CN121896830A - Carbon fiber gauze and preparation method thereof, and carbon fiber reinforced composite material - Google Patents
Carbon fiber gauze and preparation method thereof, and carbon fiber reinforced composite materialInfo
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Abstract
The disclosure provides a carbon fiber gauze, a preparation method thereof and a carbon fiber reinforced composite material. The carbon fiber gauze comprises chopped carbon fibers and carbon nanotubes, wherein the carbon nanotubes are bonded to the chopped carbon fibers through a high polymer adhesive, and the carbon nanotubes account for 1.8-18.6% of the carbon fiber gauze by mass. The carbon fiber gauze organically combines the chopped carbon fibers with the carbon nanotubes to construct a unique multi-scale-level toughening structure. When the carbon fiber gauze is used in a carbon fiber composite material, the chopped carbon fibers play roles in crack bridging and deflection between layers, and can effectively inhibit the expansion of microcracks. The carbon nano tube absorbs energy in a resin-rich region at the crack tip of the carbon fiber composite material through mechanisms such as pulling out, breaking and the like, so that the initiation of nano-scale cracks is inhibited. In addition, the carbon nano tube is bonded to the chopped carbon fiber through the high polymer adhesive, so that the carbon nano tube can be firmly fixed on the chopped carbon fiber, and the functional stability of the carbon fiber gauze or the carbon fiber composite material is ensured.
Description
Technical Field
The disclosure relates to the technical field of composite materials, in particular to a carbon fiber gauze and a preparation method thereof, and a carbon fiber reinforced composite material.
Background
Carbon fiber reinforced matrix Composites (CFRP) have been widely used in high performance applications such as aerospace main load bearing structures, wind turbine blades, and battery shells for electric vehicles due to their excellent specific strength and specific stiffness. However, the inherent weakness of laminate composites is their interlaminar properties, which make them extremely susceptible to interlaminar delamination failure. Interlayer delamination may result from manufacturing defects, external impacts, or stress concentrations, which once occur and expand, severely impair the overall load-bearing capacity and safety of the structure, a key technical bottleneck limiting its wider application.
Disclosure of Invention
In order to solve the problems in the related art, the present disclosure provides a carbon fiber mesh yarn, a preparation method thereof, and a carbon fiber reinforced composite material.
According to a first aspect of embodiments of the present disclosure, there is provided a carbon fiber mesh comprising chopped carbon fibers and carbon nanotubes bonded to the chopped carbon fibers by a polymeric binder;
The carbon nano tube accounts for 1.8-18.6% of the carbon fiber gauze in percentage by mass.
In some embodiments of the present disclosure, the polymeric binder includes at least one of polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, or amphiphilic block copolymer.
In some embodiments of the disclosure, the polymeric binder comprises the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone, wherein the mass ratio of the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone is (1.5-2.5): 0.8-1.8): 3.1-4.0.
In some embodiments of the present disclosure, the length of the chopped carbon fiber is 0.5-30 mm, and the surface of the chopped carbon fiber includes an oxygen-containing functional group and/or a nitrogen-containing functional group.
In some embodiments of the present disclosure, the carbon fiber mesh yarn has an areal density of 15-56 g/m 2.
According to a second aspect of embodiments of the present disclosure, there is provided a method for preparing a carbon fiber mesh, the method for preparing a carbon fiber mesh as described above, the method comprising:
Dispersing chopped carbon fibers, carbon nanotubes and a high polymer binder in a solvent to form a dispersion;
dewatering the dispersion liquid through a wet-process web forming process to form a dewatered gauze;
and drying the dehydrated gauze to obtain the carbon fiber gauze.
In some embodiments of the disclosure, the concentration of the polymeric binder in the dispersion is 1.5-10wt%;
The high polymer adhesive comprises polyvinyl alcohol, polyethylene oxide and polyvinylpyrrolidone, wherein the mass ratio of the polyvinyl alcohol to the polyethylene oxide to the polyvinylpyrrolidone is (1.5-2.5) (0.8-1.8) (3.1-4.0).
In some embodiments of the present disclosure, the method of preparing further comprises:
the chopped carbon fibers are subjected to plasma treatment by an oxygen-containing gas source to introduce oxygen-containing functional groups on the surfaces of the chopped carbon fibers and/or,
And carrying out plasma treatment on the chopped carbon fiber through a nitrogen-containing air source so as to introduce nitrogen-containing functional groups on the surface of the chopped carbon fiber.
