaked with the thermosetting resin solution. In one embodiment, in the step of preparing the carbon nanotube fiber fabric impregnated with the thermosetting resin solution, the carbon nanotube fiber fabric is immersed in the thermosetting resin solution until the carbon nanotube fiber fabric is completely impregnated with the thermosetting resin solution. In some embodiments, in the step of preparing the carbon nanotube fiber fabric impregnated with the thermosetting resin solution, a vacuum assisted resin transfer molding method is adopted, so that the thermosetting resin solution completely impregnates the carbon nanotube fiber fabric. As an example, the step of mixing the carbon nanotube fiber fabric with the thermosetting resin solution is a VARTM molding process, the carbon nanotube fiber fabric is placed in a mold cavity, the thermosetting resin is injected after vacuum pumping, so that the thermosetting resin is fully impregnated into the carbon nanotube fiber fabric, and further, the viscosity of the thermosetting resin solution is adjusted to 0.1 to 0.5pa.s, so that the thermosetting resin solution has good fluidity in the mold cavity, which is beneficial for the thermosetting resin to fully impregnate the carbon nanotube fiber fabric.
In step S02, the carbon nanotube fiber fabric impregnated with the thermosetting resin solution is cured, so that the thermosetting resin on the carbon nanotube fiber fabric is cured, thereby obtaining the carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite material. As an embodiment, in the step of curing the carbon nanotube fabric impregnated with the thermosetting resin, the carbon nanotube fabric impregnated with the thermosetting resin is heated and cured at a preset temperature, and the carbon nanotube fabric impregnated with the thermosetting resin is pressed and shaped to make the surface flat. In some embodiments, the carbon nanotube fiber fabric impregnated with the thermosetting resin is heated and cured at 50-100 ℃ until the thermosetting resin on the carbon nanotube fiber fabric is completely cured. As an example, the carbon nanotube fiber fabric impregnated with the thermosetting resin is heated and cured at 50 to 100 ℃ for 2 to 15 hours. Further, the thermosetting resin solution on the carbon nanotube fiber fabric is cured by a method of electrifying and heating the carbon nanotube fiber fabric. The carbon nanotube fiber fabric has good electric conduction, the carbon nanotube fiber fabric is electrified, the carbon nanotube is electrified to generate heat, and after the temperature rises to 50-100 ℃, the thermosetting resin solution on the carbon nanotube fiber fabric can be heated and cured. In some embodiments, the current for electrifying the carbon nanotube fiber fabric is 0.1-0.6A, and the current is controlled to be 0.1-0.6A, so that the temperature can reach the curing temperature quickly, and the performance of the carbon nanotube fiber fabric is not influenced.
In summary, under the comprehensive action of the optimized process and the condition parameters such as reaction temperature, time, dosage ratio and the like obtained in the embodiment of the present invention, the carbon nanotube fiber composite material obtained by the preparation method obtained in the embodiment of the present invention has the best mechanical properties.
Correspondingly, the carbon nanotube fiber composite material prepared by the preparation method is a fiber fabric formed by compounding a carbon nanotube fiber fabric and thermosetting resin.
The carbon nanotube fiber composite material obtained by the embodiment of the invention comprises the following components: the carbon nanotube fiber fabric is used as a reinforcement, has good mechanical properties, and can be widely applied to the fields of aerospace, automobiles, wind power generation, sports equipment and the like.
Specifically, the carbon nanotube fiber composite material is a carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite material, is a cloth-shaped fiber fabric, and is formed by compounding a carbon nanotube fiber fabric and thermosetting resin, and the specific compounding process is referred to the above. In some embodiments, the thermosetting resin is coated on the surface of the carbon nanotube fiber fabric, and the thermosetting resin is filled in the gaps of the carbon nanotube fiber fabric. Different from the carbon nanotube fiber fabric, the warp and weft of the carbon nanotube fiber fabric compounded with the thermosetting resin are not easy to scatter, and a user can cut the fabric at will when using the fabric.
