CN115558238A - Super-hybrid conductive resin, prepreg, composite material and preparation method of material - Google Patents
Super-hybrid conductive resin, prepreg, composite material and preparation method of material Download PDFInfo
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- CN115558238A CN115558238A CN202211158493.2A CN202211158493A CN115558238A CN 115558238 A CN115558238 A CN 115558238A CN 202211158493 A CN202211158493 A CN 202211158493A CN 115558238 A CN115558238 A CN 115558238A
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Abstract
The invention relates to a super-hybrid conductive resin, a prepreg, a composite material and a preparation method of the material. The various mixed components of the resin in the invention are mutually independent in a dispersion system, and the resin is easy to permeate in the preparation process of the prepreg and the composite material, so that the components are mutually fused, and the preparation of the low-porosity composite material is met. The carbon nano material in the resin system can reach high content and high uniformity and is dispersed, and the resin system does not pollute the environment when preparing prepreg and composite materials. The composite material prepared by the system can reach the condition that the conventional conductive modified resin cannot reach high conductivity and excellent lightning stroke resistance.
Description
Technical Field
The invention belongs to the technical field of preparation of structural composite materials, and particularly relates to a super-hybrid conductive resin, a prepreg, a composite material and a preparation method of the material.
Background
The continuous fiber reinforced resin matrix composite material has the characteristics of higher specific strength, specific modulus and the like, and can obtain considerable weight reduction after replacing the traditional metal material in the fields of aerospace and the like. However, the composite material has poor conductivity, and is difficult to dredge lightning current in a lightning stroke process, so that the problem of lightning stroke damage is caused, and the lightning stroke damage influences the flight safety of an airplane and influences the normal operation of a wind power blade. The damage of the composite material caused by lightning stroke comprises delamination, fiber breakage, fiber burning perforation and the like, and the damage causes the bending, compression and other properties of the composite material to be greatly reduced. At present, the method of surface-paving metal mesh and metal coating is commonly adopted for the composite material to prevent lightning stroke, however, the method obviously increases the weight of the composite material, for example, the total weight of the copper mesh paved in the 2A area and the resin attached to the surface is more than 150g/m 2 。
In recent years, the development of composite materials having high lightning strike resistance and high mechanical properties by themselves has become another important direction, and a general method is to modify the composite materials in a conductive manner to improve the conductivity of the composite materials themselves, especially in the thickness direction. In addition, the conductivity of the composite material is improved, the composite material can be used for lightning protection, the electromagnetic shielding performance of the composite material can be improved, the piezoelectric modification of the composite material is realized, and the antistatic performance of the composite material is realized.
Increasing the electrical conductivity of the composite is often achieved by adding conductive fillers to the composite. Among many conductive fillers, carbon-based materials are the first choice for modifying materials because of their higher conductivity and lower density. The main method for adding the carbon-based nanomaterial into the composite material can comprise the following steps: (1) Directly dispersing the carbon nano material in resin, and then preparing a corresponding prepreg; (2) Growing a carbon nano material on the surface of the carbon fiber to form a hybrid structure; (3) Preparing a carbon-based material into a conductive thin layer, and then intercalating the conductive thin layer between the layers of the composite material in an intercalation mode. The conductivity of the composite material can be improved to a certain extent by various methods, typically, the thickness-direction conductivity of the composite material is between 0.1 and 0.7S/cm, the performance of resisting lightning stroke damage is also improved to a certain extent, and the damage area is reduced.
However, the prior art has a number of deficiencies. As for the method of directly introducing the carbon nanomaterial into the resin, first, it is difficult for the carbon nanomaterial to be uniformly dispersed into conventional epoxy resins and bismaleimide resins, and it is more difficult to achieve uniform dispersion at high concentration; secondly, when the addition amount is high, the viscosity of the resin dispersion system can greatly increase along with the increase of the dispersion amount, when the dispersion amount is high, if no organic solvent is added, the related process of the composite material can hardly be carried out, such as the addition of the organic solvent, and the environmental pollution problem and the porosity problem are brought, and the porosity of the composite material with the high carbon nano tube addition amount reaches 1-4% (Composites Science and Technology,222 (2022) 109369); thirdly, the modified composite material still has low conductivity, and when the adding amount is low, the conductivity of the composite material system with high conductivity is hardly improved and generally does not exceed 0.15S/cm, and when the adding amount is high, the conductivity of the composite material system is generally not more than 0.7S/cm. When the content of the carbon nano material is low, the modified composite material is difficult to play an effective lightning stroke resisting role. For the method of growing and hybridizing carbon nanotubes to the surface of the fiber and the composite material of carbon nanotube film and bucky paper intercalation, the conductivity of each system in the literature does not exceed 0.8S/cm either, because of the limitation of the conductive contacts of the different layers and the conductive contacts between intercalation and layering. In addition, the method of growing carbon nanotubes on the fiber has the problems of difficult preparation and deteriorated fiber performance; the carbon nanotube film intercalation composite material causes a problem of significant decrease in interlayer properties.
Therefore, the technical problems to be solved include: (1) How to realize high content and good dispersion of the carbon nano material; (2) How to realize higher conductivity of the composite material with the same content of the carbon nano material, namely how to realize effective conductive connection function of the carbon nano material; (3) The problem of manufacturability of the prepreg and the composite material during high carbon nano material content is solved, so that the composite material with low porosity and high performance is obtained; (5) How to avoid the problem of environmental pollution in the preparation process of the material.
Disclosure of Invention
The invention mainly aims at the problems and provides a super-hybrid conductive resin, a prepreg, a composite material and a preparation method of the material, aiming at realizing the low porosity and high conductivity of the conductive nano modified composite material and meeting the technological requirements of the composite material, thereby meeting the requirements of a resin system and a prepreg system for resisting lightning stroke damage or meeting the requirements of other functional composite materials.
In order to achieve the above object, the present invention provides a super-hybrid conductive resin, which comprises an aqueous liquid dispersion system composed of a resin microsphere emulsion, a curing agent, and an aqueous dispersion liquid of a carbon nanomaterial, or a water-free resin obtained by removing water from the aqueous liquid dispersion system; wherein, in each composition excluding water in the super-hybrid conductive resin, the total content of the carbon nano-material is 1-25 wt%, and the content of the resin microsphere and the curing agent is 50-99 wt%.
