CN108794979B - High-compression-strength and high-tensile-ratio carbon fiber composite material and preparation method thereof - Google Patents

High-compression-strength and high-tensile-ratio carbon fiber composite material and preparation method thereof Download PDF

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CN108794979B
CN108794979B CN201810268251.6A CN201810268251A CN108794979B CN 108794979 B CN108794979 B CN 108794979B CN 201810268251 A CN201810268251 A CN 201810268251A CN 108794979 B CN108794979 B CN 108794979B
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carbon fiber
composite material
strength
resin
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CN108794979A (en
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冯志海
朱世鹏
杨云华
李龙
潘月秀
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China Academy of Launch Vehicle Technology CALT
Aerospace Research Institute of Materials and Processing Technology
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Aerospace Research Institute of Materials and Processing Technology
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

The invention discloses a carbon fiber composite material with high compression strength and high tensile ratio and a preparation method thereof, belonging to the field of composite materials. The composite material comprises a resin matrix and reinforcing fibers, wherein the reinforcing fibers are carbon fibers with the fiber monofilament diameter of 5.4-7.0 mu m, and the resin matrix comprises the following components in parts by mass: 100 parts of resin, 30-60 parts of curing agent, 0.5-2 parts of accelerator and 0.1-3 parts of inorganic nanoparticles. The composite material has excellent mechanical properties, particularly high compressive strength and good balance of compression and tension, can be used for preparing main bearing structural members of aerospace aircrafts, and can also meet the requirements of the fields of high-speed rails, automobiles and other industrial equipment on light-weight high-strength, compressive strength and high-tension-ratio composite materials.

Description

High-compression-strength and high-tensile-ratio carbon fiber composite material and preparation method thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a carbon fiber composite material with high compression strength and high tensile ratio, and a preparation method and application thereof.
Background
Carbon fiber composite materials are widely used in load-bearing structures due to their excellent properties of low density, high modulus strength, and the like. At present, the advanced composite material for national defense equipment in China adopts the first-generation advanced composite material represented by T300 and T700-grade carbon fiber reinforced epoxy, the tensile strength is 1300-1500 MPa, and the tensile modulus is 120-140 GPa. The tensile strength of the second-generation advanced composite material taking the T800-grade carbon fiber as the reinforcement can reach 2400-2800 MPa, and the tensile modulus can reach 150-170 GPa. The new generation of important equipment in China has urgent need for the second generation of advanced composite materials.
With the continuous improvement of the tensile strength of the carbon fibers by reducing the diameter, the tensile strength of the composite material is correspondingly and greatly improved, but the compressive strength and the bending strength of the composite material are not obviously improved. For example, the diameter and tensile strength of the Dongli T300 carbon fiber in Japan are typically 7 μm and 3530MPa, and the diameter and tensile strength of the Dongli T800H carbon fiber are typically 5 μm and 5490MPa, respectively. For the epoxy resin-based unidirectional composite material laminate, the tensile strength of the T800-grade carbon fiber composite material is improved from about 1600MPa to about 2800MPa of the T300 composite material, the compressive strength is basically maintained at about 1500MPa, the ratio of the compressive strength to the tensile strength (called the compression-tension ratio for short) is also reduced from about 0.9 to about 0.5, and the bending strength is reduced from 1800MPa to about 1600 MPa.
The balance performance of compression, bending and compression and tension is low, so that the carbon fiber composite material member is easy to damage when compressed and bent, the application of the carbon fiber composite material member is limited, the weight reduction effect is reduced, and the use requirement of novel equipment is difficult to meet.
Disclosure of Invention
The invention aims to provide a carbon fiber composite material with high compressive strength and high tensile ratio and a preparation method thereof. The composite material provided by the invention has excellent mechanical properties, especially the characteristics of high compressive strength and high tensile ratio, can be used for preparing a novel main bearing structural member of an aerospace aircraft, and can also meet the requirements of the fields of high-speed rails, automobiles and other industrial equipment on the light-weight high-compressive strength and high-tensile ratio composite material.
