CN113463376A - Preparation method of nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber - Google Patents
Preparation method of nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber. The method comprises the following steps: firstly, removing agents from carbon fibers, secondly, preparing a nano-cellulose aqueous solution, a carbon nano-tube aqueous solution and a mixed solution of the nano-cellulose aqueous solution and the carbon nano-tube aqueous solution, thirdly, preparing a polyvinyl alcohol aqueous solution, finally depositing the nano-cellulose, the carbon nano-tube and the polyvinyl alcohol on the surface of a uniformly laid carbon fiber tow by adopting a vacuum filtration method, then turning the carbon fiber tow by 180 degrees, and finally, carrying out suction filtration on the nano-cellulose, the carbon nano-tube and the polyvinyl alcohol to obtain the nano-cellulose/carbon nano-tube/polyvinyl alcohol synergistically modified carbon fibers. The preparation method of the invention forms a super-hydrogen bond network on the surface of the fiber, improves the interface bonding strength of the composite material by 54.2-120.7%, does not reduce the strength of the carbon fiber, and has the advantages of simplicity, convenience, high efficiency, greenness and low cost.
Description
Technical Field
The invention belongs to the technical field of surface and interface modification application of materials, and particularly relates to a preparation method of a nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber.
Background
With the increasing development of national economy, the carbon fiber resin matrix composite material has more and more extensive application in various fields and increasing use amount, and meanwhile, the carbon fiber resin matrix composite material also puts higher and higher requirements on the performance of the carbon fiber resin matrix composite material in the national defense fields of aerospace, ships, energy sources and the like. However, the surface of the carbon fiber lacks active functional groups, so that the carbon fiber is high in inertia, poor in wettability with resin and low in interface strength, and does not meet the requirements of the national defense field on high-performance carbon fiber resin matrix composite materials. Therefore, it is necessary to modify the surface of the carbon fiber to improve the bonding strength between the carbon fiber and the resin and to better exert the excellent properties of the carbon fiber itself.
With the development of nanotechnology, nanoreinforcement is considered to be one of the most promising reinforcement materials for significantly improving the overall performance of carbon fiber reinforced composites, where carbon nanotubes and nanocellulose have been widely used for modifying carbon fibers as a representative of one-dimensional nanomaterials. However, most of the modification methods require catalysts, organic reagents, high temperature, harsh reaction conditions, high cost, and the like, which are not beneficial for large-scale application or environmental pollution, and therefore, development of a simple, efficient, green, and low-cost modification method is urgently needed. The polyvinyl alcohol is a pollution-free, easily degradable and high-molecular chemical raw material with good water solubility, has good cohesiveness, and has high potential value in improving the interfacial bonding strength of the composite material by combining the polyvinyl alcohol with the carbon nano tube and the nano cellulose.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon fiber synergistically modified by nano-cellulose/carbon nano-tube/polyvinyl alcohol, which can greatly improve the interface bonding strength of a carbon fiber resin matrix composite material, and meanwhile, the method does not reduce the strength of the carbon fiber, and is simple, efficient, green and low in cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
1) condensing and refluxing the carbon fiber tows in an acetone solution, then cleaning the carbon fiber tows by using deionized water and drying the carbon fiber tows in vacuum;
2) respectively preparing a nano-cellulose aqueous solution and a carbon nano-tube aqueous solution with the mass fraction of 0.01-5% which are uniformly dispersed;
3) preparing a polyvinyl alcohol aqueous solution with the mass fraction of 0.01-2%, and stirring to obtain a uniformly dispersed polyvinyl alcohol aqueous solution;
4) uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, wherein the mass ratio of the nano-cellulose aqueous solution to the carbon nano-tube aqueous solution is 1: (0.1-5) mixing the two aqueous solutions, uniformly dispersing the two aqueous solutions by magnetic stirring to obtain a nano-cellulose/carbon nano-tube mixed solution, carrying out suction filtration on the nano-cellulose/carbon nano-tube mixed solution, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution to deposit the nano-cellulose/carbon nano-tube mixed solution and the polyvinyl alcohol aqueous solution on the surface of a carbon fiber bundle; then turning the carbon fiber tows for 180 degrees, carrying out suction filtration on the nano-cellulose/carbon nanotube mixed solution and polyvinyl alcohol aqueous solution with the same amount to deposit the nano-cellulose/carbon nanotube mixed solution and the polyvinyl alcohol aqueous solution on the other side of the carbon fiber tows, and finally drying in an oven to obtain the carbon fiber synergistically modified by the nano-cellulose/carbon nanotube/polyvinyl alcohol;
or uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the nano-cellulose aqueous solution, then carrying out suction filtration on the carbon nanotube aqueous solution, and carrying out suction filtration on the polyvinyl alcohol aqueous solution to deposit the polyvinyl alcohol aqueous solution on the surfaces of the carbon fiber tows; turning the filtered carbon fiber tows for 180 degrees, filtering the nano-cellulose aqueous solution, the carbon nanotube aqueous solution and the polyvinyl alcohol aqueous solution with the same amount, and finally drying in an oven to obtain the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber;
or uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the carbon nanotube aqueous solution, then carrying out suction filtration on the nanocellulose aqueous solution, and carrying out suction filtration on the polyvinyl alcohol aqueous solution to deposit the polyvinyl alcohol aqueous solution on the surfaces of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, filtering the carbon nanotube aqueous solution, the nano-cellulose aqueous solution and the polyvinyl alcohol aqueous solution with the same amount, and finally drying in an oven to obtain the carbon fiber synergistically modified by the nano-cellulose/the carbon nanotube/the polyvinyl alcohol.
The carbon fiber in the step 1) is a long carbon fiber.
The reflux temperature in the step 1) is 80-100 ℃, and the reflux time is 12-48 h.
The nano-cellulose in the step 2) is cellulose nanocrystal, cellulose nano-fiber or bacterial nano-cellulose.
The stirring temperature in the step 3) is 95-110 ℃, and the stirring time is 1-3 h.
The magnetic stirring speed of the step 4) is 200-800 rpm/min, and the time is 30-100 min.
And 4) carrying out suction filtration according to the volumes (ml) of the nano-cellulose/carbon nano-tube mixed solution, the nano-cellulose aqueous solution, the carbon nano-tube aqueous solution and the polyvinyl alcohol aqueous solution, wherein the diameter (cm) of the filter membrane is (0.1-5): 1.
The drying temperature of the steps 1) and 4) is 40-80 ℃, and the drying time is 2-5 h.
Compared with the prior art, the invention has the following beneficial technical effects: (1) the method realizes uniform coating of the organic-inorganic nano composite coating on the surface of the carbon fiber tows with the circumferential structure by adopting a vacuum filtration method for the first time, does not reduce the strength of the carbon fibers, and has the advantages of simplicity, convenience, high efficiency, greenness and low cost. (2) The nano-cellulose, the carbon nano-tube and the polyvinyl alcohol can form a super-hydrogen bond network on the surface of the fiber, and can obviously improve the wettability of the fiber and resin. (3) Compared with the unmodified carbon fiber composite material, the interface bonding strength of the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistic modified carbon fiber composite material is improved by 54.2-120.7%.
Drawings
Fig. 1 is a surface topography diagram of the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber prepared in example 1.
Fig. 2 is a surface topography of the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
1) condensing and refluxing the long carbon fiber tows in an acetone solution at the temperature of 80 ℃ for 24 hours, then washing the fibers by deionized water and drying the fibers in a vacuum drying oven at the temperature of 60 ℃ for 3 hours.
2) Preparing a cellulose nanofiber aqueous solution and a carbon nano tube aqueous solution which are uniformly dispersed with the mass fraction of 0.05%, mixing the two aqueous solutions, wherein the mass ratio of the cellulose nanofiber aqueous solution to the carbon nano tube aqueous solution is 1:1, and magnetically stirring at 300rpm/min for 40min to uniformly disperse the cellulose nanofiber/carbon nano tube aqueous solution to obtain a cellulose nanofiber/carbon nano tube mixed solution.