Further, the carbon nano material is one of or an intercompatible substance of carbon nano tube, graphene, carbon black, nano carbon fiber, metal-plated carbon nano tube, metal-plated graphene and metal-plated carbon nano fiber; wherein, in each composition excluding water in the super-hybrid conductive resin, the total content of the carbon nano-materials is 3-20 wt%.
Further, the resin microsphere emulsion is an epoxy resin aqueous emulsion or a bismaleimide resin aqueous emulsion, and the average epoxy value of the epoxy resin used in the epoxy resin aqueous emulsion is between 0.30 and 0.80mol/100 g.
Further, the epoxy resin used in the epoxy resin aqueous emulsion is one of E54, E51, F51, AG80, F44 and E44 or an intercompatible substance between the E54, the E51, the F51, the AG80, the F44 and the E44.
Further, the water content of the super hybrid resin of the aqueous liquid dispersion is 55 to 90wt%.
Further, the curing agent is ultrafine powder of a latent curing agent which is hardly soluble in water, and the average particle diameter of the curing agent particles is not more than 10 μm.
Further, the super-hybrid conductive resin in the water-free resin forming the water-containing liquid dispersion system or the water-removed water-containing liquid dispersion system also comprises micro-nano particles, wherein the content of the micro-nano particles is 0-50 wt%; the micro-nano particles are one of silver nanowires, silver nanosheets, polytetrafluoroethylene particles, magnetic nanoparticles, piezoelectric nanoparticles, organic micro-nano fibers and toughening agent particles or an intercompatible substance of the silver nanowires, the silver nanosheets, the polytetrafluoroethylene particles, the magnetic nanoparticles, the piezoelectric nanoparticles, the organic micro-nano fibers and the toughening agent particles, and the average particle size of the toughening agent particles is not more than 20 microns.
In order to achieve the purpose, the invention provides a super-hybrid conductive resin prepreg which is obtained by dispersing an aqueous liquid system of super-hybrid conductive resin onto unidirectional continuous fibers or continuous fiber fabrics through brushing, dipping, roller coating and spraying, and then coiling and packaging after drying or natural airing.
In order to achieve the above object, the present invention provides a super hybrid composite material prepared from the super hybrid conductive resin or the super hybrid conductive resin prepreg.
To achieve the above object, the present invention provides a method for preparing a super-hybrid composite material, comprising the steps of:
adding deionized water into the resin microsphere emulsion, and uniformly stirring to obtain diluted resin microsphere aqueous emulsion;
adding deionized water into the carbon nano-material aqueous dispersion liquid, and uniformly stirring to obtain diluted carbon nano-material aqueous dispersion liquid;
slowly adding the diluted aqueous dispersion liquid of the carbon nano-material into the diluted aqueous emulsion of the resin microspheres, and uniformly mixing to obtain a mixed liquid;
adding a curing agent into the mixed solution, and fully and uniformly stirring to obtain a water dispersion system of the super-hybrid conductive resin;
preparing the water dispersion system of the super-hybrid conductive resin into a carbon fiber prepreg of the super-hybrid conductive resin according to a prepreg forming process;
laying the carbon fiber prepreg of the super hybrid conductive resin to obtain a prefabricated body;
and forming the prefabricated body obtained by laying according to a composite material forming process to obtain the super-hybrid composite material.
The technical scheme of the invention has the following advantages: by utilizing the characteristics of environmental protection, low viscosity and the like of a water-based dispersion system and the characteristics of high dispersion and easy blending of the water-based nano dispersion system, a resin system, a conductive medium and functional micro-nano materials including a toughening agent are mixed together in a dispersion form with micro-nano dispersion uniformity degree to form a low-viscosity super-mixed conductive resin dispersion system which can be brushed, rolled, dipped and sprayed, and an organic solvent with environmental pollution is not used, so that the nano-scale dispersion of the original system is not influenced; by controlling the parameters such as the type and the content of the epoxy resin, the conductive nano content, the water content, the curing agent characteristics and the like, the preparation manufacturability of the prepreg and the composite material can be met, and the composite material with high conductivity and excellent lightning protection performance can be obtained.
Drawings
FIG. 1 is a schematic composition diagram of a super-hybrid conductive resin of the present invention.
Fig. 2 is a schematic composition diagram of a super hybrid conductive resin prepreg according to the present invention.
Fig. 3 is a schematic composition diagram of a super-hybrid composite material according to the present invention.
FIG. 4 is an SEM image of a cured substance of a super-hybrid conductive resin containing 3.6wt% (a) and 7wt% (b) of carbon nanotubes according to an embodiment of the present invention.
FIG. 5 is a photograph and C scan of a sample of a composite material prepared from a super-hybrid conductive resin (CNT content 7 wt%) without surface protection after a simulated 2A zone lightning strike according to an embodiment of the invention.
FIG. 6 is a photograph showing the simulated 2A region lightning strike damage characteristics of a CNT-modified resin carbon fiber composite prepared by a conventional solution dispersion method according to an embodiment of the present invention [ (a) 5wt% of CNT content and (b) 7wt% of CNT content ].
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings for convenience in describing the invention and for simplicity in description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered as limiting. Moreover, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. Specific meanings of the above terms in the present invention can be specifically understood by those of ordinary skill in the art.
The concept of composite material means that one material can not meet the use requirement, and two or more materials are required to be compounded together to form another material which can meet the requirement of people, namely the composite material.
Composite materials are of many kinds and generally consist of a reinforcing material and a matrix material; wherein, the matrix material includes but is not limited to epoxy resin, polyester resin, thermoplastic resin, etc.; reinforcing materials include, but are not limited to, carbon fibers, glass fibers, aramid fibers, and the like.
As an example, the present embodiment provides a method of preparing a super-hybrid composite material, comprising the steps of:
step one, adding deionized water into resin microsphere emulsion, and uniformly stirring to obtain diluted resin microsphere aqueous emulsion; the resin microsphere emulsion can be epoxy resin aqueous emulsion or bismaleimide resin aqueous emulsion.