The above purpose of the invention is mainly realized by the following technical scheme:
the carbon fiber composite material with high compressive strength and high tensile ratio comprises a resin matrix and reinforcing fibers, wherein the reinforcing fibers are carbon fibers with the fiber monofilament diameter of 5.4-7.0 mu m, and the resin matrix comprises the following components in parts by mass: 100 parts of resin, 30-60 parts of curing agent, 0.5-2 parts of accelerator and 0.1-3 parts of inorganic nanoparticles.
In an optional embodiment, the tensile strength of the reinforced fiber is 5400-6200 MPa, and the tensile modulus is 280-320 GPa.
In an alternative embodiment, the resin is at least one of 4, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin, phthalic acid diglycidyl ester epoxy resin, bisphenol a type glycidyl ether epoxy resin, bismaleimide resin; the curing agent is at least one of diamino diphenyl sulfone, diamino diphenyl methane or diphenyl methane diamine.
In an alternative embodiment, the promoter is at least one of benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, or 2-ethyl-4-methylimidazole.
In an alternative embodiment, the inorganic nanoparticles are at least one of carbon nanotubes or graphene.
A preparation method of a carbon fiber composite material with high compression strength and high tensile ratio comprises the following steps:
(1) mechanically stirring and mixing 100 parts by mass of resin, 30-60 parts by mass of curing agent, 0.5-2 parts by mass of accelerator and 0.1-3 parts by mass of inorganic nanoparticles to obtain a resin matrix;
(2) impregnating carbon fibers with the fiber monofilament diameter of 5.4-7.0 mu m into the resin matrix to prepare a prepreg;
(3) and layering and curing the prepreg to obtain the high-compression-strength and high-tensile-ratio carbon fiber composite material.
In an alternative embodiment, before impregnation, in step (2), a surface treatment liquid is impregnated on the surface of the carbon fiber, and then drying treatment is performed, wherein the surface treatment liquid comprises the following components in parts by mass:
10-20 parts of a silane coupling agent, 80-90 parts of a solution and 0.1-1 part of graphene, wherein the solution is a composition of at least one of ethanol or isopropanol and water.
In an alternative embodiment, the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or 3- (methacryloyloxy) propyltrimethoxysilane; the graphene is hydroxyl or carboxyl modified graphene.
In an alternative embodiment, the step (2) of impregnating the surface of the carbon fiber with the surface treatment liquid includes:
immersing the carbon fiber into a surface treatment liquid, drawing the carbon fiber to be separated from the surface treatment liquid at a speed of 0.1-1 m/min, drying and winding into a shaft.
In an optional embodiment, the curing in step (3) includes curing at 120-140 ℃ and 0.2-0.4 MPa for 1-2h, and then curing at 180-200 ℃ and 0.4-0.8 MPa for 2-4 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the resin system is enhanced by adopting the inorganic nanoparticles, the improvement of the rigidity of the resin matrix is realized, the problem that the carbon fibers are easy to be stably damaged under the compressive load of the composite material due to the low modulus of the resin matrix is solved, and the maximum exertion strength of the carbon fiber reinforcement is ensured, meanwhile, when the resin matrix formula provided by the embodiment of the invention is used for impregnating the medium-diameter and large-diameter high-strength medium-model carbon fiber reinforcement, the impregnation efficiency is high, the compression and bending properties of the composite material obtained after curing are greatly improved, the maximum compression strength and bending strength can reach 5MPa and 1820MPa, and the compression-tension ratio can reach 0.75;
(2) according to the invention, the high-strength medium-model carbon fiber with medium and large diameters, which is subjected to surface treatment in advance and contains functionalized graphene and a silane coupling agent, is used as a composite material reinforcement, so that the interface bonding force and the interlaminar shear performance of the carbon fiber and a resin matrix are increased, and the compression and compression-tension balance performance of the composite material is further improved;
(3) the mechanical strength of the composite material prepared by the method is greatly improved compared with that of the conventional T800-grade carbon fiber composite material, and the composite material can be used for preparing a main bearing structural member of an aerospace aircraft and can also meet the requirements of the fields of high-speed rails, automobiles and other industrial equipment on light-weight high-strength, compressive strength and high-pressure tensile ratio composite materials.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples.
