CN110540734B - Carbon nanotube composite fiber and preparation method thereof - Google Patents

Carbon nanotube composite fiber and preparation method thereof Download PDF

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CN110540734B
CN110540734B CN201910743355.2A CN201910743355A CN110540734B CN 110540734 B CN110540734 B CN 110540734B CN 201910743355 A CN201910743355 A CN 201910743355A CN 110540734 B CN110540734 B CN 110540734B
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carbon nanotube
rubber
core layer
epoxy resin
fiber core
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CN110540734A (en
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邓飞
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Shenzhen Cone Technology Co ltd
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Shenzhen Cone Technology Co ltd
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    • 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
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Abstract

The invention provides a carbon nanotube composite fiber, which comprises a carbon nanotube fiber core layer, a rubber layer and an epoxy resin layer, wherein the carbon nanotube fiber core layer is used as the core layer of the carbon nanotube composite fiber, the rubber layer is coated on the outer surface of the carbon nanotube fiber core layer, and the epoxy resin layer is coated on the surface of the rubber layer, which is deviated from the carbon nanotube fiber core layer. The rubber layer is arranged between the carbon nanotube fiber core layer and the epoxy resin layer, and the rubber has good toughness, can absorb energy and block the expansion of cracks when the material is subjected to external load, can play a good role in buffering and toughening, and improves the interface toughness of the composite material as a whole.

Description

Carbon nanotube composite fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a carbon nanotube composite fiber and a preparation method thereof.
Background
The carbon nano tube has a unique structure and excellent mechanical properties, the mechanical properties of the epoxy resin can be effectively improved by introducing the carbon nano tube into the epoxy resin, and related researches are advanced to a certain extent. The carbon nano tube can play a role in reinforcing in the epoxy resin in a fiber form, and the better the interface bonding between the carbon nano tube fiber and the resin is, the better the reinforcing effect is. However, since the difference between the thermal expansion coefficients of the epoxy resin and the carbon nanotubes is large, a large interfacial stress is generated between the epoxy resin and the carbon nanotubes, and when an external load is applied, the interfacial toughness of the material is insufficient, and the generated cracks are easily diffused to cause the material to be damaged.
In order to improve the bonding effect between the carbon nanotube fiber and the epoxy resin, a sizing agent or the like is commonly used to modify the surface of the carbon nanotube, but this may destroy the structure of the carbon nanotube itself, thereby impairing the performance thereof. Accordingly, there is a need in the art to develop a carbon nanotube fiber composite having high interfacial toughness.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to obtain a carbon nanotube composite fiber and a preparation method thereof, and aims to solve the problem of low interface toughness of the existing carbon nanotube fiber epoxy resin composite material.
Means for solving the problems
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a carbon nanotube composite fiber, which comprises a carbon nanotube fiber core layer, a rubber layer and an epoxy resin layer, wherein the rubber layer is coated on the outer surface of the carbon nanotube fiber core layer, and the epoxy resin layer is coated on the surface of the rubber layer, which is deviated from the carbon nanotube fiber core layer.
Preferably, the carbon nanotube fiber core layer is formed by combining at least one carbon nanotube fiber bundle, and the carbon nanotube fiber bundle is formed by doubling a plurality of carbon nanotube fiber yarns.
Preferably, the material of the rubber layer is end functional group liquid rubber.
Preferably, the material of the epoxy resin layer is selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.
In another aspect, the present invention provides a method for preparing the carbon nanotube composite fiber, including the following steps:
obtaining a carbon nanotube fiber core layer and rubber, and depositing the rubber on the surface of the carbon nanotube fiber core layer to prepare the carbon nanotube fiber core layer with the surface coated with a rubber layer;
and obtaining an epoxy resin solution, mixing the carbon nanotube fiber core layer coated with the rubber layer on the surface with the epoxy resin solution, and then carrying out curing treatment to obtain the carbon nanotube composite fiber.