Secondly, adding deionized water into the carbon nano-material aqueous dispersion liquid, and uniformly stirring to obtain diluted carbon nano-material aqueous dispersion liquid; the carbon nano material for preparing the carbon nano material aqueous dispersion liquid is one of carbon nano tube, graphene, carbon black, nano carbon fiber, metal-plated carbon nano tube, metal-plated graphene and metal-plated carbon nano fiber or an intercompatible substance of the carbon nano material, the graphene and the carbon nano fiber.
And thirdly, slowly adding the diluted aqueous dispersion liquid of the carbon nano material into the diluted aqueous emulsion of the resin microspheres, and uniformly mixing to obtain a mixed liquid.
Fourthly, adding a curing agent into the mixed solution, and fully and uniformly stirring to obtain a water dispersion system of the super-hybrid conductive resin; the curing agent is superfine powder of latent curing agent which is difficult to dissolve in water, and the average grain diameter of curing agent particles is not more than 10 mu m.
In the steps from the first step to the fourth step of this example, the content of the carbon nanomaterial is 1 to 25wt%, and the content of the epoxy resin microspheres and the curing agent thereof is 50 to 99wt% in the composition that the obtained water dispersion system of the super-hybrid conductive resin does not contain water; in some preferred embodiments, a material for preparing an aqueous dispersion system of a super-hybrid conductive resin may be added with a bulk of other nano-materials, such as micro-nano particles with a content of 0-50 wt%, wherein the micro-nano particles may be silver nanowires, silver nanosheets, polytetrafluoroethylene particles, magnetic nanoparticles, piezoelectric nanoparticles, organic micro-nano fibers, toughening agent particles, etc. to improve the performance, and the average particle size of the toughening agent particles is not more than 20 μm.
And fifthly, preparing the carbon fiber prepreg of the super hybrid conductive resin from the water dispersion system of the super hybrid conductive resin prepared in the fourth step according to a prepreg forming process.
In the step, the aqueous dispersion system of the super-hybrid conductive resin is dispersed on unidirectional continuous fibers or continuous fiber fabrics by methods of brushing, dipping, roller coating, spraying and the like, and then is dried or naturally aired, wound and packaged to obtain corresponding prepreg; it is noted that the process for preparing the prepreg is not limited thereto.
And sixthly, laying the carbon fiber prepreg of the super hybrid conductive resin to obtain a prefabricated body.
And seventhly, forming the prefabricated body obtained by laying the layers according to a composite material forming process to obtain the super-hybrid composite material.
In the step, a plurality of carbon fiber prepregs are cut and layered according to the layering sequence to obtain a composite material preform, the composite material preform is molded according to the autoclave molding process, and the composite material is taken out after curing molding and cooling to obtain the high-content carbon nanotube modified composite material.
This example also provides a super-hybrid conductive resin which can be used as a material having high conductivity and excellent mechanical properties, and the conductivity of the cured resin can be 0.1 to 1S/cm. As shown in fig. 1, the super-hybrid conductive resin comprises an aqueous liquid dispersion system composed of a resin microsphere emulsion 1, a curing agent 5 and an aqueous dispersion liquid of carbon nano-materials (carbon nano-materials 2 and water 4), or a water-free resin formed by removing water from the aqueous liquid dispersion system; wherein, in each composition excluding water in the super-hybrid conductive resin, the content of the carbon nano material in the aqueous dispersion liquid of the carbon nano material is 1 to 25 weight percent, and the content of the resin microsphere and the curing agent in the resin microsphere emulsion is 50 to 99 weight percent; as a preferred example of this embodiment, the formed aqueous liquid dispersion system or the water-free resin obtained by dewatering the aqueous liquid dispersion system may contain micro-nano particles 3, and when the micro-nano particles 3 are contained, the content of the micro-nano particles is 0 to 50wt%.
In this example, when the carbon nanomaterial from which the aqueous dispersion of carbon nanomaterials is prepared is one of carbon nanotubes, graphene, carbon black, filamentous nanocarbons, metal-coated carbon nanotubes, metal-coated graphene, metal-coated carbon nanofibers, or an intercalant therebetween, the total content of carbon nanomaterials in the composition excluding water in the resin is 3 to 20wt%.
In this example, the water content of the super hybrid resin of the aqueous liquid dispersion is 55 to 90wt%.
The aqueous liquid dispersion system composed of the resin microsphere emulsion 1, the curing agent 5 and the aqueous dispersion liquid of the carbon nano material (the carbon nano material 2 and the water 4) can be used for preparing the super-hybrid conductive resin prepreg and the super-hybrid composite material; the water-free resin obtained by removing water from the aqueous liquid dispersion system consisting of the resin microsphere emulsion 1, the curing agent 5 and the carbon nano material aqueous dispersion (the carbon nano material 2 and the water 4) can be used for preparing the super-hybrid composite material and can also be used for other purposes.
The embodiment also provides a super-hybrid conductive resin prepreg, which is prepared from the aqueous dispersion system (containing water) of the super-hybrid conductive resin prepared in the above embodiment, and fig. 2 is a schematic composition diagram of the prepared super-hybrid conductive resin prepreg, wherein the prepreg comprises resin microspheres 1-1 or microdroplets, carbon nano-materials 2, micro-nano particles 3 or toughening agents, continuous reinforcing fibers 6, and a curing agent 5.
The embodiment also provides a super-hybrid composite material, the composite material is prepared by using the super-hybrid conductive resin (which may or may not contain water) prepared in the above embodiment or the super-hybrid conductive resin prepreg prepared in the above manner as a raw material, and fig. 3 is a composition schematic diagram of the super-hybrid composite material, wherein the super-hybrid composite material includes a cured resin matrix 1-2, a carbon nanomaterial 2, a micro-nano particle 3 or a toughening agent, and a continuous reinforcing fiber 6.
1) The super-hybrid resin prepared by the implementation method can solve the problem of dispersion of carbon nano materials in high-viscosity resin:
the embodiment is prepared by blending a nano dispersion system, and the conductive carbon nano material and the resin emulsion form homogeneous phase blending of liquid phase, so that the dispersion is good, the agglomeration of the carbon nano material hardly exists, and the mass fraction of the carbon nano material dispersed in the resin can reach more than 50wt% after water is removed. A typical picture of the carbon nanotube dispersion after the resin is cured is shown in fig. 4. As can be seen from fig. 4, this example achieved a high content of good dispersion of the carbon nanomaterial.