3) Preparing a polyvinyl alcohol aqueous solution with the mass fraction of 1%, and stirring for 1h at 95 ℃ to obtain the uniformly dispersed polyvinyl alcohol aqueous solution.
4) Uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the cellulose nanofiber/carbon nanotube mixed solution according to the volume (ml) of the cellulose nanofiber/carbon nanotube mixed solution, wherein the diameter (cm) of the filter membrane is 0.2:1, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution with the volume being 3 times that of the mixed solution to deposit the polyvinyl alcohol aqueous solution on the surface of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, carrying out suction filtration on the cellulose nanofiber/carbon nanotube mixed solution with the same amount, carrying out suction filtration on the polyvinyl alcohol aqueous solution to deposit the polyvinyl alcohol aqueous solution on the other surface of the carbon fiber tows, and finally drying the carbon fiber tows at 60 ℃ for 3 hours to obtain the cellulose nanofiber/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber.
The surface appearance of the prepared cellulose nanofiber/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber is shown in figure 1, and the interfacial bonding strength of the epoxy composite material prepared by adopting the fiber is improved by 54.2 percent compared with that of an unmodified carbon fiber reinforced epoxy composite material.
Example 2:
1) the long carbon fiber tows are condensed and refluxed for 48 hours in acetone solution at the temperature of 80 ℃, then the fibers are washed by deionized water and dried for 4 hours in a vacuum drying oven at the temperature of 50 ℃.
2) Preparing a cellulose nanofiber aqueous solution and a carbon nano tube aqueous solution which are uniformly dispersed with the mass fraction of 0.05%, mixing the two aqueous solutions, wherein the mass ratio of the cellulose nanofiber aqueous solution to the carbon nano tube aqueous solution is 1:1, and magnetically stirring at 500rpm/min for 40min to uniformly disperse the cellulose nanofiber/carbon nano tube aqueous solution to obtain a cellulose nanofiber/carbon nano tube mixed solution.
3) Preparing a polyvinyl alcohol aqueous solution with the mass fraction of 1%, and stirring for 1h at 95 ℃ to obtain the uniformly dispersed polyvinyl alcohol aqueous solution.
4) Uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the cellulose nanofiber/carbon nanotube mixed solution according to the volume (ml) of the cellulose nanofiber/carbon nanotube mixed solution, wherein the diameter (cm) of the filter membrane is 0.1:1, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution with the volume being 10 times that of the mixed solution to deposit the polyvinyl alcohol aqueous solution on the surface of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, carrying out suction filtration on the cellulose nanofiber/carbon nanotube mixed solution with the same amount, carrying out suction filtration on the polyvinyl alcohol aqueous solution to deposit the polyvinyl alcohol aqueous solution on the other surface of the carbon fiber tows, and finally drying at 50 ℃ for 4 hours to obtain the cellulose nanofiber/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber.
The surface appearance of the prepared cellulose nanofiber/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber is shown in fig. 2, and the interface bonding strength of the epoxy composite material prepared by adopting the fiber is improved by 102.5 percent compared with that of an unmodified carbon fiber reinforced epoxy composite material.
Example 3:
1) the long carbon fiber tows are condensed and refluxed in acetone solution at 100 ℃ for 12 hours, then the fibers are washed by deionized water and dried in a vacuum drying oven at 80 ℃ for 3 hours.
2) Preparing uniformly dispersed cellulose nanofiber aqueous solution and carbon nanotube aqueous solution with the mass fraction of 5%.
3) Preparing a polyvinyl alcohol aqueous solution with the mass fraction of 0.01%, and stirring for 3h at 95 ℃ to obtain the uniformly dispersed polyvinyl alcohol aqueous solution.
4) Uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the cellulose nano-fiber aqueous solution according to the volume (ml) of the cellulose nano-fiber aqueous solution, wherein the diameter (cm) of the filter membrane is 0.3:1, then carrying out suction filtration on the carbon nano-tube aqueous solution with the volume 2 times that of the cellulose nano-fiber aqueous solution, and then carrying out suction filtration on the polyvinyl alcohol aqueous solution with the volume 3 times that of the cellulose nano-fiber aqueous solution to deposit the polyvinyl alcohol aqueous solution on the surface of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, carrying out suction filtration on the cellulose nanofiber and carbon nanotube aqueous solution with the same amount, carrying out suction filtration on the polyvinyl alcohol aqueous solution to deposit the polyvinyl alcohol aqueous solution on the other surface of the carbon fiber tows, and finally drying the carbon fiber tows at 80 ℃ for 3 hours to obtain the cellulose nanofiber/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber.
Compared with the interface bonding strength of the composite material prepared by compounding the prepared cellulose nanofiber/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber and epoxy resin, the interface bonding strength of the unmodified carbon fiber composite material is improved by 120.7%.
Example 4:
1) the long carbon fiber tows are condensed and refluxed for 48 hours in acetone solution at 90 ℃, then the fibers are washed by deionized water and dried for 5 hours at 40 ℃ in a vacuum drying oven.
2) Preparing a cellulose nanocrystalline aqueous solution and a carbon nano tube aqueous solution with the mass fraction of 0.01% and uniform dispersion, mixing the two aqueous solutions, wherein the mass ratio of the cellulose nanocrystalline aqueous solution to the carbon nano tube aqueous solution is 1:5, and magnetically stirring the solution at 200rpm/min for 30min to uniformly disperse the solution, thereby obtaining the cellulose nanocrystalline/carbon nano tube mixed solution.
3) Preparing a polyvinyl alcohol aqueous solution with the mass fraction of 0.05%, and stirring for 2 hours at 105 ℃ to obtain the uniformly dispersed polyvinyl alcohol aqueous solution.
4) Uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, wherein the volume (ml) of the cellulose nanocrystal/carbon nanotube mixed solution is that the diameter (cm) of the filter membrane is 5:1, carrying out suction filtration on the cellulose nanocrystal/carbon nanotube mixed solution, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution with the volume being 12 times that of the mixed solution to enable the polyvinyl alcohol aqueous solution to be deposited on the surface of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, carrying out suction filtration on the mixed solution of the cellulose nanocrystals and the carbon nanotubes with the same amount, carrying out suction filtration on the aqueous solution of the polyvinyl alcohol to deposit the aqueous solution on the other surface of the carbon fiber tows, and finally drying the carbon fiber tows at 40 ℃ for 5 hours to obtain the carbon fiber synergistically modified by the cellulose nanocrystals, the carbon nanotubes and the polyvinyl alcohol.
Compared with the interface bonding strength of the composite material prepared by compounding the prepared cellulose nanocrystal/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber and the epoxy resin, the interface bonding strength of the unmodified carbon fiber composite material is improved by 111.1%.
Example 5:
1) the long carbon fiber tows are condensed and refluxed in acetone solution at 100 ℃ for 12 hours, then the fibers are washed by deionized water and dried in a vacuum drying oven at 80 ℃ for 2 hours.
2) Preparing uniformly dispersed cellulose nano-crystal water solution and carbon nano-tube water solution with the mass fraction of 2%.
3) Preparing a polyvinyl alcohol aqueous solution with the mass fraction of 2%, and stirring for 1h at 110 ℃ to obtain the uniformly dispersed polyvinyl alcohol aqueous solution.
4) Uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on a cellulose nanocrystalline aqueous solution according to the volume (ml) of the cellulose nanocrystalline aqueous solution, wherein the diameter (cm) of the filter membrane is 1:1, then carrying out suction filtration on a carbon nanotube aqueous solution with the volume 2.5 times that of the cellulose nanocrystalline aqueous solution, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution with the volume 0.5 times that of the cellulose nanocrystalline aqueous solution to deposit the polyvinyl alcohol aqueous solution on the surface of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, carrying out suction filtration on the cellulose nanocrystal aqueous solution and the carbon nanotube aqueous solution with the same amount, carrying out suction filtration on the polyvinyl alcohol aqueous solution to enable the polyvinyl alcohol aqueous solution to be deposited on the other surface of the carbon fiber tows, and finally drying for 2 hours at 80 ℃ to obtain the cellulose nanocrystal/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber.
