CN115558238B - 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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- 229920005989 resin Polymers 0.000 title claims abstract description 169
- 239000011347 resin Substances 0.000 title claims abstract description 169
- 239000002131 composite material Substances 0.000 title claims abstract description 145
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- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 title abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 166
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- 239000002086 nanomaterial Substances 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
- 239000003822 epoxy resin Substances 0.000 claims description 77
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Classifications
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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Abstract
The invention relates to a super-hybrid conductive resin, prepreg, composite material and a preparation method of the material. The various hybrid 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 mutual fusion of the components is achieved, and the preparation of the low-porosity composite material is satisfied. The carbon nano material in the resin system can achieve high content and high uniformity dispersion, 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 high conductivity and excellent lightning strike resistance which can not be reached by the conventional conductive modified resin.
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 materials in the fields of aerospace and the like. However, the conductivity of the composite material is poor, and lightning current in the lightning stroke process is difficult to dredge, so that the lightning stroke damage problem is caused, the flight safety of an airplane is influenced by the lightning stroke damage, and the normal operation of the wind turbine blade is influenced. Damage to the composite material caused by lightning strike includes delamination, fiber breakage, fiber blowing perforation, etc., which causes a substantial reduction in the bending, compression, etc. properties of the composite material. At present, the lightning protection method of the composite material generally adopts a method of paving a metal net and a metal coating on the surface, however, the method significantly increases the weight of the composite material, for example, the total weight of the copper net paved in a 2A area and the resin attached on the surface is more than 150g/m 2.
In recent years, development of composite materials having high lightning strike resistance and high mechanical properties per se has become another important direction, and a general method is to conduct modification on the composite materials so as to improve the conductivity of the composite materials per se, particularly in the thickness direction. In addition, the conductivity of the composite material is improved, and the composite material can be used for lightning protection application, and can also be used for improving electromagnetic shielding performance of the composite material, realizing piezoelectric modification of the composite material, realizing antistatic performance of the composite material and the like.
The conductivity of the composite is often improved by adding conductive fillers to the composite. Among the conductive fillers, carbon-based materials have become the first choice for modified materials because of their higher conductivity and lower density. The main method of adding the carbon-based nanomaterial to the composite material may include: (1) Directly dispersing the carbon nano material in resin, and then preparing corresponding prepreg; (2) Growing a carbon nanomaterial on the surface of a carbon fiber to form a hybrid structure; (3) The carbon-based material is prepared as a conductive thin layer and then intercalated between the composite layers in the form of intercalation. The conductivity of the composite material can be improved to a certain extent by various methods, and the thickness of the composite material is typically 0.1-0.7S/cm in conductivity, and the lightning damage resistance is improved to a certain extent, which is shown by the reduction of the damage area.
However, the prior art has a number of disadvantages. 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 resin and bismaleimide resin, and it is more difficult to achieve uniform dispersion at a high concentration; secondly, when the addition amount is higher, the viscosity of the resin dispersion system can be greatly increased along with the increase of the dispersion amount, when the dispersion amount is higher, if no organic solvent is added, the related process of the composite material can hardly be carried out, for example, the organic solvent is added, the problem of environmental pollution and the problem of porosity are brought, and the porosity of the composite material with the addition amount of the high carbon nano tube reaches 1-4 percent (Composites SCIENCE AND Technology,222 (2022) 109369); third, the conductivity of the modified composite is still low, and when the addition amount is low, the conductivity of the composite system with high conductivity is hardly improved, generally not more than 0.15S/cm, and when the addition amount is high, generally not more than 0.7S/cm. And when the content of the carbon nano material is low, the modified composite material is difficult to play an effective lightning-proof role. For the method of growing and hybridization of carbon nanotubes to the fiber surface and for the composite material of carbon nanotube film, and bucky paper intercalation, the conductivity of each system in the literature is not more than 0.8S/cm, because the conductivity is limited by the conductive contact of different layers and the conductive contact between intercalation and layers. In addition, the method of growing carbon nanotubes onto fibers has problems of difficulty in preparation and deterioration of fiber properties; the carbon nanotube film intercalated composite material causes a problem of significant degradation of interlayer performance.
Therefore, the technical problems to be solved include: (1) How to realize the high-content good dispersion of the carbon nano material; (2) How to realize higher conductivity of the composite material when the content of the carbon nanomaterial is the same, namely how to realize effective conductive connection of the carbon nanomaterial; (3) The preparation technology problem of the prepreg and the composite material is solved when the content of the carbon nano material is high, so that the composite material with low porosity and high performance is obtained; (5) How to avoid the environmental pollution problem in the material preparation process.
Disclosure of Invention
The invention mainly aims at the problems and provides a preparation method of super hybrid conductive resin, prepreg, composite material and material, which aims at realizing low porosity and high conductivity of the conductive nano modified composite material and meeting the manufacturability requirement of the composite material, thereby meeting the requirements of a resin system and a prepreg system for resisting lightning damage or other functional composite material requirements.
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 of carbon nanomaterial, or a non-aqueous resin after water removal of 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 1-25wt%, and the content of the resin microsphere and the curing agent is 50-99wt%.