The embodiment of the invention provides a resin matrix composition, and specifically, the composition comprises the following components in parts by mass: 100 parts of resin, 30-60 parts of curing agent, 0.5-2 parts of accelerator and 0.1-3 parts of inorganic nano particles; the resin is preferably at least one of 4, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin, phthalic acid diglycidyl ester epoxy resin, bisphenol A type glycidyl ether epoxy resin or bismaleimide resin; the curing agent is preferably at least one of diaminodiphenyl sulfone, diaminodiphenyl methane or diphenyl methane diamine; the promoter is preferably at least one of benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol and 2-ethyl-4-methylimidazole; the inorganic nano-particles are preferably at least one of carbon nano-tubes or graphene, and more preferably carboxylated or hydroxylated carbon nano-tubes and carboxylated or hydroxylated graphene; according to the invention, the polyfunctional group matrix resin with high reactivity and the high-temperature curing agent are adopted, so that the interface binding force of the resin and the reinforced carbon fiber is increased, the strength and modulus of the resin matrix are improved, and the modulus of the resin matrix is further improved after the hydroxyl or carboxyl functionalized inorganic nano particles are added, so that the strength performance of the carbon fiber in the composite material prepared by adopting the resin composition is fully exerted, and the improvement of the compression performance of the composite material is facilitated.
The embodiment of the invention provides a carbon fiber composite material with high compressive strength and high tensile ratio, and particularly comprises a resin matrix and reinforcing fibers, wherein the resin matrix adopts the composition; the monofilament diameter of the preferable carbon fiber of the reinforced fiber is 5.4-7.0 μm, the tensile strength is 5400-6200 MPa, and the tensile modulus is 280-320 GPa.
According to the invention, the inorganic nanoparticles are adopted to reinforce the resin system, so that the improvement of the rigidity of the resin matrix (the tensile strength is 80-120 MPa, and the tensile modulus is 3.5-4.5 GPa) is realized, the problem that the carbon fibers are easy to break stably under the compressive load of the composite material due to the low modulus of the resin matrix is solved, and the maximum exertion strength of the carbon fiber reinforcement is ensured.
The embodiment of the invention provides a preparation method of a carbon fiber composite material with high compression strength and high tensile ratio, which comprises the following steps:
step 1, obtaining a resin matrix by using 100 parts by mass of resin, 30-60 parts by mass of a curing agent, 0.5-2 parts by mass of an accelerator and 0.1-3 parts by mass of inorganic nanoparticles;
specifically, in the embodiment of the invention, inorganic nanoparticles are uniformly dispersed in matrix resin by adopting high-speed mechanical stirring, and defoaming treatment is carried out for standby; the inorganic nano particles are preferably functionalized particles with different functional groups from the surface treatment liquid in the step 2, and can perform chemical reaction with the surface of the carbon fiber to enhance the bonding force between the resin and the fiber interface.
Step 2, impregnating carbon fibers with the fiber diameter of 5.4-7.0 mu m into the resin matrix to prepare a prepreg;
specifically, in the embodiment of the invention, in the step (2), before impregnation, a surface treatment liquid is firstly impregnated on the surface of the carbon fiber, and then drying treatment is performed, wherein the surface treatment liquid comprises the following components in parts by mass: 10-20 parts of a silane coupling agent; 80-90 parts of a solution; 0.1-1 part of graphene. The silane coupling agent is preferably at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane, and can be chemically coupled with the surface of the carbon fiber and functionalized graphene, so that the nano graphene is adhered to the surface of the carbon fiber, the surface area of the carbon fiber bonded with resin is increased, and the interface bonding force and the interlaminar shear strength are enhanced; the solution is preferably a composition of at least one of ethanol and isopropanol and water, and the graphene is preferably hydroxyl-or carboxyl-modified graphene.