Further, in some embodiments, the carbon nanotube fiber fabric includes warp and weft, the warp and/or the weft are carbon nanotube fiber bundles, and the direction in which the warp extends is the length direction of the carbon nanotube fiber fabric. In some embodiments, the carbon nanotube fiber bundle is formed by doubling a plurality of carbon nanotube fibers, for example, 50 to 120 carbon nanotube fibers. In other embodiments, the carbon nanotube fiber fabric is a plain, twill or satin weave. In still other embodiments, the carbon nanotube fiber composite has a grammage of 50-400g/m2. In still other embodiments, the carbon nanotube fiber fabric has a warp and weft density of 5 to 40 bundles/cm.
Further, in some embodiments, the thermosetting resin is at least one of an epoxy resin, a phenolic resin, an unsaturated polyester resin, a formaldehyde resin, and a furan resin.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art, and to make the progress of the carbon nanotube fiber composite material and the method for preparing the same apparent from the embodiments of the present invention, the following examples illustrate the implementation of the present invention.
Example 1
The embodiment prepares the fiber fabric, and the specific process flow is as follows:
1. preparation of carbon nanotube fiber Fabric
Depositing a catalyst layer on a substrate, placing the substrate in a chemical vapor deposition reaction furnace, introducing protective gas, heating to 700 ℃, introducing carbon source gas, and reacting for about 20min, thereby generating a uniformly-grown carbon nanotube array on the substrate;
drawing a carbon nanotube film with the width of 7.5cm from the carbon nanotube array, and twisting the film by using a twist meter, wherein the twist is 1300tpm to obtain a carbon nanotube fiber;
combining 50 carbon nanotube fibers into a bundle of carbon nanotube fibers; then, the carbon nanotube fiber bundles were woven into a cloth by a weaving machine, and the weave was a plain weave to obtain a carbon nanotube fiber fabric having a warp and weft density of 10 bundles/cm and a basis weight of about 200g/m as shown in FIG. 12。
2. Carbon nanotube fiber fabric composite thermosetting resin
Placing the carbon nanotube fiber fabric into a mold cavity by adopting a VARTM (vacuum transfer molding) molding process, vacuumizing, and injecting an epoxy resin solution to enable the epoxy resin solution to fully infiltrate the carbon nanotube fiber fabric; wherein, in the epoxy resin solution, the weight ratio of the epoxy resin to the curing agent is 100: 34;
and taking out the carbon nanotube fiber fabric fully soaked with the thermosetting resin solution, and introducing a current of 0.6A to the carbon nanotube fiber fabric to enable the temperature to be about 100 ℃, wherein the curing time is 2 hours, so that the carbon nanotube fiber fabric/thermosetting resin carbon nanotube fiber composite material shown in the figure 2 is obtained.
Example 2
The embodiment prepares the fiber fabric, and the specific process flow is as follows:
1. preparation of carbon nanotube fiber Fabric
Depositing a catalyst layer on a substrate, placing the substrate in a chemical vapor deposition reaction furnace, introducing protective gas, heating to 700 ℃, introducing carbon source gas, and reacting for about 20min, thereby generating a uniformly-grown carbon nanotube array on the substrate;
drawing a carbon nanotube film with the width of 7.5cm from the carbon nanotube array, and twisting the film by using a twist meter, wherein the twist is 1300tpm to obtain a carbon nanotube fiber;
combining 100 carbon nanotube fibers into a bundle of carbon nanotube fibers; then weaving the carbon nano tube fiber bundles into cloth by a weaving machine, wherein the weave is a plain weave, and the carbon nano tube fiber fabric is obtained, the warp and weft density of the carbon nano tube fiber fabric is 5 bundles/square centimeter, and the gram weight of the fabric is about 200g/m2。
2. Carbon nanotube fiber fabric composite thermosetting resin
Placing the carbon nanotube fiber fabric into a mold cavity by adopting a VARTM (vacuum transfer molding) molding process, vacuumizing, and injecting an epoxy resin solution to enable the epoxy resin solution to fully infiltrate the carbon nanotube fiber fabric; wherein, in the epoxy resin solution, the weight ratio of the epoxy resin to the curing agent is 100: 45;
and taking out the carbon nanotube fiber fabric fully soaked with the thermosetting resin solution, introducing 0.4A of current into the carbon nanotube fiber fabric to enable the temperature of the carbon nanotube fiber fabric to be about 80 ℃, and curing for 6 hours to obtain the carbon nanotube fiber fabric/thermosetting resin composite material.