Further, the carbon nanomaterial is one or an inter-ligand of carbon nanotubes, graphene, carbon black, carbon nanofibers, metal-plated carbon nanotubes, metal-plated graphene and metal-plated carbon nanofibers; wherein, the total content of the carbon nano material in each component excluding water in the super hybrid conductive resin is 3-20wt%.
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 interaction between the two.
Further, the water content of the superhybrid resin of the aqueous liquid dispersion is 55 to 90wt%.
Further, the curing agent is ultrafine powder of a water-insoluble latent curing agent, and the average particle diameter of the curing agent particles is not more than 10 μm.
Further, the super hybrid conductive resin in the non-aqueous resin which forms the aqueous liquid dispersion system or is dehydrated by the aqueous liquid dispersion system further comprises micro-nano particles, and the content of the micro-nano particles is 0-50wt%; wherein the micro-nano particles are one of silver nanowires, silver nano sheets, polytetrafluoroethylene particles, magnetic nano particles, piezoelectric nano particles, organic micro-nano fibers and toughening agent particles or an interaction object between the two, and the average particle size of the toughening agent particles is not more than 20 mu m.
In order to achieve the above purpose, the invention provides the super-hybrid conductive resin prepreg, which is obtained by dispersing an aqueous liquid system of the super-hybrid conductive resin on unidirectional continuous fibers or continuous fiber fabrics through brushing, dipping, roller coating and spraying, and then drying or naturally airing, and then winding and packaging.
To achieve the above object, the present invention provides a super hybrid composite material prepared from the super hybrid conductive resin or from 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 aqueous dispersion liquid of the carbon nano material, and uniformly stirring to obtain diluted aqueous dispersion liquid of the carbon nano material;
slowly adding the diluted carbon nano material aqueous dispersion liquid into the diluted resin microsphere aqueous emulsion, and uniformly mixing to obtain a mixed liquid;
adding a curing agent into the mixed solution, and fully and uniformly stirring to obtain an aqueous dispersion system of the super hybrid conductive resin;
preparing the aqueous dispersion system of the super-hybrid conductive resin into carbon fiber prepreg of the super-hybrid conductive resin according to a prepreg molding process;
Laying the carbon fiber prepreg of the super-hybrid conductive resin to obtain a preform;
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 an aqueous dispersion system and the characteristics of high dispersion and easy blending of the aqueous nano dispersion system, a resin system, a conductive medium and a functional micro-nano material comprising a toughening agent are mixed together in a dispersion form with uniform micro-nano dispersion degree to form a super-hybrid conductive resin dispersion system with low viscosity capable of being brushed, rolled, immersed and sprayed, and the nano-scale dispersibility of the original system is not influenced by using an organic solvent with environmental pollution; by controlling parameters such as the type and content of epoxy resin, the content of conductive nano-particles, the water content, the characteristic of curing agent 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 diagram showing the composition of the super hybrid conductive resin of the present invention.
Fig. 2 is a schematic diagram showing the composition of the super hybrid conductive resin prepreg of the present invention.
FIG. 3 is a schematic diagram of the composition of the super hybrid composite of the present invention.
FIG. 4 is an SEM image of a cured product 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 surface-protective, super-hybrid conductive resin (7 wt% CNT) according to an embodiment of the present invention after a lightning strike in the simulated 2A region.
FIG. 6 is a photograph of lightning damage characteristics of a simulated 2A region of a carbon fiber composite of a CNT modified resin prepared by a conventional solution dispersion method [ (a) 5wt% of CNT and (b) 7wt% of CNT ] according to an embodiment of the present invention.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The concept of composite material refers to a material which cannot meet the use requirement and needs to be compounded by two or more materials to form another material which can meet the requirements of people, namely, a composite material.
Composite materials are of many kinds and generally consist of reinforcing materials and matrix materials; wherein the base 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:
Adding deionized water into the 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 aqueous dispersion liquid of the carbon nano material, and uniformly stirring to obtain diluted aqueous dispersion liquid of the carbon nano material; the carbon nanomaterial for preparing the carbon nanomaterial aqueous dispersion liquid is one of carbon nanotubes, graphene, carbon black, carbon nanofibers, metal-plated carbon nanotubes, metal-plated graphene and metal-plated carbon nanofibers or an interaction object between the carbon nanotubes and the graphene, the carbon black, the carbon nanofibers and the metal-plated carbon nanofibers.
And thirdly, slowly adding the diluted carbon nano material aqueous dispersion liquid into the diluted resin microsphere aqueous emulsion, and uniformly mixing to obtain a mixed liquid.
Fourthly, adding a curing agent into the mixed solution, and fully and uniformly stirring to obtain an aqueous dispersion system of the super-hybrid conductive resin; the curing agent is superfine powder of water-insoluble latent curing agent, and the average particle size of the curing agent particles is not more than 10 mu m.