Preferably, the preparation method of the carbon nanotube fiber core layer 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 combining at least one carbon nanotube fiber bundle to obtain the carbon nanotube fiber core layer.
Preferably, in the step of twisting the carbon nanotube film, the carbon nanotube film with the width of 0.1m is selected for twisting; and/or
In the step of twisting the carbon nanotube film, the twist is 500-1000 tpm.
Preferably, the step of doubling a plurality of carbon nanotube fiber yarns comprises: and obtaining 80-120 carbon nanotube fiber yarns, carrying out non-twisting doubling or twisting doubling, wherein the twist degree during twisting doubling is 50-150 tpm.
Preferably, in the step of combining at least one carbon nanotube fiber bundle, a plurality of carbon nanotube fiber bundles are arranged in parallel or spirally along an axial direction of the carbon nanotube fiber core layer.
Preferably, the step of depositing the rubber solution on the surface of the carbon nanotube fiber core layer comprises: and dissolving the rubber to form a rubber solution, and enabling the carbon nano tube fiber core layer to pass through the rubber solution at a preset speed at a constant speed.
Preferably, the rubber solution contains 5.0-8.0g of the rubber per 100ml of the rubber solution, and the rubber is a terminal functional group liquid rubber.
Preferably, the preset speed is 0.004-0.02 m/s.
Preferably, the epoxy resin solution comprises epoxy resin and a curing agent, and the mass ratio of the curing agent to the epoxy resin is (20-30): 100.
Preferably, the step of performing a curing process comprises: heating at 80-150 deg.C for 4-6 hr.
Effects of the invention
The carbon nanotube composite fiber obtained by the invention comprises the carbon nanotube fiber core layer, the rubber layer and the epoxy resin layer, wherein the rubber layer is arranged between the carbon nanotube fiber core layer and the epoxy resin layer, and the rubber has good toughness, can absorb energy and block the expansion of cracks when the material is subjected to external load, and can play a good role in buffering and toughening, thereby improving the interface toughness of the composite material. Moreover, the prepared carbon nano tube fiber can be observed in a microscope to have whisker-shaped filaments which are characteristics of silk threads, and the whiskers and the rubber layer are physically combined, so that the combination strength is also improved. In addition, the rubber can be uniformly coated on the carbon nanotube fiber, and the rubber, the carbon nanotube fiber and the epoxy resin have good binding force, so that the good interface binding strength between the carbon nanotube fiber and the epoxy resin can be ensured.
According to the preparation method of the carbon nanotube composite fiber, the rubber layer and the epoxy resin layer are sequentially coated on the surface of the carbon nanotube fiber, so that the carbon nanotube composite fiber with high interface toughness is prepared.
Drawings
FIG. 1 is a longitudinal cross-sectional view of a carbon nanotube composite fiber according to a preferred embodiment of the present invention;
FIG. 2 is a cross-sectional view of a carbon nanotube composite fiber according to an embodiment of the present invention;
fig. 3 is a transverse cross-sectional view of a carbon nanotube composite fiber according to an embodiment of the present invention.
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.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
A carbon nanotube composite fiber, as shown in fig. 1, includes a carbon nanotube fiber core layer, a rubber layer and an epoxy resin layer, wherein the rubber layer is coated on the outer surface of the carbon nanotube fiber core layer, and the epoxy resin layer is coated on the surface of the rubber layer away from the carbon nanotube fiber core layer.
The carbon nanotube composite fiber provided by the embodiment of the invention comprises a carbon nanotube fiber core layer, a rubber layer and an epoxy resin layer, wherein the carbon nanotube fiber core layer is used as the core layer of the carbon nanotube composite fiber, and the rubber layer is arranged between the carbon nanotube fiber core layer and the epoxy resin layer. In addition, the rubber has good binding force with the carbon nano tube and the epoxy resin, and the good interface binding strength between the carbon nano tube and the epoxy resin can be ensured.
