CN110509629B - Carbon fiber-carbon nanotube interwoven layer composite material and preparation method thereof - Google Patents
Carbon fiber-carbon nanotube interwoven layer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon fiber-carbon nanotube interweaved layer composite material and a preparation method thereof, wherein the composite material is a three-dimensional interweaved layer structure and comprises a plurality of layers of carbon fiber unidirectional cloth which are arranged in a laminating way, carbon nanotube film narrow bands for interweaving the plurality of layers of carbon fiber unidirectional cloth together and epoxy resin filled in gaps, and in the three-dimensional interweaved layer structure, the carbon nanotube film narrow bands are penetrated in the latitudinal direction and the thickness direction, so that the plurality of layers of carbon fiber unidirectional cloth have integrity, the load transmission between the layers is more facilitated, and the conductivity in the thickness direction and the conductivity in the latitudinal direction can be improved. The carbon nanotube film is used as a continuous aggregate, so that the problems of agglomeration, uneven dispersion and the like do not exist; moreover, the carbon nanotube film is utilized to carry out three-dimensional interweaving and layering on the carbon fibers, so that the composite material becomes a whole, and the improvement on the performance is integrated; in addition, the preparation process of the composite material is simple and easy to operate, and does not involve dangerous gases such as hydrogen, methane and the like.
Description
Technical Field
The invention relates to the technical field of hybrid composite materials, in particular to a carbon fiber-carbon nanotube interwoven layer composite material and a preparation method thereof.
Background
The development of carbon fiber reinforced resin matrix Composite (CFRP) has become a mature structural material and is widely applied to the fields of aviation, aerospace, automobiles, sports and the like. Due to the surface inertness and lack of surface functional groups of the carbon fibers, the fiber/resin interface bonding strength of the CFRP is low, which limits the load transfer and affects the overall performance of the CFRP, and the epoxy resin with too low conductivity fills the gaps between the carbon fiber tows, which causes the CFRP to have low conductivity parallel to the alignment direction of the carbon fibers, which both greatly limit the application of the CFRP.
Since the discovery of Carbon Nanotubes (CNTs) in 1991, they have been widely used in the fields of supercapacitors, shape memory, high damping materials and structural materials, by virtue of their large aspect ratio structures, excellent mechanical, electrical and thermal properties, and the like. As researchers continue to explore, CNT macrosomes, such as CNT arrays, CNT films, and resin-based composites thereof, have also been shown to have excellent mechanical and functional properties.
Aiming at the problem of poor performance of a CFRP interface and an interlayer, a hybrid composite material (a composite material prepared by reinforcing the same matrix or a plurality of matrixes by two or more than two reinforcements) can be prepared in a carbon fiber/carbon nanotube hybrid mode, and the bonding performance and the interlayer performance of the CFRP interface are enhanced.
At present, the preparation method of the CNT modified continuous fiber resin-based composite material comprises the following three methods: 1. the dispersion method comprises the steps of firstly dispersing CNT powder into a resin matrix, and then compounding the resin matrix and fibers to prepare a three-phase hybrid composite material, wherein the CNT powder is easy to agglomerate to cause the problem of uneven dispersion and influence the overall performance of the composite material; 2. the CNT is used for modifying the fiber, the most common methods are a chemical vapor deposition method, an electrophoretic deposition method, a jet deposition method, a sizing agent method, a chemical grafting method and a suspension deposition method, the experimental requirement of the method is high, the operation is complex, and dangerous gases such as hydrogen, methane and the like are required; 3. the carbon nanotube aggregate reinforced continuous fiber resin-based composite material adopts a carbon nanotube aggregate which has a Z-direction puncture of a carbon nanotube forest or array perpendicular to a fiber direction and a carbon nanotube film laminated structure parallel to the fiber direction, the carbon nanotube array experiment operation is complex, the preparation process is complicated, the improvement on the performance of the composite material is only limited to the layer with the carbon nanotube aggregate, and the improvement effect on the overall performance of the composite material is weaker.
Disclosure of Invention
In view of the above, the invention provides a carbon fiber-carbon nanotube interwoven layer composite material and a preparation method thereof, which are used for solving the problems of uneven dispersion, complex preparation process, poor overall performance improvement effect and the like existing in the conventional mixing method.
Therefore, the invention provides a carbon fiber-carbon nanotube interwoven layer composite material, which comprises the following components: the carbon fiber composite material comprises a plurality of layers of carbon fiber unidirectional cloth which are arranged in a stacked manner, carbon nanotube film narrow bands which interweave the plurality of layers of carbon fiber unidirectional cloth together, and epoxy resin which is filled in gaps among the carbon fibers and the carbon nanotube film narrow bands; wherein,
the positions of the tows of each carbon fiber unidirectional cloth in the multi-layer carbon fiber unidirectional cloth correspond to each other;
the carbon nanotube film narrow band is interwoven with layers along the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth, and two ends of the carbon nanotube film narrow band are respectively adhered to the multiple layers of carbon fiber unidirectional cloth.
In a possible implementation manner, in the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, the number of carbon fiber tows between two adjacent interpenetrations of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth laminating direction is 1-3.
In a possible implementation manner, in the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, the plurality of carbon nanotube film narrow bands interweave the plurality of layers of carbon fiber unidirectional cloth together;
the carbon nanotube films are arranged in a narrow band along the extending direction of the carbon fibers.
The invention also provides a preparation method of the carbon fiber-carbon nanotube interweaved layer composite material, which comprises the following steps:
s1: a first sealing adhesive tape is stuck to a position, corresponding to a tow gap, of the lower surface of the first layer of carbon fiber unidirectional cloth, and a plurality of fixing pieces are inserted into the position, corresponding to the tow gap, of the upper surface of the first layer of carbon fiber unidirectional cloth; the fixing pieces penetrate through the tow clearance and are inserted into the first sealing rubber strip, and the fixing pieces are arranged along the extending direction of the carbon fibers;
s2: the rest carbon fiber unidirectional cloth passes through the fixing pieces layer by layer and is laid together with the first layer of carbon fiber unidirectional cloth, and a second sealing strip is stuck above the fixing pieces after the laying is finished; the tow gap positions of the carbon fiber unidirectional cloth in the multi-layer carbon fiber unidirectional cloth correspond to each other;
s3: clamping two ends of the multi-layer carbon fiber unidirectional cloth by using a clamp, and vertically placing the multi-layer carbon fiber unidirectional cloth;
s4: pretreating the carbon nanotube film;
s5: cutting the pretreated carbon nanotube film into narrow carbon nanotube film strips, adhering one end of the narrow carbon nanotube film strip to the multi-layer carbon fiber unidirectional cloth, adhering the other end of the narrow carbon nanotube film strip to the tail of the blade, performing interweaving and layering on the multi-layer carbon fiber unidirectional cloth along the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth by using the blade, adhering the remaining narrow carbon nanotube film strips to the multi-layer carbon fiber unidirectional cloth after the interweaving and layering are finished, cutting off the redundant narrow carbon nanotube film strips, and removing the clamp holder, the first sealing rubber strips, the fixing pieces and the second sealing rubber strips to obtain a carbon fiber-carbon nanotube interweaving and layering structure;
s6: performing epoxy resin soaking treatment on the carbon fiber-carbon nanotube interwoven layer structure, and obtaining carbon fiber-carbon nanotube interwoven layer structure prepreg after redundant epoxy resin in the carbon fiber-carbon nanotube interwoven layer structure flows out;
s7: and carrying out hot-pressing treatment on the carbon fiber-carbon nanotube interwoven layer structure prepreg to obtain the carbon fiber-carbon nanotube interwoven layer composite material.
In a possible implementation manner, in the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material provided by the present invention, after the step S3 is executed and before the step S4 is executed, the method further includes the following steps:
s8: a weight is suspended from the lower end of the lower gripper.
In a possible implementation manner, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, in the process of interweaving and layering, the number of carbon fiber tows between two adjacent interpenetrations of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth laying direction is 1-3.
In a possible implementation manner, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the present invention, step S4 is performed to pre-process a carbon nanotube film, which specifically includes the following steps:
s41: carrying out heat treatment on the carbon nanotube film, and cleaning;
s42: adding m-chloroperoxybenzoic acid and dichloromethane into a beaker and stirring to obtain a mixed solution;
s43: folding the cleaned carbon nanotube film for multiple times, and inserting breathable tetrafluoro cloth on the upper and lower surfaces of the folded carbon nanotube film and between layers; wherein, the folded carbon nanotube film can be flatly laid at the bottom of the beaker filled with the mixed solution;
s44: placing the folded carbon nanotube film and the breathable tetrafluoro cloth together at the bottom of a beaker filled with the mixed solution, and completely pressing the folded carbon nanotube film and the breathable tetrafluoro cloth into the mixed solution by using a weight;
s45: after soaking for a preset time, taking out the folded carbon nanotube film and the breathable tetrafluoro cloth, and cleaning;
s46: removing the breathable teflon cloth, unfolding and flatly paving the folded carbon nanotube film on the polytetrafluoroethylene film, paving a layer of polytetrafluoroethylene film on the carbon nanotube film, and rolling back and forth for a plurality of times by using a roller;
s47: and carrying out hot-pressing treatment on the rolled carbon nanotube film and the polytetrafluoroethylene film.