In the steps from the first step to the fourth step of the embodiment, the obtained water dispersion system of the super hybrid conductive resin does not contain water, the content of the carbon nano material is 1 to 25 weight percent, and the content of the epoxy resin microsphere and the curing agent thereof is 50 to 99 weight percent; in some preferred embodiments, the material for preparing the water dispersion system of the super hybrid conductive resin may be added with a conglomeration of other nano materials, for example, micro-nano particles with the content of 0-50wt%, wherein the micro-nano particles can be silver nanowires, silver nano sheets, polytetrafluoroethylene particles, magnetic nano particles, piezoelectric nano particles, organic micro-nano fibers, toughening agent particles and the like to improve the performance, and the average particle size of the toughening agent particles is not more than 20 μm.
And fifthly, preparing the water dispersion system of the super-hybrid conductive resin prepared in the fourth step into the carbon fiber prepreg of the super-hybrid conductive resin according to a prepreg molding 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 brushing, dipping, roller coating, spraying and other methods, and then is dried or naturally dried, rolled and packaged to obtain corresponding prepreg; it should be noted that the process for preparing the prepreg is not limited thereto.
And sixthly, layering the carbon fiber prepreg of the super-hybrid conductive resin to obtain a preform.
And seventh, forming the prefabricated body obtained by layering according to a composite material forming process to obtain the super hybrid composite material.
In the step, the carbon fiber prepreg is cut into a plurality of pieces, the layers are laid according to the laying sequence, a composite material preform is obtained, the composite material preform is molded according to an autoclave molding process, and the composite material is taken out after solidification molding and cooling, so that the composite material modified by the high-content carbon nano tube is obtained.
The embodiment also provides a super hybrid conductive resin which can be used as a raw material with high conductivity and excellent mechanical properties, and the conductivity of a resin cured product can reach 0.1-1S/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 nanomaterial (carbon nanomaterial 2 and water 4), or a non-aqueous resin after the aqueous liquid dispersion system is dehydrated; wherein, in each composition of the super hybrid conductive resin excluding water, the content of the carbon nanomaterial in the carbon nanomaterial aqueous dispersion is 1-25wt%, and the content of the resin microspheres and the curing agent in the resin microsphere emulsion is 50-99wt%; the aqueous liquid dispersion or the non-aqueous resin after the water removal of the aqueous liquid dispersion may contain the micro-nano particles 3, and the micro-nano particles 3 may be contained in an amount of 0 to 50wt% in the case of containing the micro-nano particles 3.
In this embodiment, when the carbon nanomaterial in the aqueous dispersion liquid of the carbon nanomaterial is one of carbon nanotube, graphene, carbon black, carbon nanofiber, metal-plated carbon nanotube, metal-plated graphene, metal-plated carbon nanofiber, or an interaction between them, the total content of the carbon nanomaterial in the composition excluding water in the resin is 3 to 20wt%.
In this example, the water content of the superhybrid 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 super-hybrid conductive resin prepreg and super-hybrid composite material; the non-aqueous resin after water removal of the aqueous liquid dispersion system composed of the resin microsphere emulsion 1, the curing agent 5 and the aqueous dispersion liquid (the carbon nanomaterial 2 and the water 4) of the carbon nanomaterial can be also used for preparing super hybrid composite materials and other purposes.
The present embodiment also provides a super hybrid conductive resin prepreg prepared from the aqueous dispersion system (water-containing) of the super hybrid conductive resin prepared in the above embodiment, and fig. 2 is a schematic diagram of the composition of the prepared super hybrid conductive resin prepreg, wherein the prepreg comprises resin microspheres 1-1 or microdroplets, carbon nanomaterial 2, micro-nano particles 3 or tougheners, continuous reinforcing fibers 6 and curing agents 5.
The present embodiment also provides a super hybrid composite material, which is prepared from the super hybrid conductive resin (which may contain water or may not contain water) prepared in the above embodiment or the super hybrid conductive resin prepreg prepared in the above manner, and fig. 3 is a schematic composition diagram of the super hybrid composite material, where the super hybrid composite material includes a cured resin matrix 1-2, a carbon nanomaterial 2, micro-nano particles 3 or a toughening agent, and continuous reinforcing fibers 6.
1) The super hybrid resin prepared by the method can solve the problem of dispersion of the carbon nano material in the high-viscosity resin:
The conductive carbon nanomaterial and the resin emulsion are subjected to homogeneous phase blending to form a liquid phase, so that the conductive carbon nanomaterial is well dispersed, almost no agglomeration of the carbon nanomaterial exists, and the mass fraction of the dispersion of the carbon nanomaterial in the resin after moisture is removed can reach more than 50 wt%. A typical carbon nanotube dispersion picture after curing the resin is shown in fig. 4. As can be seen from fig. 4, this embodiment achieves a high content good dispersion of the carbon nanomaterial.
2) The super hybrid composite material prepared by the 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 function of the carbon nano material:
It should be noted that, in the conventional hybrid resin, gradual aggregation is unavoidable when the content of the carbon nanomaterial is high, the conductivity of the system is gradually deteriorated, and rapid aggregation failure is easy to occur when the solvent exists, so that the finally prepared casting body is not conductive.