Example 3
The embodiment prepares the fiber fabric, and the specific process flow is as follows:
1. preparation of carbon nanotube fiber Fabric
Depositing a catalyst layer on a substrate, placing the substrate in a chemical vapor deposition reaction furnace, introducing protective gas, heating to 700 ℃, introducing carbon source gas, and reacting for about 20min, thereby generating a uniformly-grown carbon nanotube array on the substrate;
drawing a carbon nanotube film with the width of 7.5cm from the carbon nanotube array, and twisting the film by using a twist meter, wherein the twist is 1300tpm to obtain a carbon nanotube fiber;
combining 120 carbon nanotube fibers into a bundle of carbon nanotube fibers; then weaving the carbon nano tube fiber bundles into cloth by a weaving machine, wherein the weave is a plain weave, and the carbon nano tube fiber fabric is obtained, the warp and weft density of the carbon nano tube fiber fabric is 5 bundles/square centimeter, and the gram weight of the fabric is about 400g/m2。
2. Carbon nanotube fiber fabric composite thermosetting resin
Placing the carbon nanotube fiber fabric into a mold cavity by adopting a VARTM (vacuum transfer molding) molding process, vacuumizing, and injecting an epoxy resin solution to enable the epoxy resin solution to fully infiltrate the carbon nanotube fiber fabric; wherein, in the epoxy resin solution, the weight ratio of the epoxy resin to the curing agent is 100: 45;
and taking out the carbon nanotube fiber fabric fully soaked with the thermosetting resin solution, introducing 0.6A of current to the carbon nanotube fiber fabric to enable the temperature of the carbon nanotube fiber fabric to be about 100 ℃, and curing for 6 hours to obtain the carbon nanotube fiber fabric/thermosetting resin composite material.
Example 4
The embodiment prepares the fiber fabric, and the specific process flow is as follows:
1. preparation of carbon nanotube fiber Fabric
Depositing a catalyst layer on a substrate, placing the substrate in a chemical vapor deposition reaction furnace, introducing protective gas, heating to 700 ℃, introducing carbon source gas, and reacting for about 20min, thereby generating a uniformly-grown carbon nanotube array on the substrate;
drawing a carbon nanotube film with the width of 7.5cm from the carbon nanotube array, and twisting the film by using a twist meter, wherein the twist is 1300tpm to obtain a carbon nanotube fiber;
combining 50 carbon nanotube fibers into a bundle of carbon nanotube fibers; then, the user can use the device to perform the operation,weaving the carbon nano tube fiber bundles into cloth by a weaving machine, wherein the weave is a plain weave, and the carbon nano tube fiber fabric is obtained, the warp and weft density of the carbon nano tube fiber fabric is 40 bundles/square centimeter, and the gram weight of the fabric is about 400g/m2。
2. Carbon nanotube fiber fabric composite thermosetting resin
Placing the carbon nanotube fiber fabric into a mold cavity by adopting a VARTM (vacuum transfer molding) molding process, vacuumizing, and injecting an epoxy resin solution to enable the epoxy resin solution to fully infiltrate the carbon nanotube fiber fabric; wherein, in the epoxy resin solution, the weight ratio of the epoxy resin to the curing agent is 100: 45;
and taking out the carbon nanotube fiber fabric fully soaked with the thermosetting resin solution, introducing 0.1A of current to the carbon nanotube fiber fabric to enable the temperature of the carbon nanotube fiber fabric to be about 50 ℃, and curing for 15 hours to obtain the carbon nanotube fiber fabric/thermosetting resin composite material.