In the embodiment of the invention, the carbon fiber is preferably immersed in the surface treatment liquid, the carbon fiber is pulled to be separated from the surface treatment liquid at the speed of 0.1-1 m/min, and the carbon fiber is dried and wound into a shaft, so that the surface treatment liquid is uniformly immersed on the surface of the fiber, and the problem that the mechanical property of the composite material is reduced due to the formation of aggregates by the nano particles caused by excessive immersion amount of the surface treatment liquid or the interface property with the resin cannot be effectively improved due to the fact that the nano particles are less coated on the surface of the fiber caused by too little immersion amount.
And 3, layering and curing the prepreg to obtain the high-compression-strength and high-tension-ratio carbon fiber composite material.
Specifically, the embodiment of the invention comprises curing at 120-140 ℃ and 0.2-0.4 MPa for 1-2h, and then curing at 170-190 ℃ and 0.4-0.8 MPa for 2-4 h.
The following are several specific examples of the present invention, and the raw materials and reagents used in each example are commercially available products, wherein the TG800 high strength medium model carbon fiber is purchased from shanxi steel carbon materials ltd. Tensile properties of the resin casting were tested as specified in GB/T16421-1996. The tensile property, the compression property, the bending property and the interlaminar shear property of the unidirectional composite material are respectively tested according to the regulations in GB/T3354-1982, GB/T3856-2008, GB/T3356-1999 and JC/T773-2010, and the compression strength after impact is tested according to the regulations in GB/T21239-2007.
Example 1
The TG800 high-strength medium-model carbon fiber (the tensile strength is 6200MPa, the tensile modulus is 295GPa) with the fiber monofilament diameter of 5.4 mu m is pulled and soaked at the speed of 0.1m/min, and is dried and rolled by surface treatment fluid, and the surface treatment fluid consists of the following components in parts by mass: 20 parts of gamma-aminopropyltriethoxysilane, 18 parts of ethanol, 62 parts of water and 0.1 part of hydroxylated graphene;
mixing 68 parts of 4, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin, 32 parts of bisphenol A type glycidyl ether epoxy resin, 60 parts of diaminodiphenyl sulfone, 0.5 part of benzyldimethylamine and 0.1 part of carboxylated graphene at a high speed, and uniformly stirring to prepare a matrix resin system; impregnating carbon fibers subjected to surface treatment in advance into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (130 ℃/0.3MPa/1h) + (180 ℃/0.6MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 2
The preparation method comprises the following steps of (1) drawing and infiltrating TG800 high-strength medium model carbon fibers (the tensile strength is 6200MPa and the tensile modulus is 295GPa) with the fiber monofilament diameter of 5.4 mu m at the speed of 0.1m/min, drying and rolling the drawn and infiltrated carbon fibers after the drawn and infiltrated carbon fibers pass through surface treatment liquid, wherein the surface treatment liquid comprises 20 parts of gamma-aminopropyltriethoxysilane, 18 parts of ethanol, 62 parts of water and 0.1 part of hydroxylated graphene;
mixing 68 parts of 4, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin, 32 parts of bisphenol A type glycidyl ether epoxy resin, 60 parts of diaminodiphenyl sulfone, 0.5 part of benzyldimethylamine and 0.5 part of carboxylated carbon nanotubes uniformly at a high speed, and stirring to prepare a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (130 ℃/0.3MPa/1h) + (180 ℃/0.6MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 3
The TG800 high-strength medium-model carbon fiber (the tensile strength is 5400MPa, the tensile modulus is 320GPa) with the fiber monofilament diameter of 5.4 mu m is pulled and soaked at the speed of 0.5m/min, and then the carbon fiber is dried and rolled by surface treatment fluid, wherein the surface treatment fluid consists of the following components in parts by mass: 15 parts of gamma-glycidyl ether oxypropyltrimethoxysilane, 18 parts of ethanol, 62 parts of water and 0.5 part of carboxylated graphene;