The super hybrid conductive resin in the embodiment is a conglomerate of dispersed resin nanoparticles, carbon nanomaterial and other nanomaterial, and the resin nanoparticles have the functions of highly dispersing and distributing templates to the carbon nanomaterial and prevent self-aggregation of the carbon nanomaterial. Therefore, the percolation 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 the present embodiment is used to prepare a composite material, the weak interaction and mutual separation between the carbon nanomaterial and the resin improves the conductive overlap between the carbon nanotubes, which makes the final composite material have high conductivity. The thickness and conductivity of several typical composite materials prepared by using the super hybrid conductive resin are shown in table 1, and corresponding comparison is given, and it can be seen that the conductivity of the composite materials is far higher than that of the composite materials with high carbon nanotube content obtained by the conventional technology and the composite materials obtained by other carbon nanotube modification technologies under the same carbon nanotube content.
TABLE 1 conductivity of composite materials prepared with super hybrid conductive resins
And 1, two carbon nano tubes and graphene hybridized carbon fiber reinforced epoxy resin matrix composite materials are injected, and self-made.
And (2) injection: 2wt% of single-wall carbon nano tube modified resin-based carbon fiber composite material.
And (3) injection: the thickness of the interlayer full-insert layer reaches 150 mu m of carbon fiber composite material of the base paper.
And (4) injection: carbon fiber reinforced composites with carbon nanotubes grown in situ.
And (5) injection: 3wt% of a carbon black modified resin-based carbon fiber composite material with enhanced conductivity.
And (6) injection: composite materials obtained from conventional high carbon nanotube content resins (Composites SCIENCE AND Technology,222 (2022) 109369).
3) The super hybrid composite material prepared by the method can solve the preparation process problems of the prepreg and the composite material when the content of the carbon nano material is high:
The conventional resin with high carbon nanomaterial content has very high viscosity, a large amount of organic solvent is needed to be added for reducing the viscosity for preparing the composite material, so that the environment is polluted, and after the organic solvent is added, the carbon nanomaterial is extremely easy to quickly 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 in the composite material is improved.
The super hybrid conductive resin of the embodiment is a system of co-dispersing resin nano-microspheres and carbon nano-materials, wherein the carbon nano-materials are wrapped around the resin nano-microspheres, the resin nano-microspheres are broken and permeate in gaps and fiber layers of the nano-materials under the forming pressure and temperature, and the curing agent is diffused in the resin, so that the good low-pore composite material is finally formed. Microsphere emulsions prepared with epoxy resins having a relatively high epoxy value with a relatively low viscosity are advantageous for such penetration curing, so that in a preferred embodiment the average epoxy value of the epoxy resin used to prepare the emulsion should have a lower limit of 0.30 or higher, but the use of epoxy resins having a too high epoxy value with too low a viscosity is detrimental to the stability of the superhybrid resin system, and so that the average epoxy value of the preferred embodiment should have an upper limit of 0.80 or lower, so that the emulsion has a relatively good penetration under curing heat conditions. Typical epoxy resins such as E54, E51, AG80, F51, F44, E44 and the like and their mixed resins are preferable, but the low epoxy resin with high viscosity such as CYD-014 should not be used singly in the present resin system, but can be used in the present system by being matched with the high epoxy resin such as AG80 to be in an appropriate epoxy value range.
When applied to the preparation of prepregs, the aqueous dispersion of the super hybrid conductive resin is used in the embodiment, and the water content in the dispersion is 55-90 wt% so as to achieve good manufacturability and avoid aggregation in the system. When the resin is applied to the preparation of a composite material, the mass fraction of the carbon nano material in the resin of the embodiment is still lower than 20wt% (excluding water), and when the mass fraction of the carbon nano material is lower than 15wt%, the resin can have good manufacturability, the requirements of the volume fraction control of the composite material fiber and the conventional autoclave curing process are met, the prepared composite material is difficult to observe pores under a metallographic optical microscope, the prepared composite material has very low porosity, and the porosity obtained through testing and comparison are shown in table 2. In order to achieve good lightning protection performance, the mass fraction of the carbon nanomaterial should not be lower than 3wt%.
TABLE 2 porosity of composite materials prepared with super hybrid conductive resins
Note 1 composite materials obtained from conventional high carbon nanotube content resins (Composites SCIENCE AND Technology,222 (2022) 109369).
4) The super hybrid composite material prepared by the method can solve the problem of environmental pollution in the material preparation process:
Conventional dispersing of high concentration dispersed carbon nanomaterial into high viscosity resin often requires dilution and viscosity reduction with organic solvents, typically acetone, N-dimethylformamide, N-methylpyrrolidone are common solvents, but the presence of organic solvents, good compatibility of organic solvents and epoxy resins makes 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, and the compatibility of water and resin phases is poor, and the aqueous phase and nanophase are separated from each other, so that the moisture in the aqueous phase and nanophase is easily removed to become dry resin and prepreg.
5) The super hybrid composite material prepared by the method has other effects:
the composite material prepared by the super hybrid conductive resin has good mechanical properties, the bending strength of the twill T300-level carbon fiber fabric composite material reaches 730MPa, the interlayer shearing strength reaches 72MPa, the interlayer shearing strength of the unidirectional T800-level carbon fiber composite material reaches 105-110 MPa, and the bending strength is improved to different degrees compared with that of a control composite material.