According to a third aspect of embodiments of the present disclosure, there is provided a carbon fiber reinforced composite material comprising a carbon fiber mesh as described above or a carbon fiber mesh as prepared by the method of preparing a carbon fiber mesh as described above.
The carbon fiber gauze provided by the present disclosure organically combines chopped carbon fibers with carbon nanotubes to construct a unique multi-scale hierarchical toughening structure. When the carbon fiber gauze is used in a carbon fiber composite material, the chopped carbon fibers play roles in crack bridging and deflection between layers, and can effectively inhibit the development of microcracks when the carbon fiber composite material is damaged by impact. The carbon nano tube absorbs energy in a resin-rich region at the crack tip of the carbon fiber composite material through mechanisms such as pulling out, breaking and the like, so that the initiation of nano-scale cracks is inhibited. In addition, the carbon nano tube is bonded to the chopped carbon fiber through the high polymer adhesive, so that the carbon nano tube can be firmly fixed on the chopped carbon fiber, the stability and the reproducibility of the function of the carbon fiber gauze or the carbon fiber composite material are ensured, and the problems that the carbon nano tube is easy to agglomerate due to Van der Waals force and is easy to fall off or migrate in subsequent processing are solved.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description, serve to explain the principles of the embodiments of the disclosure. In the drawings, like reference numerals are used to identify like elements. The drawings, which are included in the description, are some, but not all embodiments of the disclosure. Other figures can be obtained from these figures without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a method for preparing a carbon fiber mesh yarn according to an exemplary embodiment of the disclosure.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present disclosure more apparent, the technical solutions of the present disclosure will be clearly and completely described in conjunction with the embodiments of the present disclosure, and it is apparent that the described embodiments are only some embodiments of the present disclosure, but not all embodiments. Based on the embodiments in this disclosure, all other embodiments that a person of ordinary skill in the art would obtain without making any inventive effort are within the scope of protection of this disclosure. It should be noted that, without conflict, the embodiments of the present disclosure and features of the embodiments may be arbitrarily combined with each other.
The inherent weakness of laminated carbon fiber reinforced composites is their interlaminar properties, which make them extremely susceptible to interlaminar delamination failure. Interlayer delamination may result from manufacturing defects, external impacts, or stress concentrations, which once occur and expand, severely impair the overall load-bearing capacity and safety of the structure, a key technical bottleneck limiting its wider application. In the related art, various toughening strategies are adopted, such as matrix toughening, and rubber or thermoplastic particles are added into a resin matrix, so that the toughness can be improved, but the rigidity, the strength and the heat resistance (glass transition temperature Tg) of the material are often sacrificed. Thermoplastic intercalation, which is effective in toughening by inserting thermoplastic films or nonwovens between layers, generally increases the thickness and weight of the component, and may have poor interfacial compatibility with thermosetting matrix resins, and complex process integration.
Based on this, the present disclosure provides a carbon fiber veil that organically combines chopped carbon fibers with carbon nanotubes to construct a unique "multi-scale level" toughening structure. When the carbon fiber gauze is used in a carbon fiber composite material, the chopped carbon fibers play roles in crack bridging and deflection between layers, and can effectively inhibit the development of microcracks when the carbon fiber composite material is damaged by impact. The carbon nano tube absorbs energy in a resin-rich region at the crack tip of the carbon fiber composite material through mechanisms such as pulling out, breaking and the like, so that the initiation of nano-scale cracks is inhibited. In addition, the carbon nano tube is bonded to the chopped carbon fiber through the high polymer adhesive, so that the carbon nano tube can be firmly fixed on the chopped carbon fiber, the stability and the reproducibility of the function of the carbon fiber gauze or the carbon fiber composite material are ensured, and the problems that the carbon nano tube is easy to agglomerate due to Van der Waals force and is easy to fall off or migrate in subsequent processing are solved.
An exemplary embodiment of the present disclosure provides a carbon fiber mesh yarn, which includes chopped carbon fibers and carbon nanotubes bonded to the chopped carbon fibers by a polymer binder, wherein the carbon nanotubes account for 1.8-18.6% by mass of the carbon fiber mesh yarn.
