阅读说明：本技术 一种基于二维纳米材料改性碳纤维的制备方法 (Preparation method of modified carbon fiber based on two-dimensional nano material ) 是由 武清 叶紫怡 白换换 邓昊 朱建锋 于 2021-07-18 设计创作，主要内容包括：本发明公开了一种基于二维纳米材料改性碳纤维的制备方法,包括：首先对碳纤维进行去剂处理,其次配置二维纳米材料分散液,最后采用真空抽滤法将二维纳米材料分散液沉积在均匀铺放的碳纤维丝束表面,然后将沉积有二维纳米材料分散液的碳纤维丝束翻转180°,再次真空抽滤二维纳米材料分散液使其沉积在均匀铺放的碳纤维丝束另一表面,得到二维纳米材料改性的碳纤维。本发明的制备方法有效解决了现有碳纤维表面改性方法存在的降低纤维强度、工艺复杂、操作困难、污染环境、加工成本高等问题,制备的二维纳米材料改性的碳纤维使复合材料的界面粘结强度提高了12.3％～75.5％。(The invention discloses a preparation method of modified carbon fiber based on two-dimensional nano material, which comprises the following steps: firstly, removing agent from carbon fibers, secondly, preparing a two-dimensional nano material dispersion liquid, finally depositing the two-dimensional nano material dispersion liquid on the surface of the uniformly laid carbon fiber tows by adopting a vacuum filtration method, then turning the carbon fiber tows deposited with the two-dimensional nano material dispersion liquid by 180 degrees, and then carrying out vacuum filtration on the two-dimensional nano material dispersion liquid again to deposit the two-dimensional nano material dispersion liquid on the other surface of the uniformly laid carbon fiber tows, thereby obtaining the two-dimensional nano material modified carbon fibers. The preparation method effectively solves the problems of fiber strength reduction, complex process, difficult operation, environmental pollution, high processing cost and the like of the existing carbon fiber surface modification method, and the prepared two-dimensional nanomaterial modified carbon fiber improves the interface bonding strength of the composite material by 12.3-75.5%.)

1. A preparation method of modified carbon fiber based on two-dimensional nano material is characterized by comprising the following steps:

(1) condensing and refluxing the carbon fiber tows in an acetone solution, extracting, cleaning with deionized water, and drying in vacuum;

(2) dispersing the two-dimensional nano material in water or an organic solvent, and stirring to uniformly disperse the two-dimensional nano material to obtain a two-dimensional nano material dispersion liquid with the mass fraction of 0.01-5%;

(3) and (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the two-dimensional nano material dispersion liquid to enable the two-dimensional nano material dispersion liquid to be deposited on the surface of the uniformly laid carbon fiber tows, turning the carbon fiber tows deposited with the two-dimensional nano material dispersion liquid by 180 degrees, carrying out vacuum filtration on the two-dimensional nano material dispersion liquid again to enable the two-dimensional nano material dispersion liquid to be deposited on the other surface of the uniformly laid carbon fiber tows, and carrying out vacuum drying to obtain the two-dimensional nano material modified carbon fiber.

2. The method for preparing the two-dimensional nanomaterial-based modified carbon fiber according to claim 1, wherein the carbon fiber of the step (1) is a long carbon fiber.

3. The preparation method of the two-dimensional nanomaterial-based modified carbon fiber according to claim 1, wherein the condensation reflux temperature in the step (1) is 80-100 ℃ and the time is 12-48 hours.

4. The preparation method of the two-dimensional nanomaterial-based modified carbon fiber according to claim 1, wherein the two-dimensional nanomaterial of step (2) is graphene, graphene oxide, porous graphene oxide, Mxenes, nickel hydroxide nanosheets, or molybdenum disulfide.

5. The method for preparing two-dimensional nanomaterial-based modified carbon fiber according to claim 1, wherein the organic solvent of step (2) is acetone, ethanol, tetrahydrofuran, dimethylformamide, dichloromethane, xylene, or ethyl acetate.

6. The preparation method of the two-dimensional nanomaterial-based modified carbon fiber according to claim 1, wherein the stirring in the step (2) is performed by magnetic stirring at a rotation speed of 200-800 rpm/min for 30-120 min.

7. The preparation method of the two-dimensional nanomaterial-based modified carbon fiber according to claim 1, wherein the step (3) is performed by vacuum filtration of the two-dimensional nanomaterial dispersion, and the volume (ml) of the two-dimensional nanomaterial dispersion is that the diameter (cm) of the filter membrane is (0.1-5): 1.

8. The preparation method of the two-dimensional nanomaterial-based modified carbon fiber according to claim 1, wherein: and (3) drying in a vacuum drying oven at 40-80 ℃ for 2-5 h.