The composite material body prepared by the super hybrid conductive resin of the embodiment has very outstanding lightning protection performance, and only a small amount of fibers on the surface of the lightning stroke in the area 2A are simulated to break, as shown in fig. 5, the C-scan diagram of fig. 5 shows that no internal layering exists after the lightning stroke, and only ablation of the surface resin is caused, so that the possibility is brought to material repair; the photo of the comparative traditional solvent assisted prepared carbon nanotube hybrid resin matrix composite after 2A area lightning strike simulation is shown in FIG. 6, the fiber in the damage center is broken in a larger area, and the first layer and the second layer are layered in a large area.
After lightning stroke in the area 2A is simulated, the retention rate of compressive strength and the retention rate of compressive modulus of the typical composite material without surface protection reach 100%, the retention rate of bending strength of a lightning stroke damage center (100 mm in 100mm area) of the typical composite material without surface protection reaches 93-95%, the excellent lightning stroke resistance is shown, the weight gain is only 45g/m 2, and the weight gain is far lower than the weight gain of more than 150g/m 2 in the prior art.
A method of preparing a super hybrid composite material according to the present invention will be 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% of E51 epoxy resin aqueous emulsion, adding 50mL of deionized water, and uniformly stirring; then 100g of carbon nano tube aqueous dispersion slurry with the concentration of 5wt percent 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 at the same time, and uniformly mixing the two; 16.6g of 4,4' -diaminodiphenyl sulfone superfine powder with the average particle diameter of 3.5 mu m is taken and added into the mixed solution, and the mixed solution is 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 of the dispersion system is 77.6 weight percent.
(1-2) Uniformly and double-sided coating the aqueous dispersion system of the super hybrid epoxy resin on unidirectional T800 carbon fiber fabric by adopting a brushing method, enabling the resin content to be 33wt%, standing for two days to be completely dried in an environment with humidity lower than 30%, and then drying at 80 ℃ for 1h to obtain the T800 carbon fiber prepreg of the super hybrid epoxy resin.
(1-3) Cutting the T800 carbon fiber prepreg into 16 sheets of 300 mm-300 mm prepreg, layering the sheets in one direction according to [0 degree ] 16 to obtain a composite material preform, and shaping the composite material preform according to an autoclave shaping process, wherein the curing temperature is 180 ℃. Cooling to below 60 ℃ after molding, and taking out the composite material to obtain the composite material modified by the high-content carbon nano tube.
(1-4) The 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 carbon nanomaterial in the final resin dispersion system accounts for about 10.2wt% of the dry resin.
The high-content carbon nanotube modified composite material obtained by the embodiment has good conductivity and lightning stroke resistance, the thickness of the composite material reaches 1.35S/cm to the conductivity, the thickness reaches about 10 times of the conventional non-modified high-conductivity carbon fiber composite material, or 1000 times of the conventional low-conductivity composite material, the surface of the composite material is only ablated and damaged in a small area after being subjected to 2A area lightning stroke, and obvious layering damage is not visible.
Example 2:
The implementation process of the technical scheme of the embodiment is as follows:
(2-1) taking 100g of 50wt% of F51 and E51 matched epoxy resin aqueous emulsion, 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% epoxy resin aqueous emulsion; then 25g of carbon nano tube aqueous dispersion slurry with the concentration of 5wt% and 25g of graphene aqueous dispersion slurry with the concentration of 5wt% are taken, 50mL of deionized water is added, and the mixture is stirred uniformly; slowly adding the diluted carbon nano tube and graphene aqueous co-dispersion slurry into the diluted epoxy resin aqueous emulsion, continuously stirring at the same time, and uniformly mixing the two; adding 10g of ultrafine particles of phenolphthalein modified polyether-ether-ketone (PEK-C) with average particle diameter of 7 μm into the mixed solution, and stirring for 10 minutes while carrying out ultrasonic oscillation to uniformly disperse the whole; then 16.6g of 4,4' -diamino diphenyl sulfone superfine powder with the average grain diameter of 2.5 mu m is taken and added into the mixed solution to be fully and uniformly stirred. Obtaining the water dispersion system of the super-hybrid conductive epoxy resin 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 and double-sided coating the aqueous dispersion system of the super-hybrid epoxy resin on the CF3031 twill woven carbon fiber fabric by adopting a brushing method, so that the resin content in the prepreg is 42wt%, and the prepreg is dried at 80 ℃ for 1h to be basically dried, and then is dried at 100 ℃ in vacuum for 1h to obtain the CF3031 carbon fiber fabric prepreg of the super-hybrid epoxy resin.
(2-3) Cutting the prepreg into pieces of 300mm, 8 pieces of prepreg according to the layering sequence of [45 degrees, 0 degrees, 45 degrees, 0 degrees and 45 degrees ], and then forming the prepreg by an 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 composite material modified by the high-content carbon nano tube.
(2-4) The GW3031 twill weave may be used as the above (2-2), or the amount of the aqueous slurry of graphene and carbon nanotubes may be 30g and 70g, or 20g and 80g, respectively.