Comparative example 1
This comparative example prepared a carbon nanotube/epoxy composite comprising: dispersing carbon nanotube powder in epoxy resin solution, adding curing agent for dispersion, stirring at high speed, mixing, casting in a mold for curing and forming to prepare the carbon nanotube/epoxy resin composite film.
Test example
The fiber fabrics prepared in examples 1 to 4 and the carbon nanotube/epoxy resin composite film prepared in comparative example 1 were used as test samples, and then the flexural modulus of each test sample was measured at room temperature using an electronic universal tester according to the standard ASTM D790 three-point load simple beam method, with the test results shown in table 1. From table 1, the mechanical properties of the composite material prepared by using the carbon nanotube fiber fabric as the reinforcement can be effectively improved.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Flexural modulus (GPa) | 200 | 180 | 177 | 165 | 130 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (18)
1. The preparation method of the carbon nanotube fiber composite material is characterized by comprising the following steps of:
preparing a carbon nanotube fiber fabric;
obtaining a thermosetting resin solution, and mixing the carbon nanotube fiber fabric with the thermosetting resin solution to prepare the carbon nanotube fiber fabric soaked with the thermosetting resin solution;
and curing the carbon nanotube fiber fabric soaked with the thermosetting resin solution to obtain the carbon nanotube fiber fabric/thermosetting resin composite material.
2. The method according to claim 1, wherein in the step of preparing the carbon nanotube fiber fabric impregnated with the thermosetting resin solution, the carbon nanotube fiber fabric is immersed in the thermosetting resin solution until the carbon nanotube fiber fabric is completely impregnated with the thermosetting resin solution.
3. The method of claim 1, wherein in the step of preparing the carbon nanotube fiber fabric impregnated with the thermosetting resin solution, a vacuum assisted resin transfer molding method is used to completely impregnate the carbon nanotube fiber fabric with the thermosetting resin solution.
4. The method according to claim 1, wherein in the step of curing the carbon nanotube fiber fabric impregnated with the thermosetting resin, the carbon nanotube fiber fabric impregnated with the thermosetting resin is heated and cured at a predetermined temperature, and the carbon nanotube fiber fabric impregnated with the thermosetting resin is pressed and shaped to have a flat surface.
5. The method of claim 1, wherein the carbon nanotube fiber fabric is plain, twill or satin.
6. The method of claim 1, wherein the carbon nanotube fiber fabric has a warp/weft density of 5 to 40 bundles/cm.
7. The method of claim 1, wherein the carbon nanotube fiber fabric has a grammage of 50-400g/m2。
8. The method of claim 1, wherein the carbon nanotube fiber fabric comprises warp and weft, the warp and/or the weft are carbon nanotube fiber bundles, and the extending direction of the warp is the length direction of the carbon nanotube fiber fabric.
9. The method of preparing a carbon nanotube fiber composite according to claim 1, wherein the method of preparing the carbon nanotube fiber fabric comprises the steps of:
obtaining a carbon nanotube array, pulling out a carbon nanotube film from the carbon nanotube array, and twisting the carbon nanotube film to obtain a carbon nanotube fiber;
carrying out doubling treatment on a plurality of carbon nanotube fiber yarns to obtain carbon nanotube fiber bundles;
and weaving a plurality of carbon nano tube fiber bundles into cloth to obtain the carbon nano tube fiber fabric.
10. The method of preparing a carbon nanotube fiber composite according to claim 1, wherein the thermosetting resin solution comprises: thermosetting resin and a curing agent, wherein the weight ratio of the thermosetting resin to the curing agent is 100 (30-50).