Specifically, the carbon nanotube fiber core layer is used as a core layer of the carbon nanotube composite fiber according to the embodiment of the present invention, and is a macroscopic fiber formed by combining at least one carbon nanotube fiber bundle. As shown in fig. 2, in some embodiments, in the carbon nanotube composite fiber, the carbon nanotube fiber core layer is a single carbon nanotube fiber bundle; in other embodiments, as shown in fig. 3, the carbon nanotube fiber core layer is formed by combining a plurality of carbon nanotube fibers, for example, 3 carbon nanotube fibers.
Preferably, the carbon nanotube fiber core layer is formed by combining at least one carbon nanotube fiber bundle, and the carbon nanotube fiber bundle is formed by doubling a plurality of carbon nanotube fiber yarns. When the carbon nano tube fiber core layer is observed in a microscope, the carbon nano tube fiber core layer can be found to have whisker-shaped filaments, and the carbon nano tube fiber core layer and the rubber layer are physically combined to assist in improving the combination strength. As a preferred embodiment, the carbon nanotube fiber core layer is obtained by twisting a carbon nanotube film. The carbon nanotube fiber obtained by twisting has better mechanical property, and the prepared carbon nanotube fiber can better meet the subsequent application requirements. In some embodiments, the twist of the carbon nanotube fiber core layer is 3000-10000 tpm. The carbon nanotube fiber core layer in the twist range has higher fiber strength, and when the twist is too low, the formed carbon nanotube fiber is not compact and firm, and the fiber performance is not good; when the twist is too high, the carbon nanotubes are subjected to too much tension, which may adversely affect the properties of the fiber. In other embodiments, the carbon nanotube fiber core layer has a diameter of 0.001 to 1 mm. In some embodiments, the preparation of the carbon nanotube fiber core layer comprises: selecting an ultralong carbon nanotube array with the diameter of 6-10nm and the length of 100-.
Specifically, the rubber layer is arranged between the carbon nanotube fiber core layer and the epoxy resin layer, and has good toughness, so that when the material is subjected to external load, the rubber layer can absorb energy and block the expansion of cracks, thereby playing a good role in buffering and toughening, and improving the interface toughness of the composite material as a whole.
Furthermore, the rubber layer has good bonding force with the carbon nano tube and the epoxy resin, and the good interface bonding strength between the carbon nano tube and the epoxy resin can be ensured. Preferably, the material of the rubber layer is preferably a functional group-terminated liquid rubber. The end functional group liquid rubber is a telechelic liquid polymer with active end groups at two ends, the active end groups comprise hydroxyl, carboxyl, amino and the like, and the interface binding force between the rubber layer and the epoxy resin layer can be effectively enhanced through the reaction between the active end groups and the epoxy resin groups, so that the interface toughening effect of the rubber layer is effectively improved. In some embodiments, the terminal-functional liquid rubber is selected from at least one of nitrile rubber, polysulfide rubber, polyurethane rubber, and silicone rubber; in other embodiments, the terminal functional group liquid rubber has a molecular weight of 2000-.
Specifically, the epoxy resin layer is a cured epoxy resin material thin layer and is arranged on the surface of the rubber layer, which is far away from the carbon nanotube fiber core layer. In an embodiment of the present invention, the material of the epoxy resin layer is selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.
In a preferred embodiment, in the carbon nanotube composite fiber, the volume of the carbon nanotube fiber core layer is 50% to 60% of the total volume of the carbon nanotube composite fiber. The volume of the rubber layer is 5% -15% of the carbon nano tube composite fiber, and the content of the rubber layer is too low to achieve the effect of interface toughening; too high a content will rather impair the mechanical properties. As another preferred embodiment, the volume of the epoxy resin layer is 25% -35% of the carbon nanotube composite fiber, the content of the epoxy resin layer is too low, the resin phase on the stressed section is reduced, the stress bearing point is too high, and the material strength and the modulus are poor; the epoxy layer content is too high and the presence of the rubber layer is not sufficient to prevent the propagation of cracks in the epoxy matrix.
The following is a specific embodiment of the method for producing the carbon nanotube composite fiber.