2) The super-hybrid composite material prepared by the implementation method can solve the problem that the composite material has higher conductivity when the content of the carbon nano material is the same, namely how to realize the effective conductive connection effect of the carbon nano material:
it should be noted that in the conventional hybrid resin, gradual aggregation cannot be avoided when the content of the carbon nanomaterial is high, the conductivity of the system gradually becomes poor, and rapid aggregation failure easily occurs in the presence of a solvent, so that the finally prepared casting body is not conductive.
The super-hybrid conductive resin in the embodiment is a stacking body of dispersed resin nanoparticles, carbon nanomaterials and other nanomaterials, and the resin nanoparticles play a role in highly dispersing and distributing templates for the carbon nanomaterials and prevent the carbon nanomaterials from self-aggregating. Therefore, the seepage threshold of the material is greatly reduced, the conductivity is greatly improved, and the storage stability is improved.
Therefore, when the super-hybrid conductive resin in this embodiment is used to prepare a composite material, the weak interaction and separation between the carbon nano-materials and the resin improves the conductive bridging between the carbon nanotubes, which makes the final composite material have high conductivity. The thickness conductivity of several typical composite materials prepared by using super-hybrid conductive resin is shown in table 1, and corresponding comparison is given, so that the conductivity of the composite material is far higher than that of the composite material with high carbon nanotube content obtained by the conventional technology and the composite material obtained by other carbon nanotube modification technologies under the same carbon nanotube content.
TABLE 1 conductivity of composites prepared with super hybrid conductive resins
And (3) injecting 1, self-preparing two carbon nanotube and graphene hybrid carbon fiber reinforced epoxy resin matrix composite materials.
Note 2:2wt% of single-walled carbon nanotube modified resin-based carbon fiber composite material.
Note 3: the interlayer full interlayer thickness reaches 150 mu m of the carbon fiber composite material of the base paper.
Note 4: carbon fiber reinforced composite material with in-situ grown carbon nanotubes.
Note 5:3wt% of carbon black modified resin-based carbon fiber composite material with enhanced conductivity.
Note 6: conventional high carbon nanotube content resins (Composites Science and Technology,222 (2022) 109369).
3) The super-hybrid composite material prepared by the implementation method can solve the problem of manufacturability of prepreg and composite material in high carbon nano-material content:
the conventional resin with high content of the carbon nano material has high viscosity, a large amount of organic solvent is required to be added for reducing the viscosity when the resin is used for preparing a composite material, so that the environmental pollution is caused, and after the organic solvent is added, the carbon nano material is easy to rapidly agglomerate, so that the manufacturability and the dispersibility are poor. In addition, the carbon nano material and the resin in the prepreg after the organic solvent is removed have better compatibility, the fluidity and the permeability of the resin are reduced, and the porosity of the composite material is improved.
The super-hybrid conductive resin of the embodiment is a system in which the resin nano-microspheres and the carbon nano-material are co-dispersed, the carbon nano-material is wrapped around the resin nano-microspheres, the resin nano-microspheres are broken under the molding pressure and temperature, and permeate into the gaps and the fiber layer of the nano-material, and the curing agent is diffused in the resin, so that a good low-porosity composite material is finally formed. The use of a microsphere emulsion prepared with a relatively high epoxy value epoxy resin having a relatively low viscosity facilitates such penetration curing, and therefore in a preferred embodiment the lower average epoxy value of the epoxy resin used to prepare the emulsion should be higher than 0.30, while the use of an epoxy resin having an excessively high epoxy value, which is too low in viscosity, is detrimental to the stability of the super-hybrid resin system, and therefore the upper average epoxy value of a preferred embodiment should be lower than 0.80, thus providing good penetration under the heating conditions for curing. Typical epoxy resins such as E54, E51, AG80, F51, F44, E44 and the like and mixed resins thereof are preferred, but high-viscosity low epoxy value resins such as CYD-014 and the like are not used singly in the resin system, but can be adjusted to an appropriate epoxy value range by being matched with high-epoxy value resins such as AG80 and the like, and then applied to the system.
When applied to the preparation of prepregs, the present example used an aqueous dispersion of a super hybrid conductive resin, where the water content was 55 to 90wt% to achieve good manufacturability and avoid aggregation inside the system. When the carbon nanomaterial is applied to composite material preparation, the mass fraction of the carbon nanomaterial in the resin of the embodiment is still lower than 20wt% (excluding water), and when the mass fraction of the carbon nanomaterial is lower than 15wt%, the carbon nanomaterial has good manufacturability, and meets the requirements of composite material fiber volume fraction control and a conventional autoclave curing process, and the prepared composite material has low porosity as shown by difficult observation under a metallographic optical microscope, and the tested porosity and comparison are shown in table 2. In order to realize good lightning protection performance, the mass fraction of the carbon nano material is not less than 3wt%.
TABLE 2 porosity of composites prepared with super-hybrid conductive resins
Note 1 composite materials from conventional high carbon nanotube content resins (Composites Science and Technology,222 (2022) 109369).
4) The super-hybrid composite material prepared by the implementation method can solve the problem of environmental pollution in the material preparation process:
conventional dispersion of highly concentrated dispersed carbon nanomaterials into high viscosity resins often requires dilution with organic solvents and viscosity reduction, acetone, N-dimethylformamide, N-methylpyrrolidone are common solvents, but the presence of organic solvents, good compatibility of organic solvents and epoxy resins make removal of these solvents difficult, resulting in residues in the system, and the use of large amounts of organic solvents also presents environmental problems. The system in this example is an aqueous phase system, no organic solvent is used, the compatibility between water and resin is poor, the aqueous phase and the nano phase are separated from each other, and the water in the aqueous phase and the nano phase are easily removed to form a dry resin and a dry prepreg.
5) The super-hybrid composite material prepared by the implementation method has other effects:
the composite material prepared from the super-hybrid conductive resin has good mechanical property, the bending strength of the twill T300-grade carbon fiber fabric composite material reaches 730MPa, the interlaminar shear strength reaches 72MPa, and the interlaminar shear strength of the unidirectional T800-grade carbon fiber composite material reaches 105-110 MPa, which are all improved to different degrees compared with the control composite material.