In a possible implementation manner, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, in step S1, a first sealing adhesive tape is pasted at a position corresponding to a tow gap on the lower surface of a first layer of carbon fiber unidirectional cloth, and a plurality of fixing pieces are inserted from a position corresponding to the tow gap on the upper surface of the first layer of carbon fiber unidirectional cloth; each fixing piece penetrates through the tow gap and is inserted into the first sealing rubber strip, and the fixing pieces are arranged along the extending direction of the carbon fibers, and the method specifically comprises the following steps:
s11: a first sealing adhesive tape is stuck to the position, corresponding to the clearance between one tow, of the lower surface of the first layer of carbon fiber unidirectional cloth; the sticking position of the first sealing rubber strip is close to one edge of the first layer of carbon fiber unidirectional cloth, and the edge is parallel to the extending direction of the carbon fibers;
s12: inserting a plurality of fixing pieces from the positions, corresponding to the tow gaps, of the upper surface of the first layer of carbon fiber unidirectional cloth; the fixing pieces penetrate through the tow gap and are inserted into the first sealing rubber strip, and the fixing pieces are arranged along the extending direction of the carbon fibers.
In a possible implementation manner, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, step S5 is to cut the pretreated carbon nanotube film into a carbon nanotube film narrow band, stick one end of the carbon nanotube film narrow band to the multi-layer carbon fiber unidirectional cloth, stick the other end to the tail of the blade, utilize the blade to interweave and lay up the multi-layer carbon fiber unidirectional cloth along the arrangement direction of each carbon fiber in each layer of carbon fiber unidirectional cloth, stick the remaining carbon nanotube film narrow band to the multi-layer carbon fiber unidirectional cloth after the interweaving and laying, cut off the remaining carbon nanotube film narrow band, remove the holder and the first sealing adhesive tape, each fixing piece and the second sealing rubber strip are used for obtaining a carbon fiber-carbon nanotube interweaving and layering structure, and the method specifically comprises the following steps:
s51: cutting the pretreated carbon nanotube film into a plurality of carbon nanotube film narrow bands, and removing the polytetrafluoroethylene film on the upper surface and the lower surface of each carbon nanotube film narrow band;
s52: taking a dried carbon nanotube film narrow band, wherein one end of the carbon nanotube film narrow band is adhered to the multilayer carbon fiber unidirectional cloth, and the other end of the carbon nanotube film narrow band is adhered to the tail part of the blade; the sticking position of the carbon nanotube film narrow band on the multilayer carbon fiber unidirectional cloth is close to the first sealing rubber strip or the second sealing rubber strip and is far away from the clamp;
s53: interweaving and layering the multi-layer carbon fiber unidirectional cloth along the arrangement direction of each carbon fiber in each layer of carbon fiber unidirectional cloth by using a blade, adhering the remaining carbon nanotube film narrow bands on the multi-layer carbon fiber unidirectional cloth after interweaving and layering are finished, and cutting off the redundant carbon nanotube film narrow bands to finish interweaving and layering of one carbon nanotube film narrow band;
repeating the steps S52 and S53 until the interweaving and the layering of all the carbon nano tube film narrow bands are completed,
s54: removing the clamp holder, the first sealing rubber strips, the fixing pieces and the second sealing rubber strips to obtain a carbon fiber-carbon nanotube interweaving layer structure; wherein each of the carbon nanotube films has a narrow band aligned in the extending direction of the carbon fiber.
In a possible implementation manner, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the present invention, after the interwoven layer of one carbon nanotube film narrow band is completed, before the interwoven layer of the next carbon nanotube film narrow band is performed, the following steps are further included:
s55: polishing the tail part of the blade by using sand paper, and removing the residual carbon nanotube film adhered to the tail part of the blade; or, the residual carbon nanotube film adhered to the tail part of the blade is removed by a scraper.
The invention provides the carbon fiber-carbon nanotube interweaving layer composite material and the preparation method thereof, the composite material is a three-dimensional interweaving layer structure and comprises a plurality of layers of carbon fiber unidirectional cloth which are arranged in a laminating way, carbon nanotube film narrow bands which interweave the plurality of layers of carbon fiber unidirectional cloth together, and epoxy resin which is filled in carbon fiber gaps and carbon nanotube film narrow band gaps, in the three-dimensional interweaving layer structure, the narrow carbon nanotube film has the interpenetration in the latitudinal direction, namely the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth, and also has the interpenetration in the thickness direction, namely the stacking direction of the carbon fiber unidirectional cloth, the multi-layer carbon fiber unidirectional cloth has integrity, is more favorable for the transmission of load between layers, and can improve the conductivity in the thickness direction, namely the stacking direction of the carbon fiber unidirectional cloth, and the conductivity in the weft direction, namely the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth. The carbon nanotube film is used as a continuous aggregate, so that the problems of agglomeration, uneven dispersion and the like do not exist; moreover, the carbon nanotube film is utilized to carry out three-dimensional interweaving and layering on the carbon fibers, so that the composite material becomes a whole, and the improvement on the performance is integrated; in addition, the preparation process of the composite material is simple and easy to operate, and does not involve dangerous gases such as hydrogen, methane and the like. The weft conductivity of the carbon fiber-carbon nanotube interwoven layer composite material can reach 72.8S/m, and the thickness direction conductivity can reach 7.98S/m.
Drawings
FIG. 1 is a schematic structural diagram of a carbon fiber-carbon nanotube interwoven layer composite material provided by the present invention;
FIG. 2 is a second schematic structural diagram of a carbon fiber-carbon nanotube interwoven layer composite material provided by the present invention;
FIG. 3 is a flow chart of a method for preparing a carbon fiber-carbon nanotube interwoven layer composite material according to the present invention;
FIG. 4a is a schematic structural diagram illustrating the step S1 of the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material according to the present invention;
FIG. 4b is a schematic structural diagram after step S1 in the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material provided by the invention is performed;
FIG. 4c is a schematic structural diagram illustrating the step S2 of the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material according to the present invention;
FIG. 4d is a schematic structural diagram after step S2 in the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material provided by the invention is performed;
FIG. 4e is a schematic structural diagram after step S3 in the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material provided by the invention is performed;
FIG. 4f is a schematic structural diagram illustrating the step S4 of the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material according to the present invention;
FIG. 4g is a schematic structural diagram after step S4 in the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material provided by the invention is performed;
FIG. 5 is a schematic view of a hot press configuration;
FIG. 6 is a second flowchart of a method for preparing a carbon fiber-carbon nanotube interwoven layer composite material according to the present invention;
FIG. 7 is a third flowchart of a method for preparing a carbon fiber-carbon nanotube interwoven layer composite material according to the present invention;
FIG. 8 is a graph of interlaminar shear strength data for a carbon fiber-carbon nanotube interwoven ply composite in example 1 of the present invention;
FIG. 9 is a chart of the conductivity data of the weft direction of the carbon fiber-carbon nanotube interwoven layer composite in example 2 of the present invention;
FIG. 10 is a thickness direction conductivity data graph of the carbon fiber-carbon nanotube interwoven layer composite material in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only illustrative and are not intended to limit the present application.
The invention provides a carbon fiber-carbon nanotube interweaving and layering composite material, as shown in figure 1, which comprises: a plurality of layers of carbon fiber unidirectional cloth 1 (fig. 1 takes four layers of carbon fiber unidirectional cloth 1 as an example) which are arranged in a stacked manner, a carbon nanotube film narrow band 2 which interweaves the plurality of layers of carbon fiber unidirectional cloth 1, and epoxy resin which is filled in the gap between the carbon fiber 3 and the carbon nanotube film narrow band 2; wherein,
the positions of the filament bundle gaps of the carbon fiber unidirectional cloth 1 in the multi-layer carbon fiber unidirectional cloth 1 correspond to each other; as shown in fig. 1, in the first layer of carbon fiber unidirectional cloth, a tow gap between a first carbon fiber and a second carbon fiber on the left side, and a tow gap between a first carbon fiber and a second carbon fiber on the left side, correspond to each other in the fourth layer of carbon fiber unidirectional cloth from bottom to top; the upper and lower positions of a tow gap between the second carbon fiber and the third carbon fiber on the left side in the first layer of carbon fiber unidirectional cloth, a tow gap between the second carbon fiber and the third carbon fiber on the left side in the second layer of carbon fiber unidirectional cloth, a tow gap between the second carbon fiber and the third carbon fiber on the left side in the third layer of carbon fiber unidirectional cloth and a tow gap between the second carbon fiber and the third carbon fiber on the left side in the fourth layer of carbon fiber unidirectional cloth correspond to each other; and so on;
the carbon nanotube film narrow band 2 is interlaced along the arrangement direction (X-axis direction shown in fig. 1) of the carbon fibers 3 in each layer of the carbon fiber unidirectional cloth 1, and both ends of the carbon nanotube film narrow band 2 are respectively adhered to the multi-layer carbon fiber unidirectional cloth 1.