Correspondingly, the preparation method of the carbon nanotube composite fiber comprises the following steps.
S01, obtaining a carbon nanotube fiber core layer and rubber, and depositing the rubber on the surface of the carbon nanotube fiber core layer to prepare the carbon nanotube fiber core layer with the surface coated with a rubber layer;
s02, obtaining an epoxy resin solution, mixing the carbon nanotube fiber core layer coated with the rubber layer on the surface with the epoxy resin solution, and then curing to obtain the carbon nanotube composite fiber.
According to the preparation method of the carbon nanotube composite fiber, which is obtained by the embodiment of the invention, the rubber layer and the epoxy resin layer are sequentially coated and arranged on the surface of the carbon nanotube fiber core layer, so that the carbon nanotube composite fiber with high interface toughness is prepared.
Specifically, in step S01, the rubber is deposited on the surface of the carbon nanotube fiber core layer to prepare a carbon nanotube fiber core layer coated with a rubber layer on the surface. Preferably, the step of depositing the rubber on the surface of the carbon nanotube fiber core layer comprises: and dissolving the rubber to form a rubber solution, and enabling the carbon nano tube fiber core layer to pass through the rubber solution at a preset speed at a constant speed. In some embodiments, the carbon nanotube fiber core layer passes through the rubber solution at a constant speed of 0.004-0.2m/s, so that the rubber solution is uniformly coated on the surface of the carbon nanotube fiber core layer, and the thickness of the rubber layer is ensured to be uniform.
Further, the rubber solution mainly includes rubber and a first solvent, and preferably, the rubber solution includes 5.0 to 8.0g of rubber per 100ml, so that the rubber can be uniformly coated on the surface of the carbon nanotube fiber core layer. When the concentration of the rubber is lower than 5.0g/100mL, the rubber layer coated on the surface of the carbon nanotube fiber core layer is too thin, so that the rubber layer can not completely cover the carbon nanotube fiber core layer; when the concentration of the rubber is more than 8.0g/100mL, part of the rubber can agglomerate on the surface of the carbon nanotube fiber core layer, so that the thickness of the rubber layer is uneven. Preferably, the first solvent is at least one selected from the group consisting of acetone, butanone, cyclohexane, benzene, xylene, and ethyl acetate, which can sufficiently completely dissolve the rubber.
The carbon nanotube fiber core layer is substantially the same as the carbon nanotube fiber core layer in the carbon nanotube composite fiber, and the rubber is substantially the same as the rubber in the carbon nanotube composite fiber, so that details are not repeated here for saving space.
As a preferred embodiment, the method for preparing the carbon nanotube fiber core layer 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, combining at least one carbon nanotube fiber bundle to obtain the carbon nanotube fiber core layer.
More specifically, in step S011, the carbon nanotube film is drawn from the carbon nanotube array to obtain the raw material carbon nanotubes for preparing the carbon nanotube fiber, and the suggestion drawn from the carbon nanotube array briefly states that the carbon nanotubes in the carbon nanotube film, which have the positive effect of the carbon nanotubes prepared by the method, are arranged in order and have uniform length and diameter.
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 the width of 0.1m is selected for twisting; and in the step of twisting the carbon nanotube film, twisting the carbon nanotube film according to the twist of 500-1000 tpm.
In step S012, a plurality of carbon nanotube filaments are subjected to a doubling process to obtain a carbon nanotube fiber bundle. Further, the step of doubling the plurality of carbon nanotube fiber yarns comprises: and obtaining 80-120 carbon nanotube fiber yarns, carrying out non-twisting doubling or twisting doubling, wherein the twist degree during twisting doubling is 50-150 tpm.
In step S013, at least one of the carbon nanotube fiber bundles is combined to obtain the carbon nanotube fiber core layer. Preferably, in the step of combining at least one carbon nanotube fiber bundle, a plurality of carbon nanotube fiber bundles are arranged in parallel or spirally along an axial direction of the carbon nanotube fiber core layer. Furthermore, a plurality of carbon nano tube fiber bundles are combined in an external force compaction mode. In some embodiments, the external force densification is preferably a twisting process.