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 modified carbon fibers based on a two-dimensional nano material.

Background

Two-dimensional nanomaterials, which are substances having external dimensions less than 100nm in two dimensions, have excellent electrical, optical, thermal and mechanical properties, and are widely used as reinforcements to modify carbon fibers to improve the interface bonding strength between the fibers and resin. At present, common methods for preparing two-dimensional nano material modified carbon fibers comprise a sizing method, a chemical grafting method, a chemical vapor deposition method, an electrophoretic deposition method and the like, but most of the methods are easy to generate fiber surface defects to reduce the fiber strength, or have the problems of complex process, difficult operation, environmental pollution, high processing cost and the like. Therefore, it is very important to find a simple, environment-friendly, efficient and low-cost fiber surface modification method.

Disclosure of Invention

The invention aims to provide a preparation method of a two-dimensional nanomaterial-based modified carbon fiber, which has the advantages of simple process, environmental protection and low cost, and the prepared two-dimensional nanomaterial-based modified carbon fiber improves the interface bonding strength of a composite material by 12.3-75.5%.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

(1) condensing and refluxing the carbon fiber tows in an acetone solution, extracting, cleaning with deionized water, and drying in vacuum;

(2) dispersing the two-dimensional nano material in water or an organic solvent, and stirring to uniformly disperse the two-dimensional nano material to obtain a two-dimensional nano material dispersion liquid with the mass fraction of 0.01-5%;

(3) and (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the two-dimensional nano material dispersion liquid to enable the two-dimensional nano material dispersion liquid to be deposited on the surface of the uniformly laid carbon fiber tows, turning the carbon fiber tows deposited with the two-dimensional nano material dispersion liquid by 180 degrees, carrying out vacuum filtration on the two-dimensional nano material dispersion liquid again to enable the two-dimensional nano material dispersion liquid to be deposited on the other surface of the uniformly laid carbon fiber tows, and carrying out vacuum drying to obtain the two-dimensional nano material modified carbon fiber.

The carbon fiber in the step (1) is long carbon fiber.

The condensation reflux temperature in the step (1) is 80-100 ℃, and the time is 12-48 h.

The two-dimensional nano material in the step (2) is graphene, graphene oxide, porous graphene oxide, Mxenes, nickel hydroxide nanosheets or molybdenum disulfide.

The organic solvent in the step (2) is acetone, ethanol, tetrahydrofuran, dimethylformamide, dichloromethane, xylene or ethyl acetate.

The stirring in the step (2) adopts magnetic stirring at the rotating speed of 200-800 rpm/min, and the stirring time is 30-120 min.

And (3) carrying out vacuum filtration on the two-dimensional nano material dispersion liquid in the step (3), wherein the volume (ml) of the two-dimensional nano material dispersion liquid is that the diameter (cm) of a filter membrane is (0.1-5): 1.

And (3) drying in a vacuum drying oven at 40-80 ℃ for 2-5 h. Compared with the prior art, the invention has the following beneficial technical effects:

(1) the vacuum filtration method is adopted to realize the uniform deposition of the two-dimensional nano material on the surface of the carbon fiber tows with the circumferential structure, and the method has the advantages of simple equipment, mild reaction conditions, no toxicity, environmental protection, low cost and high efficiency.

(2) Due to the structural particularity of the two-dimensional nanomaterial, the two-dimensional nanomaterial is more easily attached to carbon fiber tows wrapping a circumferential structure, and compared with unmodified carbon fibers, the two-dimensional nanomaterial modified carbon fibers have larger specific surface area and chemical modification possibility, the interaction between the fibers and resin is increased, and the wettability is improved.

(3) Compared with the unmodified carbon fiber composite material, the interface bonding strength of the two-dimensional nano material modified carbon fiber composite material is improved by 12.3-75.5%.

Drawings

Fig. 1 is a surface topography of the graphene oxide-modified carbon fiber prepared in example 1.

Fig. 2 is a surface topography of the porous graphene oxide-modified carbon fiber prepared in example 3.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

Example 1

(1) Condensing and refluxing long carbon fiber tows in an acetone solution at 80 ℃ for 24 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 60 ℃ for 3 hours;

(2) dispersing graphene oxide in an aqueous solution, and magnetically stirring at 300rpm/min for 40min to uniformly disperse the graphene oxide to obtain a graphene oxide dispersion liquid with the mass fraction of 1%;

(3) and (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the graphene oxide dispersion liquid according to the volume (ml) of the graphene oxide dispersion liquid, wherein the diameter (cm) of the filter membrane is 0.1:1, so that the graphene oxide dispersion liquid is deposited on the surface of the uniformly laid carbon fiber tows, then overturning the carbon fiber tows deposited with the graphene oxide dispersion liquid by 180 degrees, carrying out vacuum filtration on the same amount of graphene oxide dispersion liquid again, so that the graphene oxide dispersion liquid is deposited on the other surface of the uniformly laid carbon fiber tows, and drying in a vacuum drying box at 60 ℃ for 3 hours, so as to obtain the graphene oxide modified carbon fiber.