The composite material body prepared by the super-hybrid conductive resin has very outstanding lightning protection performance, only a few fibers on the surface are broken after 2A area lightning stroke is simulated, as shown in FIG. 5, a C scanning chart of FIG. 5 shows that no internal layering exists after the lightning stroke, and only the resin on the surface is ablated, which brings possibility for material repair; a picture of a carbon nanotube hybrid resin-based composite material prepared by the traditional solvent in a comparative mode after simulating lightning stroke in a 2A area is shown in figure 6, fibers in a damage center are broken in a large area, and one layer and the second layer are layered in a large area.
After 2A area lightning stroke is simulated, the compressive strength retention rate and the compressive modulus retention rate of the typical composite material without surface protection reach 100%, the bending strength retention rate of a lightning stroke damage center (100mm x 100mm area) of the typical composite material without surface protection reaches 93-95%, the excellent lightning stroke resistance is shown, and the weight is increased by only 45g/m 2 Far lower than prior art 150g/m 2 The weight gain is as above.
The method for preparing the super-hybrid composite material provided by the invention is described in detail with reference to specific examples.
Example 1:
the implementation process of the technical scheme of the embodiment is as follows:
(1-1) taking 100g of 50wt% E51 epoxy resin aqueous emulsion, adding 50mL of deionized water, and uniformly stirring; then 100g of 5wt% carbon nanotube aqueous dispersion slurry is taken, 50mL of deionized water is added, and the mixture is stirred uniformly; slowly adding the diluted carbon nano tube aqueous dispersion slurry into the diluted epoxy resin aqueous emulsion, continuously stirring, and uniformly mixing the diluted carbon nano tube aqueous dispersion slurry and the diluted epoxy resin aqueous emulsion; 16.6g of 4,4' -diamino diphenyl sulfone superfine powder with the average particle size of 3.5 mu m is added into the mixed solution and fully and uniformly stirred to obtain an aqueous dispersion system (excluding water) of the super-hybrid epoxy resin with the carbon nano tube content of 7.05 weight percent, wherein the water content in the dispersion system is 77.6 weight percent.
(1-2) uniformly coating the aqueous dispersion system of the super-hybrid epoxy resin on a unidirectional T800 carbon fiber fabric on two sides by a brush coating method to enable the resin content to be 33wt%, standing for two days at room temperature in an environment with the humidity lower than 30% until the resin is completely dried, and then drying for 1h at 80 ℃ to obtain the T800 carbon fiber prepreg of the super-hybrid epoxy resin.
(1-3) cutting the T800 carbon fiber prepreg into 300mm-300mm pieces of 16 pieces of prepreg according to the angle of 0 DEG] 16 And (3) performing unidirectional layering to obtain a composite material prefabricated body, and then molding according to an autoclave molding process, wherein the curing temperature is 180 ℃. And cooling to below 60 ℃ after the molding is finished, and taking out the composite material to obtain the high-content carbon nanotube modified composite material.
(1-4) the above-mentioned 100g of the aqueous dispersion slurry of carbon nanotubes having a concentration of 5wt% may be replaced with 100g of the aqueous dispersion slurry of carbon nanotubes having a concentration of 5wt% and 50g of the aqueous dispersion slurry of graphene having a concentration of 5wt%, and the weight percentage of the carbon nanomaterials in the final resin dispersion system is about 10.2wt% based on the dry resin.
The composite material modified by the high-content carbon nano tube obtained by the embodiment has good conductivity and lightning stroke resistance, the thickness-direction conductivity of the composite material reaches 1.35S/cm, which is about 10 times that of the conventional non-modified high-conductivity carbon fiber composite material or 1000 times that of the conventional low-conductivity composite material, and the surface of the composite material is only subjected to ablation damage with a small area after being subjected to lightning stroke in a 2A area, so that obvious layered damage cannot be seen.
Example 2:
the implementation process of the technical scheme of the embodiment is as follows:
(2-1) taking 100g of 50wt% of the matched epoxy resin aqueous emulsion of F51 and E51, wherein the mass ratio of the F51 to the E51 is 3:2 or 1:4, adding 50mL of deionized water into the emulsion, uniformly stirring, and diluting to obtain 33.3wt% of epoxy resin aqueous emulsion; then taking 25g of 5wt% carbon nanotube aqueous dispersion slurry and 25g of 5wt% graphene aqueous dispersion slurry, adding 50mL of deionized water, and uniformly stirring; slowly adding the diluted carbon nano tube and graphene aqueous co-dispersion slurry into the diluted epoxy resin aqueous emulsion, continuously stirring, and uniformly mixing the diluted carbon nano tube and graphene aqueous co-dispersion slurry; taking 10g of superfine particles of phenolphthalein modified polyether ether ketone (PEK-C), adding the superfine particles with the average particle diameter of 7 mu m into the mixed solution, and stirring for 10 minutes while carrying out ultrasonic oscillation to ensure that the whole particles are uniformly dispersed; then 16.6g of 4,4' -diamino diphenyl sulfone superfine powder with the average grain diameter of 2.5 mu m is added into the mixed solution and fully and evenly stirred. Obtaining the water dispersion system of the super-hybrid conductive epoxy resin co-mixed by the carbon nano tube, the graphene and the PEK-C, DDS. In the dispersion system, the water content was 71.3wt%, and the carbon nanomaterial content in the resin after water removal was 3.16wt%.
(2-2) uniformly coating the water dispersion system of the super-hybrid epoxy resin on a CF3031 twill-woven carbon fiber fabric on both sides by adopting a brush coating method to ensure that the resin content in the prepreg is 42wt%, drying for 1h at 80 ℃ to be basically dry, and then drying for 1h in vacuum at 100 ℃ to obtain the CF3031 carbon fiber prepreg fabric of the super-hybrid epoxy resin.
(2-3) cutting the prepreg into 8 pieces of 300mm/300mm prepreg, obtaining a composite material preform according to the layering sequence of [45 degrees, 0 degrees, 45 degrees, 0 degrees and 45 degrees ], and then molding according to an autoclave molding process, wherein the curing temperature is 180 degrees/2 hours. And cooling to below 60 ℃ after the molding is finished, and taking out the composite material to obtain the high-content carbon nanotube modified composite material.