mixing 65 parts of diglycidyl phthalate epoxy resin, 35 parts of bisphenol A type glycidyl ether epoxy resin, 50 parts of diaminodiphenylmethane, 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol and 0.5 part of hydroxylated graphene at a high speed, and uniformly stirring to prepare a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the high-compression-strength and high-tension-ratio carbon fiber composite material, wherein the curing process is (120 ℃/0.2MPa/2h) + (180 ℃/0.4MPa/3 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 4
The TG800 high-strength medium-model carbon fiber (the tensile strength is 5400MPa, the tensile modulus is 320GPa) with the fiber monofilament diameter of 5.4 mu m is pulled and soaked at the speed of 0.5m/min, and then the carbon fiber is dried and rolled by surface treatment fluid, wherein the surface treatment fluid consists of the following components in parts by mass: 15 parts of gamma-glycidyl ether oxypropyltrimethoxysilane, 18 parts of ethanol, 62 parts of water and 0.5 part of carboxylated graphene;
mixing 65 parts of diglycidyl phthalate epoxy resin, 35 parts of bisphenol A type glycidyl ether epoxy resin, 50 parts of diaminodiphenylmethane, 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol and 1 part of hydroxylated carbon nanotube uniformly at a high speed, and stirring to prepare a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the high-compression-strength and high-tension-ratio carbon fiber composite material, wherein the curing process is (120 ℃/0.2MPa/2h) + (180 ℃/0.4MPa/3 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 5
The TG800 high-strength medium-model carbon fiber (the tensile strength is 6000MPa, the tensile modulus is 280GPa) with the fiber monofilament diameter of 5.8 mu m is drawn and soaked at the speed of 1m/min, and then the carbon fiber is dried and rolled up after passing through surface treatment liquid, wherein the surface treatment liquid comprises the following components in parts by mass: 15 parts of gamma-aminopropyltriethoxysilane, 30 parts of isopropanol, 55 parts of water and 1 part of carboxylated graphene;
mixing 58 parts of 4, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin, 42 parts of bisphenol A type glycidyl ether epoxy resin, 50 parts of diaminodiphenyl sulfone, 2 parts of benzyldimethylamine and 1 part of hydroxylated graphene at a high speed, and uniformly stirring to prepare a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing work is (120 ℃/0.2MPa/2h) + (180 ℃/0.4MPa/3 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 6
The TG800 high-strength medium-model carbon fiber (the tensile strength is 6000MPa, the tensile modulus is 280GPa) with the fiber monofilament diameter of 5.8 mu m is drawn and soaked at the speed of 1m/min, and then the carbon fiber is dried and rolled up after passing through surface treatment liquid, wherein the surface treatment liquid comprises the following components in parts by mass: 15 parts of gamma-aminopropyltriethoxysilane, 30 parts of isopropanol, 55 parts of water and 1 part of carboxylated graphene;
mixing 58 parts of 4, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin, 42 parts of bisphenol A type glycidyl ether epoxy resin, 50 parts of diaminodiphenyl sulfone, 2 parts of benzyldimethylamine and 2 parts of hydroxylated carbon nanotubes, uniformly stirring at a high speed, and preparing a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the high-compression-strength and high-tension-ratio carbon fiber composite material, wherein the curing process is (120 ℃/0.2MPa/2h) + (180 ℃/0.4MPa/3 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 7
The TG800 high-strength medium-model carbon fiber (the tensile strength is 6000MPa, the tensile modulus is 292GPa) with the fiber monofilament diameter of 6.0 mu m is drawn and soaked at the speed of 1m/min, and then the carbon fiber is dried and rolled up after passing through surface treatment liquid, wherein the surface treatment liquid comprises the following components in parts by mass: 10 parts of 3- (methacryloyloxy) propyltrimethoxysilane, 38 parts of isopropanol, 52 parts of water and 1 part of carboxylated graphene;
mixing 74 parts of bismaleimide resin, 26 parts of bisphenol A type glycidyl ether epoxy resin, 30 parts of diphenylmethane diamine, 2 parts of 2-ethyl-4-methylimidazole and 3 parts of hydroxylated carbon nano tube, uniformly stirring at a high speed, and preparing a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (140 ℃/0.4MPa/2h) + (180 ℃/0.8MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 8