In this embodiment, the chopped carbon fibers are organically combined with the carbon nanotubes to construct a unique "multi-scale hierarchical" toughening structure. When the carbon fiber gauze is used in a carbon fiber composite material, the chopped carbon fibers play roles in crack bridging and deflection between layers, and can effectively inhibit the development of microcracks when the carbon fiber composite material is damaged by impact. The carbon nano tube absorbs energy in a resin-rich region at the crack tip of the carbon fiber composite material through mechanisms such as pulling out, breaking and the like, so that the initiation of nano-scale cracks is inhibited. The synergistic effect of the chopped carbon fibers and the carbon nanotubes gives the carbon fiber composite excellent interlayer fracture toughness of type I (open type) and type II (shear type). When the content of the carbon nano tube is too low, the inhibition effect on cracks is not obvious, and the mechanical property or the functionality of the carbon fiber gauze or the carbon fiber composite material cannot be effectively improved. When the content of the carbon nanotubes is too high, agglomeration of the carbon nanotubes on the chopped carbon fibers may be caused, which may rather reduce the performance and increase unnecessary costs. Therefore, in this embodiment, the carbon nanotubes are controlled to be 1.8-18.6% by mass of the carbon fiber mesh yarn, so as to obtain the best performance improvement of the carbon fiber mesh yarn or the carbon fiber composite material. For example, the carbon nanotubes may be 1.8%, 3.6%, 5.4%, 8.5%, 10.6%, 13.8%, 15.7% or 18.6% by mass of the carbon fiber mesh, and the carbon nanotubes may be any value between the exemplary mass percentages of the carbon fiber mesh, for example, the carbon nanotubes may be any value between 2.6 to 15.6% by mass of the carbon fiber mesh.
In this embodiment, the carbon nanotubes are bonded to the chopped carbon fibers by the polymer adhesive, so that the carbon nanotubes can be firmly fixed on the chopped carbon fibers, the stability and reproducibility of the functions of the carbon fiber gauze or the carbon fiber composite material are ensured, and the problems that the carbon nanotubes are easy to agglomerate due to van der Waals force and are easy to fall off or migrate in subsequent processing are solved.
Illustratively, the carbon nanotubes may be selected from at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes.
In an exemplary embodiment, the polymeric binder includes at least one of polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, or an amphiphilic block copolymer.
In this embodiment, the polymer binder is selected from water-soluble or water-dispersible polymer binders, so as to ensure that the polymer binder can be dispersed in an aqueous solvent together with the chopped carbon fibers and the carbon nanotubes during the preparation process of the carbon fiber gauze, temporarily fix the chopped carbon fibers and the carbon nanotubes, and provide the carbon fiber gauze with sufficient mechanical strength after drying.
The polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone or amphiphilic block copolymer polymer adhesive selected in this embodiment contains a large number of hydroxyl (-OH), ether bond (-O-), carbonyl (c=o) or pyrrolidone groups on the polymer chain, and these functional groups can generate strong interactions with the surfaces of the chopped carbon fibers and the carbon nanotubes through hydrogen bonds, van der waals forces and the like, so as to provide firm adhesion for the chopped carbon fibers and the carbon nanotubes. In addition, the high polymer adhesives have good compatibility with most resin matrixes, and when the carbon fiber gauze provided by the embodiment of the disclosure is used for preparing a carbon fiber composite material, the high polymer adhesives can promote interface combination of chopped carbon fibers and matrix resin in the preparation process of the carbon fiber composite material.
In an exemplary embodiment, the polymeric binder comprises polyvinyl alcohol, polyethylene oxide and polyvinylpyrrolidone, wherein the mass ratio of the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone is (1.5-2.5): (0.8-1.8): (3.1-4.0).