(2-4) GW3031 twill fabric can be used in (2-2), or the dosages of the graphene and carbon nano tube aqueous slurry can be respectively 30g and 70g, or 20g and 80g.
(2-5) 5wt% aqueous slurry of silver-plated graphene and silver-plated carbon nanotubes may also be used in the above (2-2), and the amount may be 10g and 60g, or 20g and 50g, respectively.
The composite material modified by the high-content carbon nano tube obtained by the embodiment has good toughness, conductivity and lightning damage resistance.
Example 3:
the implementation process of the technical scheme of the embodiment is as follows:
(3-1) 100g of an aqueous epoxy resin emulsion prepared by mixing 50wt% of AG80 and F44 in a mixing ratio of 1:1; then adding 50mL of deionized water into 100g of 5wt% aqueous dispersion slurry of carbon nanotubes and 50g of 5wt% aqueous dispersion slurry of silver-plated carbon nanotubes, silver-plated graphene or carbon nanofiber, and stirring uniformly; slowly adding the diluted carbon nano tube aqueous dispersion slurry into the diluted epoxy resin aqueous emulsion, continuously stirring, and uniformly mixing the diluted carbon nano tube aqueous dispersion slurry and the diluted epoxy resin aqueous emulsion; then adding 10g10wt% PZT nanowire aqueous dispersion slurry; adding 7g of dicyandiamide superfine powder into the mixed solution, and fully and uniformly stirring. To obtain the water dispersion system of the super-hybrid epoxy resin with the carbon nano material content of 9.3wt% containing various particles such as carbon nano tubes, PZT, curing agent and the like.
(3-2) uniformly coating the water dispersion system of the super-hybrid epoxy resin on a unidirectional T800 carbon fiber fabric in a double-sided manner by adopting a roller coating method, so that the content of the dried resin is 37wt%, directly drying the dried resin by a 10-meter-long 120-DEG oven after the roller coating, and then coiling the dried resin to obtain the T800 carbon fiber prepreg of the super-hybrid epoxy resin.
(3-3) cutting the prepreg into 16 pieces of prepreg with the length of 300mm to obtain 16 pieces of prepreg with the length of [45 degrees, 0 degrees ]45°，90°] 2S The composite material prefabricated body is obtained through the layering sequence, and then the composite material prefabricated body is formed according to the autoclave forming process, wherein the curing temperature is 180 ℃/2h. And cooling to below 60 ℃ after the molding is finished, and taking out the composite material to obtain the multifunctional modified composite material with high content of the carbon nano tube.
Example 4:
the implementation process of the technical scheme of the embodiment is as follows:
(4-1) taking 100g of 50wt% E44 epoxy resin aqueous emulsion; then 100g of graphene aqueous dispersion slurry with the concentration of 5wt%, 50g of silver-plated carbon nanotube aqueous dispersion slurry with the concentration of 5wt% and 20g of carbon nanofiber aqueous dispersion liquid with the concentration of 8wt% are taken and stirred uniformly; slowly adding the silver-plated carbon nano tube, graphene and carbon nano fiber aqueous co-dispersion slurry into an epoxy resin aqueous emulsion under stirring, continuously stirring, then adding 10g of thermoplastic polyimide ultrafine powder with the average particle size of 8.5 mu m or 2.2 mu m, and uniformly mixing the components under stirring and ultrasound; 13.8g of 4,4' -diaminodiphenyl sulfone ultrafine powder with the average particle size of 8.2 mu m is added into the mixed solution and fully and uniformly stirred. To obtain the water dispersion system of the super-hybrid conductive epoxy resin containing graphene, silver-plated carbon nano tubes, carbon nano fibers, a toughening agent and a curing agent.
(4-2) drying the aqueous dispersion system of the super-hybrid epoxy resin at the spreading state of 80 ℃ to remove moisture, thus obtaining the dry super-hybrid epoxy resin.
(4-3) carrying out compression molding on the dry super-hybrid epoxy resin, and curing at 150 ℃/2h and 180/2h to obtain the epoxy resin casting body with good conductivity and toughness.
Example 5:
the implementation process of the technical scheme of the embodiment is as follows:
(5-1) taking 100g of 40wt% bismaleimide resin aqueous emulsion; then 150g of 5wt% carbon nano tube aqueous dispersion slurry is taken, 50g of 10wt% fluorescent nano particles is taken, 2g of carbon black nano particles are taken, 50mL of deionized water is added, and the mixture is stirred uniformly under ultrasonic; slowly adding the diluted water-based dispersion slurry of the carbon nano tube, the carbon black and the fluorescent nano particles into the diluted water-based emulsion of the bismaleimide resin, continuously stirring the mixture at the same time, and uniformly mixing the diluted water-based dispersion slurry of the carbon nano tube, the carbon black and the fluorescent nano particles; and adding 5g of PEK-C powder into the dispersion liquid, and uniformly mixing under high-speed stirring to obtain the aqueous dispersion system of the super-hybrid bismaleimide resin containing solid particles such as carbon nano tubes, carbon black, fluorescent nano particles, PEK-C and the like.
(5-2) uniformly coating the water dispersion system of the super hybrid bismaleimide resin on a unidirectional ZT7H carbon fiber fabric (700 grade) on two sides by adopting a brush coating method, wherein the thickness of a single layer is 0.125mm, the resin content is 34wt%, and drying is carried out at 60 ℃ until the drying is complete, so as to obtain the ZT7H unidirectional carbon fiber prepreg of the super hybrid bismaleimide resin.
(5-3) cutting 16 carbon fiber prepregs with the size of 300mm/300mm according to the angle of [45 degrees, 0 degrees, -45 degrees and 90 degrees] 2S The composite material preform is obtained through the layering sequence, and then the composite material preform is molded according to the autoclave molding process, wherein the curing temperature is 160 ℃/2h +200 ℃/5h. Cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multielement nano modified composite material with high content of carbon nano tubes, carbon black and fluorescent nano particles.