The interface bonding strength of the composite material prepared by compounding the prepared cellulose nanocrystal/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber and the epoxy resin is improved by 90.4 percent compared with that of the unmodified carbon fiber composite material.
Example 6:
1) the long carbon fiber tows are condensed and refluxed in acetone solution at 100 ℃ for 24 hours, then the fibers are washed by deionized water and dried in a vacuum drying oven at 40 ℃ for 4 hours.
2) And preparing a uniformly dispersed bacterial nano cellulose aqueous solution and a carbon nano tube aqueous solution with the mass fraction of 0.1%.
3) Preparing 1.5 percent of polyvinyl alcohol aqueous solution by mass fraction, and stirring for 3 hours at 100 ℃ to obtain the uniformly dispersed polyvinyl alcohol aqueous solution.
4) Uniformly laying the carbon fiber tows obtained by the step 1) on a filter membrane, carrying out suction filtration on the carbon nanotube aqueous solution according to the volume (ml) of the carbon nanotube aqueous solution, wherein the diameter (cm) of the filter membrane is 2:1, then carrying out suction filtration on a bacterial nano-cellulose aqueous solution with the volume 0.3 times that of the carbon nanotube aqueous solution, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution with the volume 0.2 times that of the carbon nanotube aqueous solution to deposit the polyvinyl alcohol aqueous solution on the surface of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, carrying out suction filtration on the carbon nanotube aqueous solution and the bacterial nano-cellulose aqueous solution with the same amount, carrying out suction filtration on the polyvinyl alcohol aqueous solution to enable the polyvinyl alcohol aqueous solution to be deposited on the other surface of the carbon fiber tows, and finally drying at 40 ℃ for 4 hours to obtain the bacterial nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber.
Example 7:
1) the long carbon fiber tows are condensed and refluxed in acetone solution at 90 ℃ for 12 hours, then the fibers are washed by deionized water and dried in a vacuum drying oven at 60 ℃ for 4 hours.
2) Preparing a uniformly dispersed bacterial nano-cellulose aqueous solution and a carbon nano-tube aqueous solution with the mass fraction of 3.5%, mixing the two aqueous solutions, wherein the mass ratio of the bacterial nano-cellulose aqueous solution to the carbon nano-tube aqueous solution is 1:0.1, and magnetically stirring at 800rpm/min for 100min to uniformly disperse the two aqueous solutions to obtain a bacterial nano-cellulose/carbon nano-tube mixed solution.
3) Preparing a polyvinyl alcohol aqueous solution with the mass fraction of 0.5%, and stirring for 3h at 95 ℃ to obtain the uniformly dispersed polyvinyl alcohol aqueous solution.
4) Uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the mixed solution of the bacterial nano-cellulose and the carbon nano-tube according to the volume (ml) of the mixed solution of the bacterial nano-cellulose and the carbon nano-tube, wherein the diameter (cm) of the filter membrane is 3:1, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution with the volume being 0.1 time that of the mixed solution to enable the polyvinyl alcohol aqueous solution to be deposited on the surface of the carbon fiber tows; turning the filtered carbon fiber tows for 180 degrees, then filtering the mixed solution of the cellulose nano-fiber and the carbon nano-tube with the same amount, then filtering the polyvinyl alcohol aqueous solution to deposit on the other surface of the carbon fiber tows,
and finally drying the carbon fiber at the temperature of 60 ℃ for 4 hours to obtain the bacteria nano-cellulose/carbon nano-tube/polyvinyl alcohol synergistically modified carbon fiber.