(2-5) The above (2-2) may also use 5wt% aqueous slurry of silver-plated graphene and silver-plated carbon nanotubes in amounts of 10g and 60g, or 20g and 50g, respectively.
The high-content carbon nanotube modified composite material 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) taking 100g of 50wt% of an aqueous epoxy resin emulsion prepared by mixing AG80 and F44, wherein the mixing ratio of the two is 1:1; then 100g of carbon nano tube aqueous dispersion slurry with the concentration of 5wt% and 50g of silver plating carbon nano tube aqueous dispersion slurry or silver plating graphene aqueous dispersion slurry or carbon nano fiber aqueous dispersion slurry with the concentration of 5wt% are 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 at the same time, and uniformly mixing the two; then 10g of 10wt% PZT nanowire water dispersion slurry is added; 7g of dicyandiamide superfine powder is taken and added into the mixed solution to be fully and uniformly stirred. An aqueous dispersion of a super hybrid epoxy resin having a carbon nanomaterial content of 9.3wt% and containing a plurality of particles such as carbon nanotubes, PZT, and a curing agent was obtained.
(3-2) Uniformly coating the aqueous dispersion system of the super-hybrid epoxy resin on a unidirectional T800 carbon fiber fabric on both sides by adopting a roller coating method, enabling the content of the dried resin to be 37wt%, directly drying the resin by a 120-DEG oven with the length of 10 meters after roller coating, and then rolling the resin to obtain the T800 carbon fiber prepreg of the super-hybrid epoxy resin.
(3-3) Cutting the prepreg into 16 sheets of 300mm prepreg, obtaining a composite material preform according to the layering sequence of [45 degrees, 0 degrees, -45 degrees, 90 degrees ] 2S, and then forming according to an 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 multifunctional modified composite material with high carbon nano tubes.
Example 4:
The implementation process of the technical scheme of the embodiment is as follows:
(4-1) taking 100g of 50wt% of E44 epoxy resin aqueous emulsion; taking 100g of graphene aqueous dispersion slurry with the concentration of 5wt%, 50g of silver-plated carbon nano tube aqueous dispersion slurry with the concentration of 5wt%, and 20g of carbon nano fiber aqueous dispersion liquid with the concentration of 8wt% and uniformly stirring; slowly adding silver-plated carbon nano tube, graphene and carbon nano fiber aqueous co-dispersion slurry into epoxy resin aqueous emulsion under stirring, continuously stirring, then adding 10g of thermoplastic polyimide superfine powder, and uniformly mixing the components under stirring and ultrasonic treatment at the same time, wherein the average particle size is 8.5 mu m or 2.2 mu m; 13.8g of 4,4' -diaminodiphenyl sulfone superfine powder with the average particle size of 8.2 mu m is taken and added into the mixed solution, and the mixed solution is fully and uniformly stirred. Obtaining 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 of the above super hybrid epoxy resin in a state of being spread at 80℃to remove water, to obtain a 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% of bismaleimide resin aqueous emulsion; 150g of carbon nano tube aqueous dispersion slurry with the concentration of 5wt percent is taken, 50g of fluorescent nano particles with the concentration of 10wt percent is taken, 2g of carbon black nano particles are taken, 50mL of deionized water is added, and stirring is carried out uniformly under ultrasound; slowly adding diluted carbon nano tube, carbon black and fluorescent nano particle aqueous dispersion slurry into diluted bismaleimide resin aqueous emulsion, continuously stirring, and uniformly mixing the two; adding 5gPEK-C powder into the dispersion liquid, and uniformly mixing under high-speed stirring to obtain an aqueous dispersion system of the super hybrid bismaleimide resin containing carbon nano tubes, carbon black, fluorescent nano particles, PEK-C and other solid particles.
(5-2) Uniformly and double-sided coating the aqueous dispersion system of the super hybrid bismaleimide resin on a unidirectional ZT7H carbon fiber fabric (700 grade) by adopting a brushing method, wherein the single-layer thickness is 0.125mm, the resin content is 34wt%, and the super hybrid bismaleimide resin is dried at 60 ℃ until the super hybrid bismaleimide resin is completely dried, so that the ZT7H unidirectional carbon fiber prepreg of the super hybrid bismaleimide resin is obtained.
And (5-3) cutting 16 carbon fiber prepregs, wherein the size of the carbon fiber prepregs is 300mm, and the composite material prefabricated body is obtained according to the layering sequence of [45 degrees, 0 degrees, -45 degrees, 90 degrees ] 2S, and then the composite material prefabricated body is molded according to an autoclave molding process, and the curing temperature is 160 ℃/2h+200 ℃/5h. Cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multi-element nano modified composite material with high carbon nano tube and 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% of E51 epoxy resin aqueous emulsion, adding 50mL of deionized water for dilution, and uniformly stirring; then 50g of carbon nano tube aqueous dispersion slurry with the concentration of 5wt percent is taken, 50g of silver plating carbon nano fiber aqueous dispersion slurry with the concentration of 15wt percent is taken, 20g of graphene aqueous dispersion slurry with the concentration of 5wt percent is taken, 30mL of deionized water is added, and ultrasonic stirring is carried out uniformly; slowly adding the multi-element nano water-based dispersion slurry into diluted epoxy resin water-based emulsion, continuously stirring at the same time, and uniformly mixing the two; 20g of 4,4' -diaminodiphenyl sulfone superfine powder with the average particle size of 3 mu m is taken and added into the mixed solution, and the mixed solution is fully and uniformly stirred. Obtaining the aqueous dispersion system of the super-hybrid conductive epoxy resin co-hybrid by the carbon nano tube, the graphene and the silver-plated carbon nano fiber.