In step S02, the carbon nanotube fiber core layer coated with the rubber layer on the surface is mixed with the epoxy resin solution, so that the carbon nanotube fiber core layer coated with the rubber layer on the surface is in full contact with the epoxy resin solution, which is beneficial for the epoxy resin solution to form an epoxy resin layer on the surface of the rubber layer away from the carbon nanotube fiber core layer. In some embodiments, the step of mixing the carbon nanotube fiber core layer surface-coated with a rubber layer with the epoxy resin solution comprises: fixing the carbon nanotube fiber core layer with the surface coated with the rubber layer in a mold, and then filling an epoxy resin solution in a mold cavity, more specifically, the step of filling the epoxy resin solution in the mold cavity adopts a vacuum assisted resin transfer molding method.
In the embodiment of the invention, the epoxy resin solution comprises an epoxy resin and a curing agent, the mass ratio of the curing agent to the epoxy resin is preferably (20-30):100, and when the amount of the curing agent is too large, the resin is embrittled; when the amount of the curing agent is too small, the curing is incomplete. In some embodiments, the mass ratio of the curing agent to the epoxy resin is 20:100, 21:100, 22:100, 23:100, 24:100, 25:100, 26:100, 27:100, 28:100, 29:100, 30: 100.
Preferably, the viscosity of the epoxy resin solution is 100-500mPa.s, so as to ensure that the epoxy resin solution has good fluidity. In some embodiments, the viscosity of the epoxy resin solution is 100, 150, 250, 300, 400, 500 mpa.s.
Further, the epoxy resin is selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. The 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.
Further, the epoxy resin solution further comprises: and a second solvent for dissolving the epoxy resin and the curing agent, the second solvent preferably being at least one of acetone, butanone, xylene, n-butanol, and ethyl acetate.
In summary, under the comprehensive action of the optimized material components and the usage range thereof, the reaction temperature, the time and other condition parameters obtained in the embodiments of the present invention, and the optimization process, the carbon nanotube composite fiber obtained by the preparation method obtained in the embodiments of the present invention has the best interfacial toughness, and in some test examples, the interfacial shear strength is 20.3-24.5MPa, which is significantly better than 17.0MPa of the comparative example.
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 composite fiber and the method for preparing the same apparent from the embodiments of the present invention, the implementation of the present invention is illustrated by the following examples.
Example 1
The embodiment prepares the carbon nanotube composite fiber, and the specific process flow is as follows:
s11, pulling out 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 1000tpm to obtain carbon nanotube fiber yarns; then, carrying out doubling treatment on a plurality of carbon nanotube fiber yarns to obtain a carbon nanotube fiber bundle; then, combining a plurality of carbon nano tube fiber bundles to obtain a carbon nano tube fiber core layer with the diameter of about 0.09 mm; and adding the carbon nano tube fiber core layer into an ethanol solution for treatment, and compacting to obtain the treated carbon nano tube fiber core layer.
S12, preparing 5.5g/100mL hydroxyl-terminated nitrile rubber acetone solution. And (3) enabling the treated carbon nanotube fiber core layer to pass through the rubber solution at a constant speed of 0.004m/s, and uniformly coating a rubber layer on the surface to obtain the carbon nanotube fiber core layer coated with the rubber layer on the surface.
S13, uniformly mixing the bisphenol F type epoxy resin and diethylenetriamine according to the mass ratio of 100:25, and then adding acetone for full dilution to obtain an epoxy resin solution with the viscosity of 500 mPa.s. And then fixing the carbon nanotube fiber core layer coated with the rubber on a mold, filling an epoxy resin solution into the mold to enable the carbon nanotube fiber core layer to be fully soaked in the epoxy resin solution, curing at 120 ℃ for 6 hours, and demolding and polishing to obtain the carbon nanotube composite fiber.