The polyvinyl alcohol is mainly used as a film forming adhesive of the carbon fiber gauze, molecular chains of the polyvinyl alcohol are adsorbed on the surface of the chopped carbon fiber with larger size in the preparation process of the carbon fiber gauze, and mechanical entanglement of the chopped carbon fiber under water flow stirring is effectively prevented through a steric hindrance effect, so that the uniformity of a carbon fiber skeleton in the subsequent networking process is ensured. The synergism of polyethylene oxide and polyvinylpyrrolidone is mainly responsible for efficiently and stably dispersing the nano-scale carbon nano-tubes. Carbon nanotubes are very susceptible to agglomeration in the aqueous phase due to their large specific surface area and their strong van der waals attractive forces. Polyethylene oxide and polyvinylpyrrolidone are used as nonionic high molecular dispersing agents, molecular chains of the polyethylene oxide and polyvinylpyrrolidone can be adsorbed on the surfaces of the carbon nanotubes, and a steric hindrance repulsive layer is formed through hydrophilic chain segments stretching into an aqueous phase, so that van der Waals force is overcome, the carbon nanotube bundles are dissociated into finer bundles or single tubes, and the carbon nanotube bundles are prevented from being aggregated again. The combined use of the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone generates a synergistic effect of 1+1+1>3, the synergistic effect is targeted and stabilized for the chopped carbon fibers and the carbon nanotubes, the limitation of a single dispersing agent is avoided, and meanwhile, in the preparation process of the carbon fiber gauze, the combined use of the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone can adjust the rheological property of the dispersing liquid, so that the viscosity is moderate, the fluidity is good, and the method is suitable for the subsequent high-speed continuous wet-process networking process. The mass ratio of the polyvinyl alcohol to the polyethylene oxide to the polyvinylpyrrolidone is controlled to be (1.5-2.5): (0.8-1.8): (3.1-4.0), so that the chopped carbon fibers and the carbon nanotubes can reach an excellent dispersion state, the requirement of the process on the fluidity of the dispersion liquid can be met, and the finally prepared carbon fiber gauze has enough mechanical strength. For example, the mass ratio of polyvinyl alcohol, polyethylene oxide, and polyvinylpyrrolidone may be 1.5:0.8:3.1, 1.5:1.8:4.0, 2.0:1.0:3.5, 2.5:1.8:4.0, or 1.8:1.5:3.8, or the mass ratio of polyvinyl alcohol, polyethylene oxide, and polyvinylpyrrolidone may be any value between exemplary mass ratios, for example, the mass ratio of polyvinyl alcohol, polyethylene oxide, and polyvinylpyrrolidone may be any value between (1.8-2.2): (1.0-1.5): (3.3-3.8).
In an exemplary embodiment, the length of the chopped carbon fibers is 0.5-30 mm, and the surface of the chopped carbon fibers includes oxygen-containing functional groups and/or nitrogen-containing functional groups.
Illustratively, polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, or regenerated cellulose-based carbon fibers may be selected. Illustratively, different grades of carbon fibers such as T300, T700, T800, IM7, etc. may be used.
The length of the chopped carbon fibers is critical to ensuring the web forming process and performance of the carbon fiber gauze. When the length of the chopped carbon fibers is too short, the chopped carbon fibers are difficult to form an effective carbon fiber network, which can result in too low strength of the carbon fiber gauze, while when the length of the chopped carbon fibers is too long, the chopped carbon fibers are easy to be entangled in a dispersion liquid in the preparation process of the carbon fiber gauze, and the uniform carbon fiber gauze is difficult to form. In the embodiment, the length of the chopped carbon fibers is controlled to be 0.5-30 mm, so that the processability in the preparation process of the carbon fiber gauze and the network structural integrity of a finished carbon fiber gauze product can be balanced. For example, the length of the chopped carbon fibers may be 0.5mm, 2.5mm, 5.0mm, 8.7mm, 10.0mm, 15.3mm, 20.0mm, 25.6 or 30mm, and the length of the chopped carbon fibers may be any value between exemplary lengths, for example, the length of the chopped carbon fibers may be any value between 2 to 12 mm. Illustratively, the carbon fiber filaments may be mechanically treated to provide chopped carbon fibers of the above-described lengths.
The chopped carbon fibers may be plasma treated to introduce oxygen-containing and/or nitrogen-containing functional groups to the surface thereof. Oxygen-containing functional groups on the surface of the chopped carbon fiber, such as hydroxyl (-OH) and carboxyl (-COOH), can improve the wettability of the carbon fiber gauze with the matrix resin through the actions of hydrogen bonds and the like when the carbon fiber gauze is used for preparing a carbon fiber composite material. The nitrogen-containing functional groups on the surface of the chopped carbon fiber, such as amino (-NH 2), can cause ring-opening reaction between the introduced amino (-NH 2) and the epoxy groups of the epoxy resin to form firm covalent bonds when the carbon fiber gauze is used for preparing the carbon fiber composite material, thereby realizing the strongest interface combination of the carbon fiber gauze and the matrix resin and greatly improving the interlaminar shear strength and the impact resistance of the carbon fiber composite material.