(6-2) Drying the aqueous dispersion of the super hybrid epoxy resin (6-1) at the temperature of 80 ℃ for spreading to remove water, so as to obtain dry super hybrid epoxy resin which can be used for preparing high-conductivity resin blocks;
(6-3) coating the super hybrid epoxy resin (6-1) on a CCF800H carbon fiber unidirectional fabric to make the resin content be 38wt%, and then drying the fabric by a heating plate to obtain a dry prepreg; rolling and flattening the prepreg for standby;
And (6-4) cutting 16 carbon fiber prepregs, wherein the size of the carbon fiber prepregs is 300mm, and the composite material prefabricated body is obtained according to the layering sequence of [45 degrees, 0 degrees, -45 degrees, 90 degrees ] 2S, and then the composite material prefabricated body is molded according to an autoclave molding process, and the curing temperature is 180 ℃/2h. Cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multi-element 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 with high carbon nanotube content and 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 deionized water into the mixture to dilute the mixture by 50mL, and uniformly stirring the mixture; taking 50g of carbon nano tube aqueous dispersion slurry with the concentration of 5wt%, taking 50g of PZT nano particle aqueous dispersion slurry with the concentration of 15wt%, taking 20g of graphene aqueous dispersion slurry with the concentration of 5wt%, adding 30mL of deionized water, and uniformly stirring by ultrasound; slowly adding the multi-element nano water-based dispersion slurry into diluted epoxy resin water-based emulsion, continuously stirring at the same time, and uniformly mixing the two; 13g of 4,4' -diaminodiphenyl methane ultrafine powder is taken and added into the mixed solution, and the mixed solution is fully and uniformly stirred. And obtaining an aqueous dispersion system of the super-hybrid epoxy resin obtained by co-mixing the carbon nano tube, the graphene and the PZT particles.
(7-2) Drying the aqueous dispersion of the super-hybrid epoxy resin (7-1) at the temperature of 80 ℃ for spreading to remove water, so as to obtain 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 make the resin content be 38wt%, and then drying the fabric by a heating plate to obtain a dry prepreg; rolling and flattening the prepreg for standby;
(7-4) cutting 16 sheets of the S4 high-strength glass fiber prepreg, wherein the size of the sheet is 300mm, and the composite material preform is obtained according to the layering sequence of [45 DEG, 0 DEG, -45 DEG, 90 DEG and 2S, and then the composite material preform is molded according to an autoclave molding process, and the curing temperature is 120 ℃/2h. Cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multi-element nano modified composite material with high carbon nano tube and graphene and PZT particles.
(7-5) The PZT particles can be replaced with magnetic nano particles with the same or three times of the usage amount, so that the S4 high-strength glass fiber composite material with high carbon nano tubes, grapheme and magnetic nano particles in a multi-element nano modification way 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; then 50g of carbon nano tube aqueous dispersion slurry with the concentration of 5wt percent is taken, 50g of silver plating carbon nano tube aqueous dispersion slurry with the concentration of 5wt percent is diluted by 50mL of water and stirred uniformly; slowly adding silver-plated carbon nano tubes and carbon nano tube aqueous co-dispersion slurry into epoxy resin aqueous emulsion under stirring, continuously stirring, then adding 50g or 100g of 60wt% polytetrafluoroethylene particle dispersion emulsion with an average particle size of 1 mu m, and uniformly mixing the components under stirring and ultrasonic treatment; 15.8g of 4,4' -diaminodiphenyl sulfone superfine powder with an average particle size of 2.3 mu m is taken and added into the mixed solution, and the mixed solution is fully and uniformly stirred. Obtaining the water dispersion system of the super-hybrid conductive epoxy resin containing carbon nano tubes, silver-plated carbon nano tubes, polytetrafluoroethylene particles and curing agent.
(8-2) Drying the aqueous dispersion of the above super hybrid epoxy resin in a state of being spread at 100℃to remove water, to obtain a dry polytetrafluoroethylene-containing super hybrid conductive epoxy resin.
(8-3) Molding the dry ultra-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 low friction coefficient.