Claims (8)
1. A preparation method of nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber is characterized by comprising the following steps:
1) condensing and refluxing the carbon fiber tows in an acetone solution, then cleaning the carbon fiber tows by using deionized water and drying the carbon fiber tows in vacuum;
2) respectively preparing a nano-cellulose aqueous solution and a carbon nano-tube aqueous solution with the mass fraction of 0.01-5% which are uniformly dispersed;
3) preparing a polyvinyl alcohol aqueous solution with the mass fraction of 0.01-2%, and stirring to obtain a uniformly dispersed polyvinyl alcohol aqueous solution;
4) uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, wherein the mass ratio of the nano-cellulose aqueous solution to the carbon nano-tube aqueous solution is 1: (0.1-5) mixing the two aqueous solutions, uniformly dispersing the two aqueous solutions by magnetic stirring to obtain a nano-cellulose/carbon nano-tube mixed solution, carrying out suction filtration on the nano-cellulose/carbon nano-tube mixed solution, and then carrying out suction filtration on a polyvinyl alcohol aqueous solution to deposit the nano-cellulose/carbon nano-tube mixed solution and the polyvinyl alcohol aqueous solution on the surface of a carbon fiber bundle; then turning the carbon fiber tows for 180 degrees, carrying out suction filtration on the nano-cellulose/carbon nanotube mixed solution and polyvinyl alcohol aqueous solution with the same amount to deposit the nano-cellulose/carbon nanotube mixed solution and the polyvinyl alcohol aqueous solution on the other side of the carbon fiber tows, and finally drying in an oven to obtain the carbon fiber synergistically modified by the nano-cellulose/carbon nanotube/polyvinyl alcohol;
or uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the nano-cellulose aqueous solution, then carrying out suction filtration on the carbon nanotube aqueous solution, and carrying out suction filtration on the polyvinyl alcohol aqueous solution to deposit the polyvinyl alcohol aqueous solution on the surfaces of the carbon fiber tows; turning the filtered carbon fiber tows for 180 degrees, filtering the nano-cellulose aqueous solution, the carbon nanotube aqueous solution and the polyvinyl alcohol aqueous solution with the same amount, and finally drying in an oven to obtain the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber;
or uniformly laying the carbon fiber tows obtained by the treatment in the step 1) on a filter membrane, carrying out suction filtration on the carbon nanotube aqueous solution, then carrying out suction filtration on the nanocellulose aqueous solution, and carrying out suction filtration on the polyvinyl alcohol aqueous solution to deposit the polyvinyl alcohol aqueous solution on the surfaces of the carbon fiber tows; and turning the filtered carbon fiber tows for 180 degrees, filtering the carbon nanotube aqueous solution, the nano-cellulose aqueous solution and the polyvinyl alcohol aqueous solution with the same amount, and finally drying in an oven to obtain the carbon fiber synergistically modified by the nano-cellulose/the carbon nanotube/the polyvinyl alcohol.
2. The method for preparing the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber according to claim 1, wherein the carbon fiber of the step (1) is a long carbon fiber.
3. The method for preparing the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber according to claim 1, characterized in that: the reflux temperature in the step 1) is 80-100 ℃, and the reflux time is 12-48 h.
4. The method for preparing the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber according to claim 1, characterized in that: the nano-cellulose in the step 2) is cellulose nanocrystal, cellulose nano-fiber or bacterial nano-cellulose.
5. The method for preparing the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber according to claim 1, characterized in that: the stirring temperature in the step 3) is 95-110 ℃, and the stirring time is 1-3 h.
6. The method for preparing the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber according to claim 1, characterized in that: the magnetic stirring speed of the step 4) is 200-800 rpm/min, and the time is 30-100 min.
7. The method for preparing the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber according to claim 1, characterized in that: and 4) carrying out suction filtration according to the volumes (ml) of the nano-cellulose/carbon nano-tube mixed solution, the nano-cellulose aqueous solution, the carbon nano-tube aqueous solution and the polyvinyl alcohol aqueous solution, wherein the diameter (cm) of the filter membrane is (0.1-5): 1.
8. The method for preparing the nano-cellulose/carbon nanotube/polyvinyl alcohol synergistically modified carbon fiber according to claim 1, characterized in that: the drying temperature of the steps 1) and 4) is 40-80 ℃, and the drying time is 2-5 h.
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