In an exemplary embodiment, the areal density of the carbon fiber veil is 15 to 56 g/m 2 and the thickness of the carbon fiber veil is 50 to 100 μm.
The surface density and thickness of the carbon fiber gauze can be selected according to different application scenes, for example, the carbon fiber gauze is used as a surface layer or an interlayer, when the carbon fiber gauze is used for a light product or a scene requiring surface functionality, the carbon fiber gauze with lower surface density and lower thickness can be selected, and when the carbon fiber gauze is required to provide a remarkable structural reinforcing effect, the carbon fiber gauze with higher surface density and higher thickness can be selected. For example, the areal density of the carbon fiber mesh may be 15 g/m 2、20.6g/m2、30.7g/m2、45.1g/m2 or 56 g/m 2, or the areal density of the carbon fiber mesh may be any value between the exemplary areal densities, for example, the areal density of the carbon fiber mesh may be any value between 20.1-50.7 g/m 2. For example, the thickness of the carbon fiber mesh may be 50 μm, 65 μm, 75 μm, 80 μm, 90 μm or 100 μm, and the thickness of the carbon fiber mesh may be any value between exemplary thicknesses, for example, the thickness of the carbon fiber mesh may be any value between 60 to 80 μm.
An exemplary embodiment of the present disclosure provides a method for preparing a carbon fiber mesh yarn, for preparing the carbon fiber mesh yarn as described above, as shown in fig. 1, the method comprising:
s100, dispersing the chopped carbon fibers, the carbon nanotubes and the polymer binder in a solvent to form a dispersion liquid.
Illustratively, the solvent may be an aqueous solvent, such as deionized water. The chopped carbon fibers, the carbon nanotubes and the polymeric binder are added to deionized water, and in order to ensure uniform dispersion of the components, the dispersion of the components can be promoted by combining mechanical stirring (rotation speed 200-1500 rpm) with ultrasonic treatment. The ultrasonic treatment helps to break up the agglomerates of carbon nanotubes to form a uniform, stable dispersion.
S200, dewatering the dispersion liquid through a wet-process net forming process to form a net yarn after dewatering.
In step S100, the polymer binder, the chopped carbon fibers and the carbon nanotubes are jointly dispersed in a solvent to form a dispersion liquid, and the polymer binder can fix the chopped carbon fibers and the carbon nanotubes, so that the carbon nanotubes are locked in a carbon fiber skeleton, the stability and the reproducibility of a carbon fiber gauze preparation process and functions are ensured, and the problems that the carbon nanotubes are easy to agglomerate due to van der waals force and are easy to fall off or migrate in a wet-process networking process are solved.
In step S200, the uniform dispersion may be pumped into a wet-laid apparatus, for example, to dewater on a moving wire to form a wet-laid yarn. The surface density and thickness of the gauze can be accurately regulated and controlled by controlling the amounts and the net speed of the chopped carbon fibers, the carbon nanotubes and the polymer binder, so that the dehydrated gauze is formed. When the stable and homogeneous dispersion liquid is dehydrated on the net curtain, the carbon nano tubes are solidified into the net yarn structure after dehydration, the chopped carbon fibers with larger size form a porous framework, and the stably dispersed carbon nano tubes and the high molecular adhesive are physically trapped and uniformly deposited on the nodes of the framework and the surfaces of the chopped carbon fibers, so that a three-dimensional interpenetrating network structure penetrating the whole is finally formed.
And S300, drying the dehydrated gauze to obtain the carbon fiber gauze.
And drying the dehydrated gauze at 80-120 ℃ through a hot air or vacuum oven to obtain the final flexible carbon fiber gauze.
In the embodiment, the carbon fiber gauze is prepared by adopting a wet-process networking process, and the process has high production efficiency and controllable cost, and is easy to realize large-scale industrial production. The prepared carbon fiber gauze has stable shape and easy operation, and can be integrated into the preparation flow of carbon fiber composite materials such as prepreg layering, autoclave curing or resin transfer molding. In addition, the wet-process networking process can realize synchronous deposition and self-assembly of chopped carbon fibers, carbon nanotubes and a high polymer adhesive on a microscopic scale, and form a three-dimensional network structure with all components uniformly distributed and physically interpenetrating in the thickness direction of the whole carbon fiber gauze. This is fundamentally different from the two-dimensional laminate structure formed by the spray coating method in which the functional component is concentrated only on the surface. The unique three-dimensional network structure maximizes the effective bonding at the chopped carbon fiber nodes, provides a structural basis for the carbon fiber gauze or the carbon fiber composite material to realize efficient multi-scale load transmission, gives the carbon fiber composite material good damage tolerance, and meets the application requirements of high-end application, such as safety key type application requirements of aviation bearing structures and the like.