11. The method of claim 10, wherein the thermosetting resin is at least one of epoxy resin, phenol resin, unsaturated polyester resin, formaldehyde resin, and furan resin.
12. A carbon nanotube fiber composite material is characterized in that the carbon nanotube fiber composite material is a fiber fabric formed by compounding a carbon nanotube fiber fabric and a thermosetting resin.
13. The carbon nanotube fiber composite according to claim 12, wherein the thermosetting resin is coated on the surface of the carbon nanotube fiber fabric, and the thermosetting resin is filled in the voids of the carbon nanotube fiber fabric.
14. The carbon nanotube fiber composite of claim 12, wherein the carbon nanotube fiber fabric is a plain, twill or satin weave.
15. The carbon nanotube fiber composite of claim 12, wherein said carbon nanotube fiber fabric has a warp and weft density of 5 to 40 bundles/cm.
16. The carbon nanotube fiber composite of claim 12, wherein the grammage of the carbon nanotube fiber fabric is 50-400g/m2。
17. The carbon nanotube fiber composite according to claim 12, wherein the carbon nanotube fiber fabric comprises warp and weft, the warp and/or the weft are carbon nanotube fiber bundles, and the direction in which the warp extends is the length direction of the carbon nanotube fiber fabric.
18. The carbon nanotube fiber composite of claim 12, wherein the thermosetting resin is at least one of an epoxy resin, a phenolic resin, an unsaturated polyester resin, a formaldehyde resin, and a furan resin.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2019/104759 WO2021042384A1 (en) | 2019-09-06 | 2019-09-06 | Carbon nanotube fiber composite material and preparation method therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110799592A true CN110799592A (en) | 2020-02-14 |
Family
ID=69448528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980001641.XA Pending CN110799592A (en) | 2019-09-06 | 2019-09-06 | Carbon nanotube fiber composite material and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110799592A (en) |
| WO (1) | WO2021042384A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111705391A (en) * | 2020-06-08 | 2020-09-25 | 深圳烯湾科技有限公司 | Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material |
| CN111764026A (en) * | 2020-06-08 | 2020-10-13 | 深圳烯湾科技有限公司 | Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material |
| CN112662010A (en) * | 2020-12-21 | 2021-04-16 | 远景能源有限公司 | Continuous carbon nanotube fiber reinforced resin matrix composite material, wind power blade and preparation method thereof |
| CN116876196A (en) * | 2023-06-27 | 2023-10-13 | 江西省纳米技术研究院 | Drawing enhancement method and system for carbon nanotube fibers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103850114A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for electro-enhancement of carbon nano tube fiber |
| WO2018047718A1 (en) * | 2016-09-07 | 2018-03-15 | ヤマハ株式会社 | Anisotropic strain sensor sheet and clothing |
| CN108120670A (en) * | 2016-11-29 | 2018-06-05 | 上海大学 | The test of fiber resin composite material interface shearing performance and ameliorative way under high temperature |
| CN108284619A (en) * | 2018-02-11 | 2018-07-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of interlayer toughened composite material, preparation method and application |
| CN108656652A (en) * | 2017-03-30 | 2018-10-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano-tube fibre composite material and preparation method |
-
2019
- 2019-09-06 WO PCT/CN2019/104759 patent/WO2021042384A1/en active Application Filing
- 2019-09-06 CN CN201980001641.XA patent/CN110799592A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103850114A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for electro-enhancement of carbon nano tube fiber |
| WO2018047718A1 (en) * | 2016-09-07 | 2018-03-15 | ヤマハ株式会社 | Anisotropic strain sensor sheet and clothing |
| CN108120670A (en) * | 2016-11-29 | 2018-06-05 | 上海大学 | The test of fiber resin composite material interface shearing performance and ameliorative way under high temperature |
| CN108656652A (en) * | 2017-03-30 | 2018-10-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano-tube fibre composite material and preparation method |