Example 6:
the implementation process of the technical scheme of the embodiment is as follows:
(6-1) taking 100g of 50wt% E51 epoxy resin aqueous emulsion, adding 50mL of deionized water for dilution, and uniformly stirring; taking 50g of 5wt% carbon nanotube aqueous dispersion slurry, taking 50g of 15wt% silver-plated carbon nanofiber aqueous dispersion slurry, taking 20g of 5wt% graphene aqueous dispersion slurry, adding 30mL of deionized water, and ultrasonically stirring uniformly; slowly adding the multi-element nano water-based dispersion slurry into diluted epoxy resin water-based emulsion, continuously stirring, and uniformly mixing the two; adding 20g of 4,4' -diamino diphenyl sulfone superfine powder with the average particle size of 3 mu m into the mixed solution, and fully and uniformly stirring. Obtaining the water dispersion system of the super-hybrid conductive epoxy resin which is formed by mixing the carbon nano tube, the graphene and the silver-plated carbon nano fiber.
(6-2) drying the aqueous dispersion system of the super-hybrid epoxy resin in the step (6-1) at the temperature of 80 ℃ to remove moisture, thus obtaining the dry super-hybrid epoxy resin which can be used for preparing a high-conductivity resin block;
(6-3) coating the super-hybrid epoxy resin (6-1) on a CCF800H carbon fiber unidirectional fabric to enable the resin content to be 38wt%, and then drying through a heating plate to obtain a dry prepreg; rolling and flattening the prepreg for later use;
(6-4) cutting 16 carbon fiber prepregs with the size of 300mm/300mm according to the angle of [45 degrees, 0 degrees, -45 degrees and 90 degrees] 2S The composite material prefabricated body is obtained through layering sequence, and then the composite material prefabricated body is formed according to the autoclave forming process, wherein the curing temperature is 180 ℃/2h. And cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multielement conductive nano modified composite material with high content of carbon nano tubes, graphene and silver-plated carbon nano fibers.
(6-5) the silver-plated carbon nanofiber can be replaced by equivalent magnetic nanoparticles or PZT nano piezoelectric powder, so that the multifunctional modified composite material modified by high-content carbon nanotubes, graphene, magnetic nanoparticles or piezoelectric nanoparticles is obtained.
Example 7:
the implementation process of the technical scheme of the invention is as follows:
(7-1) taking 100g of 50wt% of E51 or E54 epoxy resin aqueous emulsion, adding 50mL of deionized water for dilution, and uniformly stirring; taking 50g of 5wt% aqueous dispersion slurry of carbon nanotubes, taking 50g of 15wt% aqueous dispersion slurry of PZT nanoparticles, taking 20g of 5wt% aqueous dispersion slurry of graphene, adding 30mL of deionized water, and ultrasonically stirring uniformly; slowly adding the multi-element nano water-based dispersion slurry into diluted epoxy resin water-based emulsion, continuously stirring, and uniformly mixing the two; 13g of 4,4' -diaminodiphenylmethane ultrafine powder is added into the mixed solution and stirred fully and uniformly. And obtaining the water dispersion system of the super-hybrid epoxy resin with the carbon nano-tube, the graphene and the PZT particles being co-mixed.
(7-2) drying the aqueous dispersion system of the super-hybrid epoxy resin in the step (7-1) at the temperature of 80 ℃ to remove moisture, thus obtaining the dry super-hybrid epoxy resin which can be used for preparing high-conductivity casting bodies;
(7-3) coating the super-hybrid epoxy resin (7-1) on an S4 high-strength glass fiber unidirectional fabric to ensure that the resin content is 38wt%, and then drying by a heating plate to obtain a dry prepreg; rolling and flattening the prepreg for later use;
(7-4) cutting 16 pieces of the S4 high-strength glass fiber prepreg with the size of 300mm to 300mm according to the angles of [45 degrees, 0 degrees, 45 degrees and 90 degrees] 2S The composite material prefabricated body is obtained through the layering sequence, and then the composite material prefabricated body is formed according to the autoclave forming process, wherein the curing temperature is 120 ℃/2h. And cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multi-element nano modified composite material with high content of carbon nano tubes, graphene and PZT particles.
(7-5) the PZT particles can be replaced by magnetic nanoparticles with the same or three times of dosage, so that the multi-element nano modified S4 high-strength glass fiber composite material with high content of carbon nanotubes, graphene and magnetic nanoparticles is obtained.
Example 8:
the implementation process of the technical scheme of the embodiment is as follows:
(8-1) taking 100g of 50wt% E51 epoxy resin aqueous emulsion, and adding 100mL of water; taking 50g of 5wt% aqueous dispersion slurry of the carbon nano tube and 50g of 5wt% aqueous dispersion slurry of the silver-plated carbon nano tube, diluting with 50mL of water, and uniformly stirring; slowly adding silver-plated carbon nano tube and carbon nano tube aqueous co-dispersion slurry into epoxy resin aqueous emulsion under stirring, continuously stirring, then adding 50g or 100g of polytetrafluoroethylene particle dispersion emulsion with the weight percent of 60wt% and the average particle size of 1 mu m, and uniformly mixing the components under stirring and ultrasound; 15.8g of 4,4' -diaminodiphenyl sulfone ultrafine powder with the average particle size of 2.3 mu m is added into the mixed solution and stirred fully and uniformly. To obtain the water dispersion system of the super-hybrid conductive epoxy resin containing the carbon nano tube, the silver-plated carbon nano tube, the polytetrafluoroethylene particle and the curing agent.
(8-2) drying the aqueous dispersion system of the super-hybrid epoxy resin at the spreading state of 100 ℃ to remove moisture, thus obtaining the dry super-hybrid conductive epoxy resin containing polytetrafluoroethylene.
(8-3) carrying out compression molding on the dry super-hybrid epoxy resin, and curing at 150 ℃/2h and 180/2h to obtain the epoxy resin casting body with good conductivity and toughness and extremely small friction coefficient.