In an exemplary embodiment, the concentration of the polymeric binder in the dispersion is 1.5 to 10wt%. The high polymer adhesive comprises polyvinyl alcohol, polyethylene oxide and polyvinylpyrrolidone, wherein the mass ratio of the polyvinyl alcohol to the polyethylene oxide to the polyvinylpyrrolidone is (1.5-2.5) (0.8-1.8) (3.1-4.0).
The concentration of the polymeric binder in the dispersion is critical to ensure the bond firmness of the chopped carbon fibers and the carbon nanotubes. When the concentration of the polymer binder in the dispersion is too low, the binding force of the polymer binder on the chopped carbon fibers and the carbon nanotubes is insufficient, the carbon nanotubes are not firmly fixed on the chopped carbon fibers, and the strength of the prepared carbon fiber gauze is poor. When the concentration of the polymer binder in the dispersion is too high, the dispersion is viscous and poor in fluidity, uniform wet-laid cannot be performed, and the carbon fiber gauze after drying is too hard and brittle. Therefore, in this embodiment, the concentration of the polymer binder in the dispersion is controlled to be 1.5-10wt%, so that the dispersion can be ensured to have proper viscosity to facilitate forming, and the carbon fiber gauze with higher strength can be formed after drying. For example, the concentration of the polymeric binder in the dispersion may be 1.5wt%, 4.3wt%, 8.6wt%, or 10wt%, and the concentration of the polymeric binder in the dispersion may be any value between exemplary concentrations, for example, the concentration of the polymeric binder in the dispersion may be any value between 3.5 to 9.4 wt%.
The polyvinyl alcohol is mainly used as a film forming adhesive of the carbon fiber gauze, molecular chains of the polyvinyl alcohol are adsorbed on the surfaces of the chopped carbon fibers with larger sizes in the preparation process of the carbon fiber gauze, and mechanical entanglement of the chopped carbon fibers under water flow stirring is effectively prevented through a steric hindrance effect, so that uniformity of a carbon fiber skeleton in the wet-process networking process is ensured. The synergism of polyethylene oxide and polyvinylpyrrolidone is mainly responsible for efficiently and stably dispersing the nano-scale carbon nano-tubes. Carbon nanotubes are very susceptible to agglomeration in the aqueous phase due to their large specific surface area and their strong van der waals attractive forces. Polyethylene oxide and polyvinylpyrrolidone are used as nonionic high molecular dispersing agents, molecular chains of the polyethylene oxide and polyvinylpyrrolidone can be adsorbed on the surfaces of the carbon nanotubes, and a steric hindrance repulsive layer is formed through hydrophilic chain segments stretching into an aqueous phase, so that van der Waals force is overcome, the carbon nanotube bundles are dissociated into finer bundles or single tubes, and the carbon nanotube bundles are prevented from being aggregated again. The combined use of the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone generates a synergistic effect of 1+1+1>3, the synergistic effect is targeted and stabilized for the chopped carbon fibers and the carbon nanotubes, the limitation of a single dispersing agent is avoided, and meanwhile, in the preparation process of the carbon fiber gauze, the combined use of the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone can adjust the rheological property of the dispersing liquid, so that the viscosity is moderate, the fluidity is good, and the method is suitable for the subsequent high-speed continuous wet-process networking process. The mass ratio of the polyvinyl alcohol to the polyethylene oxide to the polyvinylpyrrolidone is controlled to be (1.5-2.5): (0.8-1.8): (3.1-4.0), so that the chopped carbon fibers and the carbon nanotubes can reach an excellent dispersion state, the requirement of the process on the fluidity of the dispersion liquid can be met, and the finally prepared carbon fiber gauze has enough mechanical strength. For example, the mass ratio of polyvinyl alcohol, polyethylene oxide, and polyvinylpyrrolidone may be 1.5:0.8:3.1, 1.5:1.8:4.0, 2.0:1.0:3.5, 2.5:1.8:4.0, or 1.8:1.5:3.8, or the mass ratio of polyvinyl alcohol, polyethylene oxide, and polyvinylpyrrolidone may be any value between exemplary mass ratios, for example, the mass ratio of polyvinyl alcohol, polyethylene oxide, and polyvinylpyrrolidone may be any value between (1.8-2.2): (1.0-1.5): (3.3-3.8).