| CN108284619A (en) * | 2018-02-11 | 2018-07-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of interlayer toughened composite material, preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111705391A (en) * | 2020-06-08 | 2020-09-25 | 深圳烯湾科技有限公司 | Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material |
| CN111764026A (en) * | 2020-06-08 | 2020-10-13 | 深圳烯湾科技有限公司 | Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material |
| CN112662010A (en) * | 2020-12-21 | 2021-04-16 | 远景能源有限公司 | Continuous carbon nanotube fiber reinforced resin matrix composite material, wind power blade and preparation method thereof |
| CN116876196A (en) * | 2023-06-27 | 2023-10-13 | 江西省纳米技术研究院 | Drawing enhancement method and system for carbon nanotube fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021042384A1 (en) | 2021-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110799592A (en) | Carbon nanotube fiber composite material and preparation method thereof | |
| Yao et al. | Interfacial improvement of carbon fiber/epoxy composites using one-step method for grafting carbon nanotubes on the fibers at ultra-low temperatures | |
| Yao et al. | Fracture investigation of functionalized carbon nanotubes-grown carbon fiber fabrics/epoxy composites | |
| Das et al. | Preparation, development, outcomes, and application versatility of carbon fiber-based polymer composites: a review | |
| EP2660385B1 (en) | Lightning strike protection material | |
| CN106671525B (en) | The highly conductive and high Reinforced structure composite material and preparation method of hybrid modification | |
| CN109206146B (en) | Carbon fiber/nanofiber synergistic tough ceramic matrix composite and preparation method thereof | |
| Hu et al. | Process and mechanical properties of carbon/carbon–silicon carbide composite reinforced with carbon nanotubes grown in situ | |
| CN111101371A (en) | High-performance carbon nanotube/carbon composite fiber and rapid preparation method thereof | |
| CN106866148A (en) | The SiC of SiC nanowire In-sltu reinforcementf/ SiC ceramic matrix composite material and preparation method thereof | |
| Tian et al. | Nanofiber–sheathed structure for enhancing interfacial properties of basalt fiber-reinforced composites | |
| CN115071166B (en) | Modified continuous carbon fiber reinforced polyether ether ketone composite laminate and preparation method thereof | |
| Feng et al. | Interfacial improvement of carbon fiber/epoxy composites by incorporating superior and versatile multiscale gradient modulus intermediate layer with rigid-flexible hierarchical structure | |
| CN110284322A (en) | Carbon-based fire-retardant compound fabric of a kind of compliant conductive fever and preparation method thereof | |
| Li et al. | Simultaneous enhancement of electrical conductivity and interlaminar shear strength of CF/EP composites through MWCNTs doped thermoplastic polyurethane film interleaves | |
| Kong et al. | Intensive and thermally conductive boron nitride/aramid nanofiber composite fibers fabricated via a wet spinning technique | |
| CN106905546B (en) | A kind of preparation method of high-strength and high-conductivity composite fiber-reinforced composite material | |
| CN110028329B (en) | A kind of high thermal conductivity ceramic matrix composite material and preparation method thereof | |
| CN110029523B (en) | A kind of grafted nanofiber reinforced carbon fiber paper and preparation method thereof | |
| CN102951919B (en) | Method for growing beta-SiC nano fiber in situ in C/SiC composite material | |
| CN105859303B (en) | A kind of carbon/carbon compound material precast body and preparation method thereof | |
| CN1260277C (en) | Method for preparing thermoplastic blended resin based composite material | |
| Liu et al. | Enhancement of thermal conductivity and abrasion resistance of woody carbon fiber composites via boride catalysis | |
| CN112941704B (en) | Preparation method of three-dimensional spacer fabric reinforced porous composite material | |
| CN116396590A (en) | A kind of electrospinning functional prepreg containing nanoparticles and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200214 |
|
| RJ01 | Rejection of invention patent application after publication |