The carbon fiber-carbon nanotube interwoven layer composite material provided by the invention is a three-dimensional interwoven layer structure and comprises a plurality of layers of carbon fiber unidirectional cloth which are arranged in a laminating way, a carbon nanotube film narrow band which interweaves the plurality of layers of carbon fiber unidirectional cloth together and epoxy resin which is filled in a carbon fiber gap and a carbon nanotube film narrow band gap, wherein in the three-dimensional interwoven layer structure, the carbon nanotube film narrow band has the interpenetration in the latitudinal direction, namely the arrangement direction (the X-axis direction shown in figure 1) of the carbon fiber in each layer of carbon fiber unidirectional cloth, and also has the interpenetration in the thickness direction, namely the carbon fiber unidirectional cloth lamination direction (the Z-axis direction shown in figure 1), so that the multi-layer carbon fiber unidirectional cloth has integrity, is more favorable for the transmission of load between layers, and can improve the conductivity in the thickness direction, namely the carbon fiber unidirectional cloth lamination direction (the Z-axis direction shown in figure 1) and the latitudinal direction, namely the arrangement direction (the X-axis direction The electrical conductivity of (1). The carbon nanotube film is used as a continuous aggregate, so that the problems of agglomeration, uneven dispersion and the like do not exist; moreover, the carbon nanotube film is utilized to carry out three-dimensional interweaving and layering on the carbon fibers, so that the composite material becomes a whole, and the improvement on the performance is integrated; in addition, the preparation process of the composite material is simple and easy to operate, and does not involve dangerous gases such as hydrogen, methane and the like.
In specific implementation, in the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, the higher the interwoven layer density of the three-dimensional interwoven layer structure is, the stronger the stability of the three-dimensional interwoven layer structure is, so that, in order to ensure that the three-dimensional interwoven layer structure has stronger stability, the number of carbon fiber tows between two adjacent interpenetrations of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth laminated direction cannot be too large, preferably, the number of carbon fiber tows between two adjacent interpenetrations of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth laminated direction can be 1-3 tows, more preferably, the number of carbon fiber tows between two adjacent interpenetrations of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth laminated direction can be 1-2 tows, and optimally, the number of carbon fiber tows between two adjacent interpenetrations of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth laminated direction can be 1 tow, for example, as shown in fig. 2, the number of carbon fiber bundles between two adjacent insertions of the carbon nanotube film narrow strip 2 in the stacking direction (Z-axis direction shown in fig. 2) of the carbon fiber unidirectional cloth 1 is 1 bundle.
In the concrete implementation, in the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, in order to further improve the stability of the three-dimensional interwoven layer structure, multiple layers of carbon fiber unidirectional cloth can be interwoven together by using multiple carbon nanotube film narrow bands, as shown in fig. 1, five carbon nanotube film narrow bands 2 are used to interweave multiple layers of carbon fiber unidirectional cloth 1 together, each carbon nanotube film narrow band 2 is interwoven and layered along the arrangement direction (X-axis direction shown in fig. 1) of carbon fibers 3 in each layer of carbon fiber unidirectional cloth 1, the number of carbon fiber tows between two adjacent interpenetrations of each carbon nanotube film narrow band 2 along the lamination direction (Z-axis direction shown in fig. 1) of the carbon fiber unidirectional cloth 1 is two, and five carbon nanotube film narrow bands 2 are arranged along the extension direction (Y-axis direction shown in fig. 1) of the carbon fibers 3.
In specific implementation, in the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, the carbon fibers of the carbon fiber unidirectional cloth can be T series and/or M series, that is, the carbon fibers of the carbon fiber unidirectional cloth can be T series, or the carbon fibers of the carbon fiber unidirectional cloth can also be M series, or the carbon fibers of the carbon fiber unidirectional cloth can also be T series and M series, which is not limited herein; the T-series carbon fiber may be one or more of T300, T700S, T800H and T1000, and the M-series carbon fiber may be one or more of M40J, M55J and M60J, which are not limited herein.
In a specific implementation, in the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, a carbon nanotube film (CNT film) is preferably a commercially available source, and the thickness of the carbon nanotube film is preferably 1 to 15 μm, more preferably 5 to 10 μm, and most preferably 6 to 8 μm; the width of the carbon nanotube film narrow band is preferably 1-15 mm, more preferably 3-8 mm, and most preferably 5-6 mm; the length of the narrow carbon nanotube film strip is determined according to the size of a specific part, and can be calculated according to parameters such as the number of times of penetration in the thickness direction, i.e., the stacking direction of the carbon fiber unidirectional cloth (such as the Z-axis direction shown in fig. 1 and 2), the length of the composite part in the 90-degree direction, the thickness of the single-layer carbon fiber unidirectional cloth, and the like, and the calculation formula is as follows: n isZ·(df·nf)+lf+Lm＝lCWherein n isZD represents the number of interpenetration of the narrow band of the carbon nanotube film in the thickness directionfDenotes the thickness, n, of a single-layer carbon fiber unidirectional clothfIndicates the number of layers of the carbon fiber unidirectional cloth, lfIndicates the length, L, of the final composite part in the 90 degree directionmThe residual length L of the narrow band of the carbon nanotube film is shownmPreferably 1-10 cm, more preferably 3-7 cm, and most preferably 5cm, lCRepresents the total length of the narrow band of carbon nanotube film; the surface density of the carbon nanotube film is preferably 0.5-6 g/m2More preferably 1 to 5g/m2Most preferably 2 to 3g/m2(ii) a The carbon nanotube film is preferably a multi-walled carbon nanotube film, and the number of walls of the multi-walled carbon nanotube film is preferably 3 to 7, and more preferably 4 to 6. Moreover, the carbon nanotubes in the carbon nanotube film can be randomly arranged without any special requirements.
In a specific implementation, in the carbon fiber-carbon nanotube interwoven lay-up composite material provided by the present invention, the epoxy resin may be any kind of epoxy resin contained in the carbon fiber prepreg, for example, one or more of 603 resin, BC12 resin, and E51 resin, which is not limited herein. The carbon fiber prepreg comprises a carbon fiber component and an epoxy resin component, and the mass content of the epoxy resin in the carbon fiber prepreg is preferably 30-50%, more preferably 35-45%, and most preferably 40%.