The surface morphology of the prepared graphene oxide modified carbon fiber is shown in figure 1, and the interfacial bonding strength of the epoxy composite material prepared by the fiber is improved by 12.3 percent compared with that of an unmodified carbon fiber reinforced epoxy composite material.

Example 2

(1) Condensing and refluxing the long carbon fiber tows in an acetone solution at 80 ℃ for 48 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 80 ℃ for 2 hours;

(2) dispersing graphene oxide in dimethylformamide, and magnetically stirring at 200rpm/min for 30min to uniformly disperse the graphene oxide to obtain a graphene oxide dispersion liquid with the mass fraction of 0.01%;

(3) and (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the graphene oxide dispersion liquid according to the volume (ml) of the graphene oxide dispersion liquid, wherein the diameter (cm) of the filter membrane is 2:1, so that the graphene oxide dispersion liquid is deposited on the surface of the uniformly laid carbon fiber tows, then overturning the carbon fiber tows deposited with the graphene oxide dispersion liquid by 180 degrees, carrying out vacuum filtration on the same amount of graphene oxide dispersion liquid, so that the graphene oxide dispersion liquid is deposited on the other surface of the uniformly laid carbon fiber tows, and drying for 2 hours in a vacuum drying box at 80 ℃ to obtain the graphene oxide modified carbon fiber.

The interface bonding strength of the prepared graphene oxide modified carbon fiber reinforced epoxy composite material is improved by 75.5% compared with that of an unmodified carbon fiber reinforced epoxy composite material.

Example 3

(1) Condensing and refluxing the long carbon fiber tows in an acetone solution at 90 ℃ for 12 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 40 ℃ for 5 hours.

(2) And dispersing the porous graphene oxide in ethanol, and magnetically stirring at 800rpm/min for 120min to uniformly disperse the porous graphene oxide to obtain a porous graphene oxide dispersion liquid with the mass fraction of 5%.

(3) And (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the porous graphene oxide dispersion liquid according to the volume (ml) of the porous graphene oxide dispersion liquid, wherein the diameter (cm) of the filter membrane is 0.3:1, depositing the porous graphene oxide dispersion liquid on the surface of the uniformly laid carbon fiber tows, turning the carbon fiber tows deposited with the porous graphene oxide dispersion liquid by 180 degrees, carrying out vacuum filtration on the same amount of the porous graphene oxide dispersion liquid to deposit the porous graphene oxide dispersion liquid on the surface of the uniformly laid carbon fiber tows, and drying for 5 hours in a vacuum drying box at 40 ℃ to obtain the porous graphene oxide modified carbon fiber.

The surface morphology of the prepared porous graphene oxide modified carbon fiber is shown in fig. 2, and the interfacial bonding strength of the epoxy composite material prepared by adopting the fiber is improved by 54.4 percent compared with that of an unmodified carbon fiber reinforced epoxy composite material.

Example 4

(1) Condensing and refluxing the long carbon fiber tows in an acetone solution at 90 ℃ for 24 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 50 ℃ for 4 hours.

(2) And dispersing the porous graphene oxide in tetrahydrofuran, and magnetically stirring at 200rpm/min for 30min to uniformly disperse the porous graphene oxide to obtain a porous graphene oxide dispersion liquid with the mass fraction of 0.05%.

(3) And (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the porous graphene oxide dispersion liquid according to the volume (ml) of the porous graphene oxide dispersion liquid, wherein the diameter (cm) of the filter membrane is 1:1, so that the porous graphene oxide dispersion liquid is deposited on the surface of the uniformly laid carbon fiber tows, turning the carbon fiber tows, on which the porous graphene oxide dispersion liquid is deposited, by 180 degrees, carrying out vacuum filtration on the same amount of the porous graphene oxide dispersion liquid, so that the porous graphene oxide dispersion liquid is deposited on the other surface of the uniformly laid carbon fiber tows, and drying in a vacuum drying box at 50 ℃ for 4 hours, so as to obtain the porous graphene oxide modified carbon fiber.

Example 5

(1) Condensing and refluxing the long carbon fiber tows in an acetone solution at 100 ℃ for 12 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 70 ℃ for 2 hours.