The TG800 high-strength medium-model carbon fiber (the tensile strength is 6000MPa, the tensile modulus is 292GPa) with the fiber monofilament diameter of 6.0 mu m is drawn and soaked at the speed of 1m/min, and then the carbon fiber is dried and rolled up after passing through surface treatment liquid, wherein the surface treatment liquid comprises the following components in parts by mass: 10 parts of 3- (methacryloyloxy) propyltrimethoxysilane, 38 parts of isopropanol, 52 parts of water and 1 part of carboxylated graphene;
mixing 74 parts of bismaleimide resin, 26 parts of bisphenol A type glycidyl ether epoxy resin, 30 parts of diphenylmethane diamine, 2 parts of 2-ethyl-4-methylimidazole and 2 parts of hydroxylated graphene at a high speed, and uniformly stirring to prepare a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (140 ℃/0.4MPa/2h) + (200 ℃/0.8MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 9
The TG800 high-strength medium-model carbon fiber (the tensile strength is 5400MPa, the tensile modulus is 280GPa) with the fiber monofilament diameter of 7.0 μm is drawn and soaked at the speed of 1m/min, and then is dried and rolled by surface treatment fluid, wherein the surface treatment fluid consists of the following components in parts by mass: 15 parts of gamma-aminopropyltriethoxysilane, 18 parts of ethanol, 62 parts of water and 0.5 part of carboxylated graphene;
mixing 65 parts of diglycidyl phthalate epoxy resin, 35 parts of bisphenol A type glycidyl ether epoxy resin, 50 parts of diaminodiphenylmethane, 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol and 0.5 part of hydroxylated graphene at a high speed, and uniformly stirring to prepare a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the high-compression-strength and high-tension-ratio carbon fiber composite material, wherein the curing process is (120 ℃/0.2MPa/2h) + (180 ℃/0.4MPa/3 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Example 10
The TG800 high-strength medium-model carbon fiber (the tensile strength is 5400MPa, the tensile modulus is 280GPa) with the fiber monofilament diameter of 7.0 μm is drawn and soaked at the speed of 1m/min, and then is dried and rolled by surface treatment fluid, wherein the surface treatment fluid consists of the following components in parts by mass: 15 parts of gamma-aminopropyltriethoxysilane, 18 parts of ethanol, 62 parts of water and 0.5 part of carboxylated graphene;
mixing 74 parts of bismaleimide resin, 26 parts of bisphenol A type glycidyl ether epoxy resin, 30 parts of diphenylmethane diamine, 2 parts of 2-ethyl-4-methylimidazole and 2 parts of hydroxylated graphene at a high speed, and uniformly stirring to prepare a matrix resin system; impregnating the pre-treated carbon fibers into the resin matrix to prepare a prepreg; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (140 ℃/0.4MPa/2h) + (200 ℃/0.8MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Comparative example 1
A unidirectional prepreg was prepared using the matrix resin system of example 1 and a high-strength medium-modulus carbon fiber of Torilis japonica T800H (tensile strength 5490MPa, tensile modulus 294GPa) having a fiber diameter of 5.0 μm; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (130 ℃/0.3MPa/1h) + (180 ℃/0.6MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Comparative example 2
The matrix resin system and TG800 high-strength medium-model carbon fiber (tensile strength is 6200MPa, tensile modulus is 295GPa) with the fiber diameter of 5.4 mu m are adopted to directly prepare the unidirectional prepreg without surface treatment in the embodiment 1; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (130 ℃/0.3MPa/1h) + (180 ℃/0.6MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Comparative example 3
The matrix resin system of example 8 and TG800 high-strength medium-model carbon fibers (tensile strength of 6000MPa, tensile modulus of 292GPa) with fiber monofilament diameter of 6.0 μm were used to directly prepare prepreg without surface treatment; and (3) laying and curing the prepreg to obtain the carbon fiber composite material with high compressive strength and high tensile ratio, wherein the curing process is (140 ℃/0.4MPa/2h) + (200 ℃/0.8MPa/4 h). The matrix resin casting and the composite mechanical properties are shown in Table 1.