Example 2
The embodiment prepares the carbon nanotube composite fiber, and the specific process flow is as follows:
s21, 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 1200tpm to obtain a carbon nanotube fiber core layer with the diameter of about 0.09 mm; and (3) carrying out ethanol solution treatment on the carbon nanotube fiber core layer to make the carbon nanotube fiber core layer compact so as to obtain the treated carbon nanotube fiber core layer.
S22, 6.0g/100mL of polysulfide rubber acetone solution is prepared. And (3) enabling the treated carbon nanotube fiber core layer to pass through the rubber solution at a constant speed of 0.01m/s, and uniformly coating a rubber layer on the surface to obtain the carbon nanotube fiber core layer coated with the rubber layer on the surface.
S23, uniformly mixing the bisphenol F type epoxy resin and diethylenetriamine according to the mass ratio of 100:25, and then adding acetone for full dilution to obtain an epoxy resin solution with the viscosity of 500 mPa.s. Fixing the carbon nanotube fiber core layer coated with the rubber on a mold, filling an epoxy resin solution into the mold to enable the carbon nanotube fiber core layer to be fully soaked in the epoxy resin solution, then curing for 6 hours at 120 ℃, and obtaining the epoxy resin-based carbon nanotube fiber core layer after demolding and polishing.
Example 3
S31, 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 1200tpm to obtain a carbon nanotube fiber core layer with the diameter of about 0.09 mm; and (3) carrying out ethanol solution treatment on the carbon nanotube fiber core layer to make the carbon nanotube fiber core layer compact so as to obtain the treated carbon nanotube fiber core layer.
S32, 8.0g/100mL of polyurethane rubber acetone solution is prepared. And (3) enabling the treated carbon nanotube fiber core layer to pass through the rubber solution at a constant speed of 0.02m/s, and uniformly coating a rubber layer on the surface to obtain the carbon nanotube fiber core layer coated with the rubber layer on the surface.
S33, uniformly mixing the bisphenol F type epoxy resin and diethylenetriamine according to the mass ratio of 100:25, and then adding acetone for full dilution to obtain an epoxy resin solution with the viscosity of 500 mPa.s. And fixing the carbon nanotube fiber core layer coated with the rubber on a mold, filling the mold with the epoxy resin solution to enable the carbon nanotube fiber core layer to be fully soaked in the epoxy resin solution, then curing for 6 hours at 120 ℃, and obtaining the epoxy resin-based carbon nanotube fiber core layer after demolding and polishing.
Comparative example
1. 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 1200tpm to obtain a carbon nanotube fiber core layer with the diameter of about 0.09 mm; and (3) carrying out ethanol solution treatment on the carbon nanotube fiber core layer to make the carbon nanotube fiber core layer compact so as to obtain the treated carbon nanotube fiber core layer.
2. Uniformly mixing bisphenol F type epoxy resin and diethylenetriamine according to the mass ratio of 100:25, and then adding acetone for full dilution to obtain an epoxy resin solution with the viscosity of 500 mPa.s. And fixing the carbon nanotube fiber core layer coated with the rubber on a mold, filling the mold with the epoxy resin solution to enable the carbon nanotube fiber core layer to be fully soaked in the epoxy resin solution, then curing for 6 hours at 120 ℃, and obtaining the epoxy resin-based carbon nanotube fiber core layer after demolding and polishing.
Test example
Miniature dumbbell-shaped carbon nanotube fiber core samples were prepared in examples 1-3 and comparative example 1, respectively, using miniature dumbbell-shaped molds.
When the dumbbell-shaped test sample is axially stretched, the fibers in the resin can be broken, and the broken length of the fibers reaches the length of the dumbbell-shaped test sample along with the increase of the loadThe fracture will not occur after the critical length. Under orthogonal polarization, the critical fiber length l can be measured by an optical microscopec. The ultimate tensile strength sigma is measured by a tensile testerUTS(ii) a d is the fiber diameter, obtained by SEM testing. The average value of the interface shear strength shown in table 1 is obtained through multiple measurements, and it is shown that the interface toughness of the composite material can be effectively improved by arranging different rubber layers between the carbon nanotube fiber core layer and the epoxy resin layer in the embodiment of the invention, so that the interface shear strength of the carbon nanotube composite fiber is effectively improved.