In an exemplary embodiment, the method of making the carbon fiber mesh further comprises subjecting the chopped carbon fibers to a plasma treatment with an oxygen-containing gas source to introduce oxygen-containing functional groups at the surface of the chopped carbon fibers.
In this embodiment, the chopped carbon fiber is subjected to plasma treatment by an oxygen-containing gas source, such as oxygen (O 2), so that oxygen-containing polar groups, such as hydroxyl (-OH) groups and carboxyl (-COOH) groups, can be introduced into the surface of the chopped carbon fiber, and the wettability of the carbon fiber gauze with the matrix resin can be improved by the action of hydrogen bonds and the like when the carbon fiber gauze is used for preparing the carbon fiber composite material.
In an exemplary embodiment, the method of making the carbon fiber mesh further comprises subjecting the chopped carbon fibers to a plasma treatment by a nitrogen-containing gas source to introduce nitrogen-containing functional groups at the surface of the chopped carbon fibers.
In this embodiment, the chopped carbon fiber is subjected to plasma treatment by a nitrogen-containing gas source, such as nitrogen (N 2) or ammonia (NH 3), and nitrogen-containing functional groups such as amine groups (-NH 2) can be introduced into the surface of the chopped carbon fiber, so that when the carbon fiber gauze is used for preparing a carbon fiber composite material, the introduced nitrogen-containing functional groups such as amine groups (-NH 2) and epoxy groups of the epoxy resin undergo a ring-opening reaction to form a firm covalent bond, thereby realizing the strongest interface combination of the carbon fiber gauze and the matrix resin, and greatly improving the interlaminar shear strength and the impact resistance of the carbon fiber composite material.
An exemplary embodiment of the present disclosure provides a carbon fiber reinforced composite material including a carbon fiber mesh yarn as described above or a carbon fiber mesh yarn prepared by the method of preparing a carbon fiber mesh yarn as described above.
For example, the carbon fiber gauze described above or the carbon fiber gauze produced by the method for producing a carbon fiber gauze described above may be laid between layers of a prepreg such as carbon fiber/resin as a toughening intercalation. And then curing and forming by adopting the standard autoclave, mould pressing or vacuum bag and other processes to finally obtain the carbon fiber reinforced composite material. The toughness, impact resistance and interlayer performance of the carbon fiber reinforced composite material are greatly improved, and the carbon fiber reinforced composite material can be widely applied to the high-tech fields of aerospace, new energy automobiles, sports equipment, electronic equipment shells and the like, and meets the high standard requirements of the carbon fiber reinforced composite material on light weight, high strength and high functionality.
In order to more clearly explain the technical solutions provided by the exemplary embodiments of the present disclosure, specific examples of the preparation method of the carbon fiber mesh yarn provided by the exemplary embodiments of the present disclosure to prepare the carbon fiber mesh yarn provided by the exemplary embodiments of the present disclosure are given.
The chopped carbon fibers were subjected to plasma treatment by an oxygen-containing gas source (power 5W, gas pressure 100Pa, treatment duration 60 seconds)/a nitrogen-containing gas source (power 7.5W, gas pressure 80Pa, treatment duration 90 seconds).
Dispersing chopped carbon fibers, carbon nanotubes and a high polymer binder in a solvent to form a dispersion;
dewatering the dispersion liquid through a wet-process net forming process to form a net yarn after dewatering;
And drying the dehydrated gauze to obtain the carbon fiber gauze.