Based on the same inventive concept, the invention also provides a preparation method of the carbon fiber-carbon nanotube interwoven layer composite material, as shown in fig. 3, the preparation method comprises the following steps:
s1: a first sealing rubber strip 4 is stuck to a position, corresponding to a tow gap (for example, a fourth tow gap counted from the left in fig. 4 a), of the lower surface of the first layer of carbon fiber unidirectional cloth 1, as shown in fig. 4 a; a plurality of fixing pieces 5 are inserted from the positions corresponding to the tow gaps on the upper surface of the first layer of carbon fiber unidirectional cloth 1; wherein each fixing piece 5 is inserted on the first joint strip 4 through the tow gap, and each fixing piece 5 is arranged along the extending direction of the carbon fiber 3 (Y-axis direction shown in fig. 4 b), as shown in fig. 4 b;
in order to facilitate the insertion of the carbon nanotube film narrow band in the thickness direction, namely the stacking direction of the carbon fiber unidirectional cloth, a fixing sheet is required to limit the multi-layer carbon fiber unidirectional cloth; the fixing sheet can be an aluminum sheet, the length of the fixing sheet is preferably 1-8 cm, more preferably 2-6 cm, and most preferably 3-4 cm; the width of the fixing sheet is preferably 1-10 mm, more preferably 3-7 mm, and most preferably 4-5 mm; the thickness of the fixing sheet is preferably 0.1-5 mm, more preferably 0.1-2 mm, and most preferably 0.1-0.5 mm; the space between the fixing pieces is determined according to the specific carbon fiber unidirectional cloth; the first sealing rubber strip is preferably a putty strip; the carbon fibers of the carbon fiber unidirectional cloth can be T series and/or M series, that is, the carbon fibers of the carbon fiber unidirectional cloth can be T series, or the carbon fibers of the carbon fiber unidirectional cloth can also be M series, or the carbon fibers of the carbon fiber unidirectional cloth can also be T series and M series, which are not limited herein, wherein the T series carbon fibers can be one or more of T300, T700S, T800H and T1000, and the M series carbon fibers can be one or more of M40J, M55J and M60J, which are not limited herein;
s2: the rest of the carbon fiber unidirectional cloth 1 (the rest of five layers of carbon fiber unidirectional cloth 1 are taken as an example in fig. 4 c) passes through the fixing pieces 5 layer by layer and is overlaid with the first layer of carbon fiber unidirectional cloth 1 together as shown in fig. 4 c; after the paving is finished, a second sealing strip 6 is stuck above each fixing piece 5; the positions of the filament bundle gaps of the carbon fiber unidirectional cloth in the multi-layer carbon fiber unidirectional cloth 1 correspond to each other; as shown in fig. 4 d;
the limiting and laying process of the fixing pieces can ensure that the strand gaps of the multi-layer carbon fiber unidirectional cloth are positioned at the same position, provide a channel for the penetration of the carbon nanotube film narrow band in the thickness direction, namely the stacking direction of the carbon fiber unidirectional cloth, and reduce the damage to carbon fibers in the interweaving and laying process;
s3: clamping two ends of the multi-layer carbon fiber unidirectional cloth 1 by using a clamp 7 respectively, and vertically placing the multi-layer carbon fiber unidirectional cloth 1; as shown in fig. 4 e;
in particular, the gripper may be a locking pliers; alternatively, the holder can also be a binder clip; are not limited herein; the clamp is preferably a locking pliers, because the locking pliers can apply pre-tension to the multi-layer carbon fiber unidirectional cloth due to self gravity, the multi-layer carbon fiber unidirectional cloth can be kept flat and does not generate folds in the weaving process, and the quality of interweaved layers can be improved;
s4: pretreating the carbon nanotube film;
s5: cutting the pretreated carbon nanotube film into a carbon nanotube film narrow band 2, adhering one end of the carbon nanotube film narrow band 2 to the multilayer carbon fiber unidirectional cloth 1, adhering the other end to the tail part of the blade 8, and interweaving and layering the multilayer carbon fiber unidirectional cloth 1 along the arrangement direction (the X-axis direction shown in figure 4 f) of the carbon fibers 3 in each layer of the carbon fiber unidirectional cloth 1 by using the blade 8, as shown in figure 4 f; after the interweaving and layering are finished, the remaining carbon nanotube film narrow bands 2 are adhered to the multi-layer carbon fiber unidirectional cloth 1, the redundant carbon nanotube film narrow bands 2 are cut off, the clamp 7, the first sealing rubber strip 4, the fixing pieces 5 and the second sealing rubber strip 6 are removed, and a carbon fiber-carbon nanotube interweaving and layering structure is obtained, as shown in fig. 4 g;
specifically, the carbon nanotube film (CNT film) is preferably a commercially available source, and the thickness of the carbon nanotube film is preferably 1 to 15 μm, more preferably 5 to 10 μm, and most preferably 6 to 8 μm; the width of the carbon nanotube film narrow band is preferably 1-15 mm, more preferably 3-8 mm, and most preferably 5-6 mm; the length of the narrow carbon nanotube film strip is determined according to the size of a specific part, and can be calculated according to parameters such as the number of times of penetration in the thickness direction, i.e., the stacking direction of the carbon fiber unidirectional cloth (such as the Z-axis direction shown in fig. 1 and 2), the length of the composite part in the 90-degree direction, the thickness of the single-layer carbon fiber unidirectional cloth, and the like, and the calculation formula is as follows: n isZ·(df·nf)+lf+Lm＝lCWherein n isZD represents the number of interpenetration of the narrow band of the carbon nanotube film in the thickness directionfDenotes the thickness, n, of a single-layer carbon fiber unidirectional clothfIndicates the number of layers of the carbon fiber unidirectional cloth, lfIndicates the length, L, of the final composite part in the 90 degree directionmDenotes the residual length of the narrow band of the carbon nanotube film,/CRepresents the total length of the narrow band of carbon nanotube film; in the process of interweaving and layering, two ends of the narrow carbon nanotube film tape are respectively stuck to the surface of the multi-layer carbon fiber unidirectional cloth and the tail part of the blade, and part of the length is lost, so that the length of the margin needs to be increased, and the length L of the margin needs to be increasedmPreferably 1-10 cm, more preferably 3-7 cm, and most preferably 5 cm; the surface density of the carbon nanotube film is preferably 0.5-6 g/m2More preferably 1 to 5g/m2Most preferably 2 to 3g/m2(ii) a The carbon nanotube film is preferably a multi-wall carbon nanotube film, and the wall number of the multi-wall carbon nanotube is preferably 3-7, more preferably 4-6; the carbon nanotubes in the carbon nanotube film can be randomly arranged without any special requirement; the blade may be a surgical blade, preferably a medical surgical blade; the adhesive used for pasting the carbon nanotube film narrow band is preferably 502 adhesive;
s6: performing epoxy resin soaking treatment on the carbon fiber-carbon nanotube interwoven layer structure, and obtaining carbon fiber-carbon nanotube interwoven layer structure prepreg after redundant epoxy resin in the carbon fiber-carbon nanotube interwoven layer structure flows out;
specifically, the epoxy resin may be any kind of epoxy resin contained in the carbon fiber prepreg, for example, one or more of 603 resin, BC12 resin, and E51 resin, which is not limited herein. The carbon fiber prepreg comprises a carbon fiber component and an epoxy resin component, wherein the mass content of the epoxy resin in the carbon fiber prepreg is preferably 30-50%, more preferably 35-45%, and most preferably 40%;
s7: carrying out hot pressing treatment on the carbon fiber-carbon nanotube interwoven layer structure prepreg to obtain a carbon fiber-carbon nanotube interwoven layer composite material;
specifically, the hot pressing treatment is preferably performed in a hot press, the structural schematic diagram of the hot press is shown in fig. 5, a pair of flat plate molds 9 is placed on a lower heating plate of the hot press, a carbon fiber-carbon nanotube interwoven layer structure prepreg 10 to be hot pressed is placed between the two flat plate molds 9, the upper surface and the lower surface of the carbon fiber-carbon nanotube interwoven layer structure prepreg 10 are sequentially covered with breathable polytetrafluoroethylene cloth 11, an adhesive absorption layer 12 and an isolation film 13, and adhesive blocking strips 14 are placed around the carbon fiber-carbon nanotube interwoven layer structure prepreg 10 for limiting. The temperature of the hot pressing treatment is preferably 80-180 ℃, and the pressure of the hot pressing treatment is preferably 0.1-0.6 MPa. The invention has no special requirements on the specific technological process of the hot pressing treatment, and can be set according to the curing characteristics of the epoxy resin, and the epoxy resin has a corresponding curing process under general conditions and can be cured according to the corresponding curing process.
The preparation method of the carbon fiber-carbon nanotube interweaving and layering composite material provided by the invention cuts the carbon nanotube film into the narrow band of the carbon nanotube film, utilizes the narrow band of the carbon nanotube film to interweave and lay the multilayer carbon fiber unidirectional cloth, in the process of interweaving and layering, the weft direction, namely the arrangement direction (X-axis direction shown in figure 4 d) of carbon fibers in each layer of carbon fiber unidirectional fabric is penetrated, and the thickness direction, namely the stacking direction (Z-axis direction shown in figure 4 d) of the carbon fiber unidirectional fabric is penetrated, the multi-layer carbon fiber unidirectional cloth has integrity, is more beneficial to the transmission of load among layers, and can improve the conductivity in the thickness direction, namely the stacking direction (the Z-axis direction shown in figure 4 d) of the carbon fiber unidirectional cloth and the conductivity in the weft direction, namely the arrangement direction (the X-axis direction shown in figure 4 d) of the carbon fibers in each layer of the carbon fiber unidirectional cloth. The preparation process of the composite material is simple and easy to operate, and does not involve dangerous gases such as hydrogen, methane and the like; moreover, the carbon nanotube film is utilized to carry out three-dimensional interweaving and layering on the carbon fibers, so that the composite material becomes a whole, and the improvement on the performance is integrated; in addition, the carbon nanotube film is used as a continuous aggregate, and the problems of agglomeration, uneven dispersion and the like do not exist.
In specific implementation, in the method for preparing the carbon fiber-carbon nanotube interwoven ply composite material provided by the present invention, after the step S3 is executed and before the step S4 is executed, as shown in fig. 6, the method may further include the following steps:
s8: hanging a heavy object at the lower end of the lower clamp; therefore, the suspended heavy object can apply pre-tension to the multi-layer carbon fiber unidirectional cloth, so that the multi-layer carbon fiber unidirectional cloth can keep flat without generating folds in the weaving process, and the quality of the interwoven laying layer can be improved. Specifically, the suspended weight is preferably a weight, and the weight is preferably 0.5-5 kg, more preferably 0.5-2 kg, and most preferably 0.5-1 kg.