The calculation formula of the interface shear strength is as follows:
Figure BDA0002164741410000111
TABLE 1
Figure BDA0002164741410000121
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 (14)

1. The carbon nanotube composite fiber is characterized by comprising a carbon nanotube fiber core layer, a rubber layer and an epoxy resin layer, wherein the rubber layer is coated on the outer surface of the carbon nanotube fiber core layer, and the epoxy resin layer is coated on the surface of the rubber layer, which is deviated from the carbon nanotube fiber core layer;
the volume of the carbon nanotube fiber core layer is 50% -60% of the total volume of the carbon nanotube composite fiber, the volume of the rubber layer is 5% -15% of the carbon nanotube composite fiber, and the volume of the epoxy resin layer is 25% -35% of the carbon nanotube composite fiber.
2. The carbon nanotube composite fiber according to claim 1, wherein the carbon nanotube fiber core layer is formed by combining at least one carbon nanotube fiber bundle, and the carbon nanotube fiber bundle is formed by doubling a plurality of carbon nanotube fiber filaments.
3. The carbon nanotube composite fiber according to claim 1, wherein the rubber layer is made of a functional group-terminated liquid rubber.
4. The carbon nanotube composite fiber according to claim 1, wherein the epoxy resin layer is made of at least one material selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.
5. A method for preparing the carbon nanotube composite fiber according to any one of claims 1 to 4, comprising the steps of:
obtaining a carbon nanotube fiber core layer and rubber, and depositing the rubber on the surface of the carbon nanotube fiber core layer to prepare the carbon nanotube fiber core layer with the surface coated with a rubber layer;
and obtaining an epoxy resin solution, mixing the carbon nanotube fiber core layer coated with the rubber layer on the surface with the epoxy resin solution, and then carrying out curing treatment to obtain the carbon nanotube composite fiber.
6. The method for preparing the carbon nanotube fiber core layer according to claim 5, wherein the method for preparing the carbon nanotube fiber core layer 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 combining at least one carbon nanotube fiber bundle to obtain the carbon nanotube fiber core layer.
7. The method according to claim 6, wherein in the step of twisting the carbon nanotube film, a carbon nanotube film having a width of 0.1m is selected to be twisted; and/or
In the step of twisting the carbon nanotube film, the twist is 500-1000 tpm.
8. The method according to claim 6, wherein the step of doubling the plurality of carbon nanotube fiber filaments comprises: and obtaining 80-120 carbon nanotube fiber yarns, carrying out non-twisting doubling or twisting doubling, wherein the twist degree during twisting doubling is 50-150 tpm.
9. The method according to claim 6, wherein the step of combining at least one of the carbon nanotube fiber bundles comprises arranging a plurality of the carbon nanotube fiber bundles in parallel or spirally in an axial direction of the carbon nanotube fiber core layer.
10. The method according to any one of claims 5 to 9, wherein the step of depositing the rubber on the surface of the carbon nanotube fiber core layer comprises: and dissolving the rubber to form a rubber solution, and enabling the carbon nano tube fiber core layer to pass through the rubber solution at a preset speed at a constant speed.
11. The method according to claim 10, wherein the rubber solution contains 5.0 to 8.0g of the rubber per 100ml of the rubber solution, and the rubber is a terminal-functional-group liquid rubber.
12. The method for preparing in accordance with claim 10, wherein the preset speed is 0.004-0.02 m/s.
13. The production method according to any one of claims 5 to 9, characterized in that the epoxy resin solution contains an epoxy resin and a curing agent, and the mass ratio of the curing agent to the epoxy resin is (20-30): 100.
14. The production method according to any one of claims 5 to 9, wherein the step of performing the curing treatment includes: heating at 80-150 deg.C for 4-6 hr.
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