Carbon fiber gauze was prepared in examples 1-6 according to the preparation method in the specific example described above. The carbon fiber reinforced composite laminate is prepared by adopting T800-grade carbon fiber/epoxy resin unidirectional prepreg and carrying out plate making according to each mechanical property test standard, wherein carbon fiber gauze of examples 1-6 is paved between layers of the prepreg such as carbon fiber/epoxy resin and the like, and is cured for 2 hours through an autoclave process at 180 ℃. Mechanical property tests were performed according to the relevant ASTM standards, including interlaminar shear strength (ILSS, ASTM D2344), compressive strength (SACMA SRM 1), type I interlaminar fracture toughness (GIC, ASTM D5528), type II interlaminar fracture toughness (GIIC, ASTM D7905), and compressive strength after impact (CAI, ASTM D7136/D7137). See in particular table 1:
TABLE 1
In addition, the present disclosure also used a T800 grade carbon fiber/epoxy unidirectional prepreg and made a board according to each mechanical property test standard, but did not lay a carbon fiber veil, cured for 2 hours by autoclave process at 180 ℃ to produce a carbon fiber reinforced composite laminate as comparative example 1. Comparative example 1 was subjected to mechanical property testing in accordance with the relevant ASTM standard. Comparative example 1 carbon fiber reinforced composite laminate interlayer shear strength 97 MPa, compressive strength 1476 MPa, type I interlayer fracture toughness 408J/m 2, type II interlayer fracture toughness 932J/m 2, and post impact compressive strength 237 MPa.
As can be seen from the data in table 1 and comparative example 1, the mechanical properties of the carbon fiber reinforced composite laminate prepared by using the carbon fiber gauze provided by the embodiment of the present disclosure are significantly improved compared with those of comparative example 1 which is not toughened by the carbon fiber gauze.
The above descriptions may be implemented alone or in various combinations, and these modifications are within the scope of the present disclosure.
Finally it is pointed out that in the present document the term "comprising," "including," or any other variation thereof, is intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The above embodiments are merely for illustrating the technical solution of the present disclosure, and are not limiting thereof. Although the present disclosure has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that modifications may be made to the technical solutions described in the foregoing embodiments or equivalents may be substituted for some of the technical features thereof, and these modifications or substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present disclosure in essence.
Claims (9)
1. A carbon fiber mesh, characterized in that the carbon fiber mesh comprises chopped carbon fibers and carbon nanotubes bonded to the chopped carbon fibers by a polymeric binder;
The carbon nano tube accounts for 1.8-18.6% of the carbon fiber gauze in percentage by mass.
2. The carbon fiber mesh of claim 1, wherein the polymeric binder comprises at least one of polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, or amphiphilic block copolymer.
3. The carbon fiber gauze according to claim 2, wherein the polymer binder comprises the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone, and wherein a mass ratio of the polyvinyl alcohol, the polyethylene oxide and the polyvinylpyrrolidone is (1.5-2.5): 0.8-1.8): 3.1-4.0.
4. The carbon fiber mesh of claim 1, wherein the chopped carbon fibers have a length of 0.5-30 mm, and the surfaces of the chopped carbon fibers comprise oxygen-containing functional groups and/or nitrogen-containing functional groups.
5. The carbon fiber mesh of claim 1, wherein the carbon fiber mesh has an areal density of 15-56 g/m 2.
6. A method for preparing the carbon fiber gauze according to any one of claims 1 to 5, comprising:
Dispersing chopped carbon fibers, carbon nanotubes and a high polymer binder in a solvent to form a dispersion;
dewatering the dispersion liquid through a wet-process web forming process to form a dewatered gauze;
and drying the dehydrated gauze to obtain the carbon fiber gauze.
7. The method for producing a carbon fiber web as defined in claim 6, wherein the concentration of the polymer binder in the dispersion is 1.5 to 10wt%;
The high polymer adhesive comprises polyvinyl alcohol, polyethylene oxide and polyvinylpyrrolidone, wherein the mass ratio of the polyvinyl alcohol to the polyethylene oxide to the polyvinylpyrrolidone is (1.5-2.5) (0.8-1.8) (3.1-4.0).
8. The method of making a carbon fiber veil of claim 6, further comprising:
the chopped carbon fibers are subjected to plasma treatment by an oxygen-containing gas source to introduce oxygen-containing functional groups on the surfaces of the chopped carbon fibers and/or,
And carrying out plasma treatment on the chopped carbon fiber through a nitrogen-containing air source so as to introduce nitrogen-containing functional groups on the surface of the chopped carbon fiber.
9. A carbon fiber reinforced composite material, characterized in that the carbon fiber reinforced composite material comprises a carbon fiber mesh yarn according to any one of claims 1 to 5 or a carbon fiber mesh yarn prepared by the preparation method of the carbon fiber mesh yarn according to any one of claims 6 to 8.
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