In specific implementation, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, in the process of interweaving and layering, the larger the interweaving and layering density is, the stronger the stability of the obtained three-dimensional interweaving and layering structure is, therefore, in order to ensure that the three-dimensional interweaving laying layer structure has stronger stability, the number of carbon fiber tows between two adjacent times of interlinings of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth lamination direction cannot be too large, preferably, the number of carbon fiber tows between two adjacent times of interlinings of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth lamination direction can be 1-3 bundles, more preferably, the number of carbon fiber tows between two adjacent times of interlinings of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth lamination direction can be 1-2 bundles, and most preferably, the number of carbon fiber tows between two adjacent times of interlinings of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth lamination direction can be 1 bundle.
Preferably, in the preparation method of the carbon fiber-carbon nanotube interwoven ply composite material provided by the present invention, in order to prevent the carbon nanotube film narrowband from being layered in the interwoven ply process, the integrity and strength of the carbon nanotube film need to be increased, so that when the step S4 is executed to perform pretreatment on the carbon nanotube film, the method may specifically include the following steps:
s41: carrying out heat treatment on the carbon nanotube film, and cleaning;
specifically, the carbon nanotube film can be placed in an oven at 300 ℃ for heat treatment for 30min, and after being taken out, the carbon nanotube film is washed three times by deionized water to remove the dispersant on the surface of the carbon nanotube film;
s42: adding m-chloroperoxybenzoic acid and dichloromethane into a beaker and stirring to obtain a mixed solution;
specifically, m-chloroperoxybenzoic acid and dichloromethane can be mixed in a mass ratio of 1: mixing at a ratio of 100;
s43: folding the cleaned carbon nanotube film for multiple times, and inserting breathable tetrafluoro cloth on the upper and lower surfaces of the folded carbon nanotube film and between layers; wherein, the folded carbon nanotube film can be flatly laid at the bottom of the beaker filled with the mixed solution;
specifically, the folding times of the carbon nanotube film need to be adjusted according to the size of the beaker, and the folded carbon nanotube film needs to be laid on the bottom of the beaker without folds; breathable teflon cloth is inserted between the upper surface and the lower surface of the folded carbon nanotube film and between layers, so that the adhesion between the layers of the folded carbon nanotube film can be avoided; the number of the breathable tetrafluoro cloth needing to be cut is 2n+1, n is the number of folding times, and the area of the breathable tetrafluoro cloth is the same as that of the folded carbon nanotube film;
s44: placing the folded carbon nanotube film and the breathable tetrafluoro cloth together at the bottom of a beaker filled with the mixed solution, and completely pressing the folded carbon nanotube film and the breathable tetrafluoro cloth into the mixed solution by using a weight;
specifically, a small beaker can be placed above the folded carbon nanotube film and the breathable tetrafluoro cloth, and a weight of 200g is placed in the small beaker, so that the carbon nanotube film can be always kept flat and laid at the bottom of the beaker in the soaking process of the carbon nanotube film in the mixed solution, and the carbon nanotube film is prevented from floating and wrinkling; moreover, the diameter of the small beaker is slightly smaller than that of the beaker for containing the mixed solution, so that the small beaker can be completely placed in the beaker for containing the mixed solution, and can cover the carbon nanotube film as much as possible, thereby preventing the carbon nanotube film from floating and wrinkling;
s45: after soaking for a preset time, taking out the folded carbon nanotube film and the breathable tetrafluoro cloth, and cleaning;
specifically, the temperature for soaking the carbon nanotube film in the mixed solution is preferably 20-60 ℃, more preferably 20-40 ℃, and most preferably 30 ℃; the soaking time is preferably 1-5 h, more preferably 2-4 h, and most preferably 3 h; after being taken out, the mixture can be washed by dichloromethane for five times and then washed by ethanol for five times;
s46: removing the breathable teflon cloth, unfolding and flatly paving the folded carbon nanotube film on the polytetrafluoroethylene film, paving a layer of polytetrafluoroethylene film on the carbon nanotube film, and rolling back and forth for a plurality of times by using a roller;
specifically, the polytetrafluoroethylene film can avoid the generation of static electricity in the subsequent cutting process and the adverse effect on the performance of the carbon nanotube film; rolling the carbon nanotube film with a roller back and forth for several times to make the carbon nanotube film and the upper and lower polytetrafluoroethylene films tightly attached;
s47: carrying out hot pressing treatment on the rolled carbon nanotube film and the polytetrafluoroethylene film;
specifically, the hot pressing treatment may be performed in a hot press, where a pair of flat plate molds are placed in the hot press, and the polytetrafluoroethylene membrane and the carbon nanotube membrane are placed between the flat plate molds; the temperature of the hot pressing treatment is preferably 40-80 ℃, the pressure of the hot pressing treatment is preferably 0.1-0.6 MPa, the pressure is released after the pressure is maintained for 5min, the pressure is increased again, the pressure is preferably 0.1-0.6 MPa, the steps are repeated for 3 times, and the pressure is increased for 3 times in total; and repeating the steps for 3 times, pressurizing again, wherein the pressure is preferably 0.1-0.6 MPa, and releasing the pressure after maintaining the pressure for 15min to finish the pretreatment of the carbon nanotube film.
In specific implementation, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the invention, step S1, a first sealing adhesive tape is pasted on the lower surface of the first layer of carbon fiber unidirectional cloth at a position corresponding to a tow gap, and a plurality of fixing pieces are inserted from the upper surface of the first layer of carbon fiber unidirectional cloth at a position corresponding to the tow gap; each fixing piece penetrates through the tow gap and is inserted into the first sealing rubber strip, and the fixing pieces are arranged along the extending direction of the carbon fiber, as shown in fig. 7, the method specifically comprises the following steps:
s11: a first sealing adhesive tape is stuck to the position, corresponding to the clearance between one tow, of the lower surface of the first layer of carbon fiber unidirectional cloth; the sticking position of the first sealing rubber strip is close to one edge of the first layer of carbon fiber unidirectional cloth, and the edge is parallel to the extending direction of the carbon fibers; as shown in fig. 4d, the adhering position of the first sealing rubber strip 4 is close to the upper edge of the first layer of carbon fiber unidirectional cloth 1, so that a sufficient area can be reserved for interweaving and layering, and the larger the area of the interweaving and layering is, the stronger the stability of the obtained three-dimensional interweaving and layering structure is;
s12: inserting a plurality of fixing pieces from the positions, corresponding to the tow gaps, of the upper surface of the first layer of carbon fiber unidirectional cloth; wherein, each stationary blade passes this silk bundle clearance and inserts on first joint strip, and each stationary blade is arranged along the extending direction of carbon fiber.
In a specific implementation, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the present invention, step S5 is to cut the pretreated carbon nanotube film into a carbon nanotube film narrow band, stick one end of the carbon nanotube film narrow band to the multi-layer carbon fiber unidirectional cloth, stick the other end to the tail of the blade, utilize the blade to interweave and lay up the multi-layer carbon fiber unidirectional cloth along the arrangement direction of each carbon fiber in each layer of carbon fiber unidirectional cloth, stick the remaining carbon nanotube film narrow band to the multi-layer carbon fiber unidirectional cloth after the interweaving and lay-up is completed, and cut off the remaining carbon nanotube film narrow band, and remove the clamper, the first sealing adhesive tape, each fixing piece, and the second sealing adhesive tape, so as to obtain a carbon fiber-carbon nanotube interwoven layer structure, as shown in fig. 7, which specifically includes the following steps:
s51: cutting the pretreated carbon nanotube film into a plurality of carbon nanotube film narrow bands, and removing the polytetrafluoroethylene film on the upper surface and the lower surface of each carbon nanotube film narrow band;
s52: taking a carbon nanotube film narrow band, wherein one end of the carbon nanotube film narrow band is adhered to the multi-layer carbon fiber unidirectional cloth, and the other end of the carbon nanotube film narrow band is adhered to the tail part of the blade; the sticking position of the carbon nanotube film narrow band on the multi-layer carbon fiber unidirectional cloth is close to the first sealing rubber strip or the second sealing rubber strip and is far away from the clamp; as shown in fig. 4d, the sticking position of the carbon nanotube film narrow band 2 on the multi-layer carbon fiber unidirectional cloth 1 is close to the second sealing adhesive tape 6 and is far away from the clamper 7, and similarly, a sufficient area can be reserved for interweaving and layering, and the larger the area of interweaving and layering is, the stronger the stability of the obtained three-dimensional interweaving and layering structure is;
s53: interweaving and layering the multi-layer carbon fiber unidirectional cloth along the arrangement direction of each carbon fiber in each layer of carbon fiber unidirectional cloth by using a blade, adhering the residual carbon nanotube film narrow band on the multi-layer carbon fiber unidirectional cloth after interweaving and layering are finished, and cutting off the residual carbon nanotube film narrow band to finish interweaving and layering of one carbon nanotube film narrow band;
repeatedly executing the step S52 and the step S53 until the interweaving and the layering of all the carbon nanotube film narrow bands are completed; the stability of the three-dimensional interweaving layer structure can be further improved by interweaving the multi-layer carbon fiber unidirectional cloth together by using the plurality of carbon nanotube film narrow bands;
s54: removing the clamp, the first sealing rubber strip, the fixing sheets and the second sealing rubber strip to obtain a carbon fiber-carbon nanotube interwoven layer structure; wherein the narrow bands of the carbon nanotube films are arranged along the extending direction of the carbon fibers.