(8-4) spraying the double surfaces of the super hybrid epoxy resin (8-1) on a CF8010 high-strength carbon fiber plain weave fabric to enable the resin content to be 45wt%, and then drying the plain weave fabric through a heating plate to obtain a dry prepreg; rolling and flattening the prepreg for later use;
(8-5) cutting the CF8010 high-strength carbon fiber prepreg of 16 sheets with the size of 200mm × 200mm according to [45 degrees, 0 degrees, -45 degrees and 90 degrees] 2S The composite material prefabricated body is obtained through the layering sequence, and then the composite material prefabricated body is formed according to the autoclave forming process, wherein the curing temperature is 180 ℃/2h. Cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multielement nano-modified super-hybrid composite material with high conductivity and low friction coefficient.
Example 9:
the implementation process of the technical scheme of the embodiment is as follows:
(9-1) taking 100g of 50wt% E44 epoxy resin aqueous emulsion; then 100g of graphene aqueous dispersion slurry with the concentration of 5wt% and 20g of carbon nanofiber aqueous dispersion liquid with the concentration of 8wt% are taken and stirred uniformly; slowly adding the graphene and carbon nanofiber aqueous co-dispersion slurry into an epoxy resin aqueous emulsion under stirring, continuously stirring, then adding 2g of aramid pulp, and uniformly mixing the components under stirring and ultrasound simultaneously to fully disperse the aramid pulp; and (3) diluting 5.5g of triethyltetramine by 20g of deionized water, adding into the mixed solution, and fully and uniformly stirring. To obtain the water dispersion system of the super-hybrid conductive epoxy resin containing graphene, carbon nano-fiber, toughening agent and curing agent.
(9-2) drying the aqueous dispersion system of the super-hybrid epoxy resin at the spreading state of 80 ℃ to remove moisture, thus obtaining the dry super-hybrid epoxy resin. And (3) carrying out compression molding on the dry super-hybrid epoxy resin, and curing at 150 ℃/2h and 180/2h to obtain the epoxy resin casting body with good conductivity and toughness.
(9-3) the aramid pulp in (9-1) can also be changed into polyimide nano fibers, nylon nano fibers, PAN conductive nano fibers or nylon micro fibers, the addition amount is 1g or 5g, a water dispersion system of graphene, carbon nano fiber conductive modified and organic nano fiber toughened super-hybrid conductive epoxy resin with high conductivity and high toughness is obtained, and after moisture is removed and mould pressing solidification is carried out, a conductive casting body with excellent performance can be obtained.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The super-hybrid conductive resin is characterized by comprising an aqueous liquid dispersion system consisting of a resin microsphere emulsion, a curing agent and a carbon nano material aqueous dispersion liquid, or a water-free resin obtained by removing water from the aqueous liquid dispersion system; wherein, in the compositions without water in the super-hybrid conductive resin, the total content of the carbon nano-materials is 1 to 25 weight percent, and the content of the resin microspheres and the curing agent is 50 to 99 weight percent.
2. The super-hybrid conductive resin according to claim 1, wherein the carbon nanomaterial is one of carbon nanotubes, graphene, carbon black, carbon nanofibers, metal-coated carbon nanotubes, metal-coated graphene, metal-coated carbon nanofibers, or an intercompatible material between them; wherein, in each composition excluding water in the super-hybrid conductive resin, the total content of the carbon nano material is 3-20 wt%.
3. The super-hybrid conductive resin according to claim 1, wherein the resin microsphere emulsion is an aqueous epoxy resin emulsion or an aqueous bismaleimide resin emulsion, and the epoxy resin used in the aqueous epoxy resin emulsion has an average epoxy value of 0.30 to 0.80mol/100 g.
4. The super-hybrid conductive resin according to claim 3, wherein the epoxy resin used in the aqueous epoxy resin emulsion is one of E54, E51, F51, AG80, F44, E44 or their mutual coordination compounds.
5. A super-hybrid conductive resin according to claim 1, wherein the water content of the super-hybrid resin of the aqueous liquid dispersion is 55 to 90wt%.
6. A super-hybrid conductive resin according to claim 1, wherein said curing agent is a micropowder of a latent curing agent that is poorly soluble in water, wherein said micropowder has an average particle size of not more than 10 μm.
7. The super-hybrid conductive resin of claim 1, wherein the super-hybrid conductive resin in the water-free resin forming the aqueous liquid dispersion system or after the water removal of the aqueous liquid dispersion system further comprises micro-nano particles, the micro-nano particles being present in an amount of 0 to 50wt%; the micro-nano particles are one of silver nanowires, silver nanosheets, polytetrafluoroethylene particles, magnetic nanoparticles, piezoelectric nanoparticles, organic micro-nano fibers and toughening agent particles or an intercompatible substance of the silver nanowires, the silver nanosheets, the polytetrafluoroethylene particles, the magnetic nanoparticles, the piezoelectric nanoparticles, the organic micro-nano fibers and the toughening agent particles, and the average particle size of the toughening agent particles is not more than 20 microns.
8. A super-hybrid conductive resin prepreg, which is obtained by dispersing an aqueous liquid system of the super-hybrid conductive resin according to any one of claims 1 to 7 onto unidirectional continuous fibers or continuous fiber fabrics through brushing, dipping, rolling and spraying, and then drying or naturally airing, rolling and packaging.
9. A super-hybrid composite material, characterized in that it is prepared from a super-hybrid electrically conductive resin according to any of the preceding claims 1 to 7 or from a super-hybrid electrically conductive resin prepreg according to claim 8.
10. A method of preparing a super-hybrid composite, comprising the steps of:
adding deionized water into the resin microsphere emulsion, and uniformly stirring to obtain diluted resin microsphere aqueous emulsion;
adding deionized water into the carbon nano-material aqueous dispersion liquid, and uniformly stirring to obtain diluted carbon nano-material aqueous dispersion liquid;
slowly adding the diluted aqueous dispersion liquid of the carbon nano-material into the diluted aqueous emulsion of the resin microspheres, and uniformly mixing to obtain a mixed liquid;
adding a curing agent into the mixed solution, and fully and uniformly stirring to obtain a water dispersion system of the super-hybrid conductive resin;
preparing the aqueous dispersion system of the super-hybrid conductive resin into a carbon fiber prepreg of the super-hybrid conductive resin according to a prepreg forming process;
laying the carbon fiber prepreg of the super-hybrid conductive resin to obtain a prefabricated body;
and forming the prefabricated body obtained by laying the layers according to a composite material forming process to obtain the super-hybrid composite material.
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