(8-4) Spraying the double sides of the (8-1) super hybrid epoxy resin on a CF8010 high-strength carbon fiber plain weave fabric to make the resin content be 45wt%, and then drying the fabric by a heating plate to obtain a dry prepreg; rolling and flattening the prepreg for standby;
(8-5) cutting 16 sheets of CF8010 high-strength carbon fiber prepreg, wherein the size of the prepreg is 200mm by 200mm, obtaining a composite material preform according to the layering sequence of [45 DEG, 0 DEG, -45 DEG, 90 DEG and 2S, and then forming the composite material preform according to an autoclave forming process, and the curing temperature is 180 ℃/2h. Cooling to below 60 ℃ after molding, and taking out the composite material to obtain the multi-element 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% of E44 epoxy resin aqueous emulsion; then taking 100g of graphene aqueous dispersion slurry with the concentration of 5wt% and 20g of carbon nanofiber aqueous dispersion liquid with the concentration of 8wt% and uniformly stirring; slowly adding graphene and carbon nanofiber aqueous co-dispersion slurry into epoxy resin aqueous emulsion under stirring, continuously stirring, then adding 2g of aramid pulp, and uniformly mixing the components under stirring and ultrasonic simultaneously to fully disperse the aramid pulp; 5.5g of triethyltetramine is taken, diluted with 20g of deionized water, added into the mixed solution and fully and uniformly stirred. Obtaining the water dispersion system of the super-hybrid conductive epoxy resin containing the graphene, the carbon nanofiber, the toughening agent and the curing agent.
(9-2) Drying the aqueous dispersion of the above-mentioned super hybrid epoxy resin in a state of being spread at 80℃to remove water, thereby obtaining a 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 the above (9-1) can be changed into polyimide nanofiber or nylon nanofiber or PAN conductive nanofiber or nylon microfiber, and the addition amount is 1g or 5g, so as to obtain the aqueous dispersion system of the graphene, carbon nanofiber conductive modified and organic nanofiber toughened super-hybrid conductive epoxy resin with high conductivity and high toughness, and after removing moisture and die pressing and solidifying, the conductive casting body with excellent performance can be obtained.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that 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 scope of the invention.
Claims (9)
1. The super-hybrid conductive resin is characterized by comprising an aqueous liquid dispersion system formed by resin microsphere emulsion, a curing agent and carbon nano material aqueous dispersion liquid, or a non-aqueous resin after the aqueous liquid dispersion system is dehydrated; wherein, in each composition excluding water in the super hybrid conductive resin, the total content of the carbon nano material is 1 to 25 weight percent, and the content of the resin microsphere and the curing agent is 50 to 99 weight percent; the resin microsphere emulsion is epoxy resin aqueous emulsion or 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.
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-plated carbon nanotubes, metal-plated graphene, metal-plated carbon nanofibers, or an inter-ligand therebetween; wherein, in each composition excluding water in the super hybrid conductive resin, the total content of the carbon nanomaterial is 3-20wt%.
3. A superhybrid electrically conductive resin as claimed in claim 1, wherein the epoxy resin used in the aqueous emulsion of epoxy resin is one of E54, E51, F51, AG80, F44, E44 or an inter-ligand therebetween.
4. A superhybrid conductive resin according to claim 1, wherein the water content of the superhybrid resin of the aqueous liquid dispersion is 55 to 90wt%.
5. An ultra-hybrid conductive resin according to claim 1, wherein the curing agent is an ultra-fine powder of a water-insoluble latent curing agent, wherein the average particle diameter of the ultra-fine powder is not more than 10 μm.
6. The super hybrid conductive resin according to claim 1, wherein the super hybrid conductive resin in the non-aqueous resin constituting the aqueous liquid dispersion or the aqueous liquid dispersion after water removal further comprises micro-nano particles, the micro-nano particles being contained in an amount of 0 to 50wt%; wherein the micro-nano particles are one of silver nanowires, silver nano sheets, polytetrafluoroethylene particles, magnetic nano particles, piezoelectric nano particles, organic micro-nano fibers and toughening agent particles or an interaction object between the two, and the average particle size of the toughening agent particles is not more than 20 mu m.
7. A super hybrid conductive resin prepreg, characterized in that the prepreg is obtained by brushing, dipping, rolling and spraying an aqueous liquid system of the super hybrid conductive resin according to any one of claims 1-6 onto unidirectional continuous fibers or continuous fiber fabrics, drying or naturally airing, rolling and packaging.
8. A super hybrid composite material, characterized in that the composite material is prepared from the super hybrid conductive resin according to any one of the preceding claims 1-6 or from the super hybrid conductive resin prepreg according to claim 7.
9. A method of preparing the superhybrid composite material of claim 8, 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 aqueous dispersion liquid of the carbon nano material, and uniformly stirring to obtain diluted aqueous dispersion liquid of the carbon nano material;
slowly adding the diluted carbon nano material aqueous dispersion liquid into the diluted resin microsphere aqueous emulsion, and uniformly mixing to obtain a mixed liquid;
adding a curing agent into the mixed solution, and fully and uniformly stirring to obtain an aqueous dispersion system of the super-hybrid conductive resin;
preparing the aqueous dispersion system of the super-hybrid conductive resin into carbon fiber prepreg of the super-hybrid conductive resin according to a prepreg molding process;
layering the carbon fiber prepreg of the super-hybrid conductive resin to obtain a preform;
Forming the preform obtained by layering according to a composite material forming process to obtain the super hybrid composite material;
The resin microsphere emulsion is epoxy resin aqueous emulsion or 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.
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