In specific implementation, in the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the present invention, after the interwoven layer of one carbon nanotube film narrow band is completed, before the interwoven layer of the next carbon nanotube film narrow band is performed, as shown in fig. 7, the method may further include the following steps:
s55: polishing the tail part of the blade by using sand paper, and removing the residual carbon nanotube film adhered to the tail part of the blade; or, removing the residual carbon nanotube film adhered to the tail part of the blade by using a scraper; therefore, the thickness of the head part and the thickness of the tail part of the blade are basically consistent, and the blade is convenient to insert in the carbon fiber unidirectional cloth.
The following two specific examples are used to describe in detail the specific implementation process of the preparation method of the carbon fiber-carbon nanotube interwoven layer composite material provided by the present invention.
Example 1:
t300 carbon fiber unidirectional cloth (single layer thickness is about 0.20mm) is cut into 60mm × 100mm size for standby by using a wallpaper cutter and a ruler, the length of the weft direction (namely the arrangement direction of the carbon fibers) is 100mm, and the cutting number is 12. And cutting a section of sealing rubber strip for the vacuum bag, wherein the length of the sealing rubber strip is 60 mm. And taking one piece of carbon fiber unidirectional cloth, and pasting a sealing rubber strip on the carbon fiber unidirectional cloth, wherein the sealing rubber strip is aligned with one of the tow gap axes of the carbon fiber unidirectional cloth, and the selection of the tow gap should be about 3cm away from the edge of the unidirectional cloth. 6 aluminum sheets for cutting and limiting are provided, the length is 50mm, the width is 5mm, and the thickness is 0.2 mm. Six aluminum sheets sequentially penetrate through the strand clearance aligned with the sealing rubber strip and are vertically inserted into the sealing rubber strip, the six aluminum sheets are arranged in a row, the arrangement direction of the six aluminum sheets is parallel to the extending direction of the carbon fibers, and the interval between every two adjacent aluminum sheets is about 8 mm.
After the positioning of the limiting aluminum sheet is completed, the other 11 pieces of carbon fiber unidirectional cloth sequentially pass through the limiting aluminum sheet to be laid, and for the 11 pieces of carbon fiber unidirectional cloth, the clearance of a filament bundle which the limiting aluminum sheet passes through is about 3cm away from the unidirectional cloth, so that the edges of the 12 pieces of unidirectional cloth are basically aligned. After the 12 pieces of carbon fiber unidirectional cloth pass through the limiting aluminum sheets and are completely laid, a sealing rubber strip with the length of 60mm is pasted above the aluminum sheets and is compacted, so that the upper ends of the aluminum sheets are also vertically inserted into the sealing rubber strip. The two ends of 12 single-fiber unidirectional fabrics are respectively clamped by a locking pliers and are placed in a suspension mode, wherein the clamping length of the upper end is 2cm, and the clamping length of the lower end is 0.5 cm. The gravity of the locking pliers applies pre-tension to the 12 unidirectional carbon fiber cloth, so that the 12 unidirectional carbon fiber cloth is flat and has no wrinkles.
After the carbon nanotube film with the thickness of 10 μm is pretreated, the carbon nanotube film is cut into narrow carbon nanotube film strips with the size of 200mm multiplied by 5mm, and the number of the carbon nanotube film strips is 8. And after cutting, drying at 60 ℃ for 60min in a vacuum oven, and after the drying, closing the oven and cooling to room temperature along with the oven. One end of the carbon nanotube film narrow band is adhered to the tail end of the scalpel by 502 glue, the other end of the carbon nanotube film narrow band is adhered to the surface of 12 pieces of carbon fiber unidirectional cloth, the adhering position is close to the limiting aluminum sheet, and the adhering length is 25 mm. After the two ends of the carbon nanotube film narrow band are completely pasted, 12 carbon fiber unidirectional fabrics are interpenetrated in the thickness direction (namely the stacking direction of the 12 carbon fiber unidirectional fabrics) by using a scalpel blade, the carbon fiber tows spaced between every two adjacent interpenetrations are 1 tow, the interpenetration is stopped when the carbon fiber unidirectional fabrics are interpenetrated at a position 0.5cm away from the lower end of the 12 carbon fiber unidirectional fabrics, the powerful pliers below the carbon nanotube film narrow band are taken down, the carbon nanotube film narrow band is pasted on the surface of the 12 carbon fiber unidirectional fabrics, the pasting length is 50mm, and after the pasting is completed, redundant carbon nanotube film narrow bands are cut off by using scissors. And (3) clamping the lower ends of the 12 pieces of carbon fiber unidirectional cloth again by using a locking pliers, thus finishing the interweaving and layering process of the carbon nanotube film narrow band.
Polishing the carbon nanotube film narrow band on the surgical blade by using 2000-mesh abrasive paper, removing residual carbon nanotube film stuck on the surgical blade, sticking one end of the carbon nanotube film narrow band to the tail end of the surgical blade and the other end of the carbon nanotube film narrow band to the surfaces of 12 pieces of carbon fiber unidirectional cloth, wherein the sticking position is close to a limiting aluminum sheet, the interval between the limiting aluminum sheet and the previous carbon nanotube film narrow band is about 3mm, and interweaving and laying the rest 7 carbon nanotube film narrow bands according to the steps. And taking down the locking pliers, the sealing rubber strips and the aluminum sheets clamped at two ends of the 12 pieces of carbon fiber unidirectional cloth to obtain the carbon fiber-carbon nanotube interwoven layer structure.
The interwoven layer structure is flatly placed at the bottom of a glass groove with the size similar to that of the interwoven layer structure, 50g of E51 epoxy resin is taken, a BC12 curing agent is added, and the mass ratio of E51 to BC12 is 100: and 84, stirring by using a glass rod, pouring the resin mixture into a glass tank after uniformly stirring, and slowing the pouring process as much as possible to avoid generating excessive bubbles. The glass tank was immersed in a vacuum oven at 60 ℃ for 60 min. And taking the impregnated woven structure out of the glass tank, placing the woven structure on release paper and placing the release paper in a drying box, so that redundant resin flows out, and standing for 60min to obtain the carbon fiber-carbon nanotube woven structure prepreg.
Laying the prepreg with related auxiliary materials (comprising breathable polytetrafluoroethylene cloth, an adhesive absorption layer, an isolation film and a flat plate mold), and curing on a hot press under the following curing conditions: heating to 100 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 40min, pressurizing to 0.6MPa, continuously heating to 120 ℃ at the speed of 1 ℃/min, preserving heat for 3h to finish curing, cooling to 60 ℃ along with a furnace, and then releasing pressure to obtain the carbon fiber-carbon nanotube interwoven laying layer composite material.
The prepared interwoven layer composite material was cut into a size of 20mm × 10mm, and the interlaminar shear strength of sample 1 containing no carbon nanotube film and sample 2 containing carbon nanotube film was measured using a universal mechanical tester, respectively. As shown in fig. 8, the interlaminar shear strength of sample 2 containing the carbon nanotube film was increased from 36.5MPa to 40.9MPa, which is 12% higher than that of sample 1 containing no carbon nanotube film.
Example 2:
t300 carbon fiber unidirectional cloth (single layer thickness is about 0.20mm) is cut into 80mm x 200mm size for standby by using a wallpaper cutter and a ruler, the length of the weft direction (namely the arrangement direction of the carbon fibers) is 200mm, and the cutting number is 20. And cutting off a section of sealing rubber strip for the vacuum bag, wherein the length of the sealing rubber strip is 80 mm. And taking one piece of carbon fiber unidirectional cloth, and pasting a sealing rubber strip on the carbon fiber unidirectional cloth, wherein the sealing rubber strip is aligned with one of the tow gap axes of the carbon fiber unidirectional cloth, and the selection of the tow gap should be about 3cm away from the edge of the unidirectional cloth. 10 aluminum sheets for cutting and limiting are provided, the length is 60mm, the width is 3mm, and the thickness is 0.5 mm. And sequentially passing 10 aluminum sheets through the strand clearance aligned with the sealing rubber strip and vertically inserting the aluminum sheets into the sealing rubber strip, wherein the 10 aluminum sheets are arranged in a row, the arrangement direction of the 10 aluminum sheets is parallel to the extension direction of the carbon fibers, and the interval between every two adjacent aluminum sheets is about 5 mm.