Figure BDA0001611897790000101
As can be seen from the comparison of example 1 with comparative example 2, and the comparison of example 8 with comparative example 3, the compressive strength and the compression-tensile ratio of the composite material prepared by the fiber surface treatment method of the invention are obviously improved compared with the composite material without surface treatment. From examples 1 to 10, the tensile strength of the medium-large diameter TG800 high-strength medium-model carbon fiber unidirectional composite material prepared by the method is 2500-2886 MPa, the compressive strength is 1650-1885 MPa, the bending strength is 1650-1820 MPa, the interlaminar shear strength is 105-115 MPa, and the compression-tension ratio is 0.57-0.75. As can be seen from comparative example 1, the tensile strength, compressive strength, flexural strength and interlaminar shear strength of the molded carbon fiber in the high mode of Toray T800H Japan having a diameter of 5 μm prepared by the present invention were about 2806MPa, 1402MPa, 1519MPa and 100MPa, respectively, on average, and the compression-tension ratio was 0.50. Compared with the embodiment 1-10 and the comparative example 1, the medium-diameter, high-strength and medium-modulus carbon fiber composite material prepared by the method has the characteristics of higher compressive strength and pressure-tension balance performance compared with the small-diameter, high-strength and medium-modulus carbon fiber composite material, can be applied to main bearing structural members of national defense and industrial equipment such as aerospace aircrafts and the like, and fully illustrates the effect of the method.
The above description is only for the best mode of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Those skilled in the art will appreciate that the invention may be practiced without these specific details.

Claims (7)

1. A preparation method of a carbon fiber composite material with high compression strength and high tensile ratio is characterized by comprising the following steps:
(1) mechanically stirring and mixing 100 parts by mass of resin, 30-60 parts by mass of curing agent, 0.5-2 parts by mass of accelerator and 0.1-3 parts by mass of inorganic nanoparticles to obtain a resin matrix;
(2) impregnating carbon fibers with the fiber monofilament diameter of 5.4-7.0 mu m into the resin matrix to prepare a prepreg;
(3) laying and curing the prepreg to obtain the high-compression-strength and high-tensile-ratio carbon fiber composite material;
before impregnation, impregnating the surface of the carbon fiber with a surface treatment liquid, and then drying, wherein the surface treatment liquid comprises the following components in parts by mass:
10-20 parts of a silane coupling agent, 80-90 parts of a solution and 0.1-1 part of graphene, wherein the solution is a composition of at least one of ethanol or isopropanol and water;
the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane; the graphene is hydroxyl or carboxyl modified graphene.
2. The method for preparing a carbon fiber composite material with high compressive strength and high tensile ratio according to claim 1, wherein the step (2) of impregnating the surface of the carbon fiber with a surface treatment solution comprises:
immersing the carbon fiber into a surface treatment liquid, drawing the carbon fiber to be separated from the surface treatment liquid at a speed of 0.1-1 m/min, drying and winding into a shaft.
3. The method for preparing the carbon fiber composite material with high compressive strength and high tensile ratio as claimed in claim 1, wherein the curing in the step (3) comprises curing at 120-140 ℃ and 0.2-0.4 MPa for 1-2h, and then curing at 180-200 ℃ and 0.4-0.8 MPa for 2-4 h.
4. The method for preparing the carbon fiber composite material with high compressive strength and high tensile ratio as claimed in claim 1, wherein the carbon fiber has a tensile strength of 5400-6200 MPa and a tensile modulus of 280-320 GPa.
5. The method for preparing a carbon fiber composite material with high compressive strength and high tensile ratio according to claim 1, wherein the resin is at least one of 4, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin, diglycidyl phthalate epoxy resin, bisphenol a type glycidyl ether epoxy resin, bismaleimide resin; the curing agent is at least one of diamino diphenyl sulfone, diamino diphenyl methane or diphenyl methane diamine.
6. The method of making a high compressive strength and high tensile ratio carbon fiber composite as claimed in claim 1, wherein the promoter is at least one of benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, or 2-ethyl-4-methylimidazole.
7. The method of claim 1, wherein the inorganic nanoparticles are at least one of carbon nanotubes or graphene.
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