(2) And dispersing graphene in dichloromethane, and magnetically stirring at 700rpm/min for 100min to uniformly disperse the graphene to obtain a graphene dispersion liquid with the mass fraction of 3%.

(3) And (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the graphene dispersion liquid according to the volume (ml) of the graphene dispersion liquid, wherein the diameter (cm) of the filter membrane is 0.5:1 to deposit the graphene dispersion liquid on the surface of the carbon fiber tows, then overturning the carbon fiber tows deposited with the graphene dispersion liquid by 180 degrees, carrying out vacuum filtration on the same amount of graphene dispersion liquid to deposit the same on the surface of the uniformly laid carbon fiber tows, and drying for 2 hours at 70 ℃ in a vacuum drying box to obtain the graphene modified carbon fiber.

The interface bonding strength of the prepared graphene modified carbon fiber reinforced epoxy composite material is improved by 19.3% compared with that of an unmodified carbon fiber reinforced epoxy composite material.

Example 6

(1) Condensing and refluxing the long carbon fiber tows in an acetone solution at 100 ℃ for 24 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 50 ℃ for 5 hours.

(2) The Mxenes are dispersed in xylene, and are uniformly dispersed by magnetic stirring at 800rpm/min for 80min to obtain a Mxenes dispersion liquid with the mass fraction of 2.5%.

(3) And (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the Mxenes dispersion liquid according to the volume (ml) of the Mxenes dispersion liquid, wherein the diameter (cm) of the filter membrane is 5:1, so that the Mxenes dispersion liquid is deposited on the surface of the uniformly laid carbon fiber tows, then overturning the carbon fiber tows deposited with the Mxenes dispersion liquid by 180 degrees, carrying out vacuum filtration on the Mxenes dispersion liquid with the same amount so that the Mxenes dispersion liquid is deposited on the other surface of the uniformly laid carbon fiber tows, and drying for 5 hours at 50 ℃ in a vacuum drying box to obtain the Mxenes modified carbon fiber.

The interface bonding strength of the prepared Mxenes modified carbon fiber reinforced epoxy composite material is improved by 55.6 percent compared with that of an unmodified carbon fiber reinforced epoxy composite material.

Example 7

(1) Condensing and refluxing the long carbon fiber tows in an acetone solution at 80 ℃ for 48 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 50 ℃ for 5 hours.

(2) Dispersing the nickel hydroxide nanosheets in ethyl acetate, and magnetically stirring at 600rpm/min for 120min to uniformly disperse the nickel hydroxide nanosheets to obtain a nickel hydroxide nanosheet dispersion liquid with the mass fraction of 5%.

(3) And (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on 5ml of nickel hydroxide nanosheet dispersion according to the volume (ml) of the nickel hydroxide nanosheet dispersion, wherein the diameter (cm) of the filter membrane is 1.5:1, so that the nickel hydroxide nanosheet dispersion is deposited on the surface of the uniformly laid carbon fiber tows, turning the carbon fiber tows deposited with the nickel hydroxide nanosheet dispersion 180 degrees, carrying out vacuum filtration on the same amount of nickel hydroxide nanosheet dispersion so that the nickel hydroxide nanosheet dispersion is deposited on the other surface of the uniformly laid carbon fiber tows, and drying in a vacuum drying oven at 50 ℃ for 5 hours to obtain the nickel hydroxide nanosheet modified carbon fiber.

Example 8

(1) Condensing and refluxing the long carbon fiber tows in an acetone solution at 80 ℃ for 24 hours, cleaning the tows by deionized water after extraction, and drying the tows in a vacuum drying oven at 40 ℃ for 2 hours.

(2) And dispersing the molybdenum disulfide in acetone, and magnetically stirring at 600rpm/min for 30min to uniformly disperse the molybdenum disulfide to obtain a molybdenum disulfide dispersion liquid with the mass fraction of 0.05%.

(3) And (2) uniformly laying the carbon fiber tows obtained by the treatment in the step (1) on a filter membrane, carrying out vacuum filtration on the molybdenum disulfide dispersion liquid according to the volume (ml) of the molybdenum disulfide dispersion liquid, wherein the diameter (cm) of the filter membrane is 4:1, so that the molybdenum disulfide dispersion liquid is deposited on the surface of the uniformly laid carbon fiber tows, then overturning the carbon fiber tows deposited with the molybdenum disulfide dispersion liquid by 180 degrees, carrying out vacuum filtration on the same amount of the molybdenum disulfide dispersion liquid, so that the molybdenum disulfide dispersion liquid is deposited on the other surface of the uniformly laid carbon fiber tows, and drying in a vacuum drying box at 40 ℃ for 2 hours, so as to obtain the molybdenum disulfide modified carbon fiber.