After the positioning of the limiting aluminum sheet is completed, the rest 19 pieces of carbon fiber unidirectional cloth sequentially pass through the limiting aluminum sheet to be laid, and for the 19 pieces of carbon fiber unidirectional cloth, the clearance of a filament bundle which the limiting aluminum sheet passes through is about 3cm away from the unidirectional cloth, so that the edges of the 20 pieces of unidirectional cloth are basically aligned. After 20 pieces of carbon fiber unidirectional cloth pass through the limiting aluminum sheet and are completely laid, a sealing rubber strip with the length of 80mm is pasted above the aluminum sheet and is compacted, so that the upper end of the aluminum sheet is also vertically inserted into the sealing rubber strip. The two ends of 20 single-fiber unidirectional fabrics are respectively clamped by a large-scale binder clip and are placed in a suspension manner, wherein the clamping length of the upper end is 2cm, and the clamping length of the lower end is 2 cm. And a weight of 0.5kg is hung at the lower end of the lower long tail clamp to apply pre-tension to the 20 pieces of carbon fiber unidirectional cloth, so that the 20 pieces of carbon fiber unidirectional cloth are flat and have no wrinkles.
After the carbon nanotube film with the thickness of 10 μm is pretreated, the carbon nanotube film is cut into narrow carbon nanotube film strips with the size of 350mm multiplied by 10mm, and the number of the carbon nanotube film strips is 6. And after cutting, drying at 50 ℃ for 30min in a vacuum oven, and after the drying, closing the oven and cooling to room temperature along with the oven. One end of the carbon nanotube film narrow band is adhered to the tail end of the scalpel by 502 glue, the other end of the carbon nanotube film narrow band is adhered to the surface of 20 pieces of carbon fiber unidirectional cloth, the adhering position is close to the limiting aluminum sheet, and the adhering length is 25 mm. After the two ends of the carbon nanotube film narrow band are completely pasted, the surgical blade is utilized to perform interpenetration in the thickness direction (namely the stacking direction of the 20 carbon fiber unidirectional fabrics) on the 20 carbon fiber unidirectional fabrics, the carbon fiber tows spaced between every two adjacent interpenetrations are 2 tows, the interpenetration is stopped when the carbon fiber unidirectional fabrics interpenetration reaches the lower end of the 20 carbon fiber unidirectional fabrics by 2cm, the long tail clamp below the carbon fiber unidirectional fabrics is taken down to complete the interweaving and layering of the rest part, the interweaving and layering is stopped at the position 0.5cm away from the lower edge of the 20 carbon fiber unidirectional fabrics, the carbon nanotube film narrow band is pasted on the surface of the 20 carbon fiber unidirectional fabrics, the pasting length is 50mm, and after the pasting is completed, the redundant carbon nanotube film narrow band is cut off by scissors. And (3) clamping the lower ends of the 20 pieces of carbon fiber unidirectional cloth by using the long tail clamp again, thus finishing the interweaving and layering process of the carbon nanotube film narrow band.
Removing residual carbon nanotube films stuck on the scalpel blade from the carbon nanotube film narrow band on the scalpel blade by using a scraper, then taking a carbon nanotube film narrow band, sticking one end of the carbon nanotube film narrow band on the tail end of the scalpel blade and sticking the other end of the carbon nanotube film narrow band on the surface of 20 pieces of carbon fiber unidirectional cloth, wherein the sticking position is close to a limiting aluminum sheet, the interval between the carbon nanotube film narrow band and the previous carbon nanotube film narrow band is about 3mm, and interweaving and laying the rest 5 carbon nanotube film narrow bands according to the steps. And taking down the binder clips, the sealing rubber strips and the aluminum sheets which are clamped at two ends of the 20 pieces of carbon fiber unidirectional cloth to obtain the carbon fiber-carbon nanotube interwoven layer structure.
The interweaving layer structure is flatly placed at the bottom of a glass groove with the size similar to that of the interweaving layer structure, 50g of E51 epoxy resin is taken, a BC12 curing agent and an epoxy resin diluent are added, and the mass ratio of E51 to BC12 to the epoxy resin diluent is 100: 84: and 10, stirring by using a glass rod, pouring the resin mixture into a glass tank after uniformly stirring, and performing impregnation treatment for 30min, wherein the pouring process is as slow as possible to avoid generating excessive bubbles. Taking out the impregnated woven structure from a glass tank, performing double-sided adhesive absorption on the woven structure by using glass cloth, and extruding redundant resin by using a hot press, wherein the process conditions are as follows: heating to 60 ℃ at the speed of 5 ℃/min, pressurizing to 0.2MPa, heating to 75 ℃ at the speed of 5 ℃/min, preserving heat for 30min, and cooling to room temperature along with a furnace to obtain the carbon fiber-carbon nanotube woven structure prepreg.
Laying the prepreg with related auxiliary materials (comprising breathable polytetrafluoroethylene cloth, an adhesive absorption layer, an isolation film and a flat plate mold), curing on a hot press, and formulating the curing process conditions of the autoclave according to the curing reaction characteristics of the adopted BC12/E51 resin system as follows: heating from room temperature of 25 ℃ to 80 ℃ at the speed of 2 ℃/min, preserving heat for 30min, pressurizing to 0.3MPa, continuously heating to 120 ℃ at the speed of 2 ℃/min, preserving heat for 3h to finish curing, cooling to 60 ℃ at the speed of 2 ℃/min, and then unloading to obtain the carbon fiber-carbon nanotube interwoven laying layer composite material.
The prepared interwoven layer composite material is cut into the size of 60mm multiplied by 20mm, and the conductivity of the interwoven layer composite material in the thickness direction (namely the laying direction of 20 pieces of carbon fiber unidirectional cloth) and the latitudinal direction (namely the arrangement direction of the carbon fibers in the single-layer carbon fiber unidirectional cloth) is tested by using a resistance meter. As shown in fig. 9 and 10, in the latitudinal direction and the thickness direction, compared with the sample 1 without the carbon nanotube film, the conductivity of the sample 2 with the carbon nanotube film is greatly improved, and the latitudinal conductivity is improved to 72.78S/m from 4.4S/m, which is improved by 15 times; the conductivity in the thickness direction is improved to 7.98S/m from 0.56S/m, which is improved by 13 times.
The invention provides the carbon fiber-carbon nanotube interweaving layer composite material and the preparation method thereof, the composite material is a three-dimensional interweaving layer structure and comprises a plurality of layers of carbon fiber unidirectional cloth which are arranged in a laminating way, carbon nanotube film narrow bands which interweave the plurality of layers of carbon fiber unidirectional cloth together, and epoxy resin which is filled in carbon fiber gaps and carbon nanotube film narrow band gaps, in the three-dimensional interweaving layer structure, the narrow carbon nanotube film has the interpenetration in the latitudinal direction, namely the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth, and also has the interpenetration in the thickness direction, namely the stacking direction of the carbon fiber unidirectional cloth, the multi-layer carbon fiber unidirectional cloth has integrity, is more favorable for the transmission of load between layers, and can improve the conductivity in the thickness direction, namely the stacking direction of the carbon fiber unidirectional cloth, and the conductivity in the weft direction, namely the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth. The carbon nanotube film is used as a continuous aggregate, so that the problems of agglomeration, uneven dispersion and the like do not exist; moreover, the carbon nanotube film is utilized to carry out three-dimensional interweaving and layering on the carbon fibers, so that the composite material becomes a whole, and the improvement on the performance is integrated; in addition, the preparation process of the composite material is simple and easy to operate, and does not involve dangerous gases such as hydrogen, methane and the like. The weft conductivity of the carbon fiber-carbon nanotube interwoven layer composite material can reach 72.8S/m, and the thickness direction conductivity can reach 7.98S/m.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A preparation method of a carbon fiber-carbon nanotube interweaved laying composite material comprises a plurality of layers of carbon fiber unidirectional cloth which are arranged in a laminating way, a carbon nanotube film narrow band which interweaves the plurality of layers of carbon fiber unidirectional cloth together, and epoxy resin which is filled in a carbon fiber gap and a carbon nanotube film narrow band gap; the positions of the filament bundle gaps of the carbon fiber unidirectional cloth in the multi-layer carbon fiber unidirectional cloth correspond to each other; the carbon nanotube film narrow band is interwoven with layers along the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth, and two ends of the carbon nanotube film narrow band are respectively adhered to the multiple layers of carbon fiber unidirectional cloth; the method is characterized by comprising the following steps:
s1: a first sealing adhesive tape is stuck to a position, corresponding to a tow gap, of the lower surface of the first layer of carbon fiber unidirectional cloth, and a plurality of fixing pieces are inserted into the position, corresponding to the tow gap, of the upper surface of the first layer of carbon fiber unidirectional cloth; the fixing pieces penetrate through the tow clearance and are inserted into the first sealing rubber strip, and the fixing pieces are arranged along the extending direction of the carbon fibers;
s2: the rest carbon fiber unidirectional cloth passes through the fixing pieces layer by layer and is laid together with the first layer of carbon fiber unidirectional cloth, and a second sealing strip is stuck above the fixing pieces after the laying is finished; the tow gap positions of the carbon fiber unidirectional cloth in the multi-layer carbon fiber unidirectional cloth correspond to each other;
s3: clamping two ends of the multi-layer carbon fiber unidirectional cloth by using a clamp, and vertically placing the multi-layer carbon fiber unidirectional cloth;
s4: pretreating the carbon nanotube film;
s5: cutting the pretreated carbon nanotube film into narrow carbon nanotube film strips, adhering one end of the narrow carbon nanotube film strip to the multi-layer carbon fiber unidirectional cloth, adhering the other end of the narrow carbon nanotube film strip to the tail of the blade, performing interweaving and layering on the multi-layer carbon fiber unidirectional cloth along the arrangement direction of carbon fibers in each layer of carbon fiber unidirectional cloth by using the blade, adhering the remaining narrow carbon nanotube film strips to the multi-layer carbon fiber unidirectional cloth after the interweaving and layering are finished, cutting off the redundant narrow carbon nanotube film strips, and removing the clamp holder, the first sealing rubber strips, the fixing pieces and the second sealing rubber strips to obtain a carbon fiber-carbon nanotube interweaving and layering structure;
s6: performing epoxy resin soaking treatment on the carbon fiber-carbon nanotube interwoven layer structure, and obtaining carbon fiber-carbon nanotube interwoven layer structure prepreg after redundant epoxy resin in the carbon fiber-carbon nanotube interwoven layer structure flows out;
s7: carrying out hot pressing treatment on the carbon fiber-carbon nanotube interwoven layer structure prepreg to obtain a carbon fiber-carbon nanotube interwoven layer composite material;
in step S4, the method for pretreating a carbon nanotube film specifically includes the following steps:
s41: carrying out heat treatment on the carbon nanotube film, and cleaning;
s42: adding m-chloroperoxybenzoic acid and dichloromethane into a beaker and stirring to obtain a mixed solution;
s43: folding the cleaned carbon nanotube film for multiple times, and inserting breathable tetrafluoro cloth on the upper and lower surfaces of the folded carbon nanotube film and between layers; wherein, the folded carbon nanotube film can be flatly laid at the bottom of the beaker filled with the mixed solution;
s44: placing the folded carbon nanotube film and the breathable tetrafluoro cloth together at the bottom of a beaker filled with the mixed solution, and completely pressing the folded carbon nanotube film and the breathable tetrafluoro cloth into the mixed solution by using a weight;
s45: after soaking for a preset time, taking out the folded carbon nanotube film and the breathable tetrafluoro cloth, and cleaning;
s46: removing the breathable teflon cloth, unfolding and flatly paving the folded carbon nanotube film on the polytetrafluoroethylene film, paving a layer of polytetrafluoroethylene film on the carbon nanotube film, and rolling back and forth for a plurality of times by using a roller;
s47: and carrying out hot-pressing treatment on the rolled carbon nanotube film and the polytetrafluoroethylene film.
2. The method for preparing a carbon fiber-carbon nanotube interwoven ply composite material according to claim 1, further comprising the following steps after the step S3 is performed and before the step S4 is performed:
s8: a weight is suspended from the lower end of the lower gripper.
3. The preparation method of the carbon fiber-carbon nanotube interwoven layer composite material as claimed in claim 1, wherein in the process of interwoven layering, the number of carbon fiber tows between two adjacent interpenetrations of the carbon nanotube film narrow band along the laying direction of the carbon fiber unidirectional cloth is 1-3.
4. The method for preparing a carbon fiber-carbon nanotube interwoven layer composite material according to any one of claims 1 to 3, wherein in step S1, a first sealing adhesive tape is adhered to a position corresponding to a tow gap on the lower surface of a first layer of carbon fiber unidirectional cloth, and a plurality of fixing pieces are inserted from a position corresponding to the tow gap on the upper surface of the first layer of carbon fiber unidirectional cloth; each fixing piece penetrates through the tow gap and is inserted into the first sealing rubber strip, and the fixing pieces are arranged along the extending direction of the carbon fibers, and the method specifically comprises the following steps:
s11: a first sealing adhesive tape is stuck to the position, corresponding to the clearance between one tow, of the lower surface of the first layer of carbon fiber unidirectional cloth; the sticking position of the first sealing rubber strip is close to one edge of the first layer of carbon fiber unidirectional cloth, and the edge is parallel to the extending direction of the carbon fibers;
s12: inserting a plurality of fixing pieces from the positions, corresponding to the tow gaps, of the upper surface of the first layer of carbon fiber unidirectional cloth; the fixing pieces penetrate through the tow gap and are inserted into the first sealing rubber strip, and the fixing pieces are arranged along the extending direction of the carbon fibers.
5. The method for preparing a carbon fiber-carbon nanotube interwoven layer composite material according to claim 4, wherein the step S5 comprises the steps of cutting the pretreated carbon nanotube film into a narrow carbon nanotube film strip, adhering one end of the narrow carbon nanotube film strip to the multi-layer carbon fiber unidirectional cloth, adhering the other end of the narrow carbon nanotube film strip to the tail of the blade, utilizing the blade to interweave and lay the multi-layer carbon fiber unidirectional cloth along the arrangement direction of each carbon fiber in each layer of carbon fiber unidirectional cloth, adhering the remaining narrow carbon nanotube film strip to the multi-layer carbon fiber unidirectional cloth after the interweaving and laying, cutting off the redundant narrow carbon nanotube film strip, and removing the clamp, the first sealing rubber strip, each fixing piece and the second sealing rubber strip to obtain a carbon fiber-carbon nanotube interwoven layer structure, which comprises the following steps:
s51: cutting the pretreated carbon nanotube film into a plurality of carbon nanotube film narrow bands, and removing the polytetrafluoroethylene film on the upper surface and the lower surface of each carbon nanotube film narrow band;
s52: taking a carbon nanotube film narrow band, wherein one end of the carbon nanotube film narrow band is adhered to the multi-layer carbon fiber unidirectional cloth, and the other end of the carbon nanotube film narrow band is adhered to the tail part of the blade; the sticking position of the carbon nanotube film narrow band on the multilayer carbon fiber unidirectional cloth is close to the first sealing rubber strip or the second sealing rubber strip and is far away from the clamp;
s53: interweaving and layering the multi-layer carbon fiber unidirectional cloth along the arrangement direction of each carbon fiber in each layer of carbon fiber unidirectional cloth by using a blade, adhering the remaining carbon nanotube film narrow bands on the multi-layer carbon fiber unidirectional cloth after interweaving and layering are finished, and cutting off the redundant carbon nanotube film narrow bands to finish interweaving and layering of one carbon nanotube film narrow band;
repeating the steps S52 and S53 until the interweaving and the layering of all the carbon nano tube film narrow bands are completed,
s54: removing the clamp holder, the first sealing rubber strips, the fixing pieces and the second sealing rubber strips to obtain a carbon fiber-carbon nanotube interweaving layer structure; wherein each of the carbon nanotube films has a narrow band aligned in the extending direction of the carbon fiber.
6. The method for preparing a carbon fiber-carbon nanotube interwoven layer composite material according to claim 5, wherein after the interwoven layer of one carbon nanotube film narrow band is completed, before the interwoven layer of the next carbon nanotube film narrow band is carried out, the method further comprises the following steps:
s55: polishing the tail part of the blade by using sand paper, and removing the residual carbon nanotube film adhered to the tail part of the blade; or, the residual carbon nanotube film adhered to the tail part of the blade is removed by a scraper.
7. The method for preparing the carbon fiber-carbon nanotube interwoven layer composite material according to claim 1, wherein the number of carbon fiber tows between two adjacent times of interpenetrations of the carbon nanotube film narrow band along the carbon fiber unidirectional cloth lamination direction is 1-3 bundles.
8. The method for preparing a carbon fiber-carbon nanotube interwoven layer composite material according to claim 1 or 7, wherein the plurality of carbon nanotube film narrow bands interweave the plurality of layers of carbon fiber unidirectional cloth together;
the carbon nanotube films are arranged in a narrow band along the extending direction of the carbon fibers.
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