CN109910329B - Carbon nanotube interlayer reinforced resin-based laminated composite material based on weak impregnation prepreg and preparation method thereof - Google Patents
Carbon nanotube interlayer reinforced resin-based laminated composite material based on weak impregnation prepreg and preparation method thereof Download PDFInfo
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- CN109910329B CN109910329B CN201910232174.3A CN201910232174A CN109910329B CN 109910329 B CN109910329 B CN 109910329B CN 201910232174 A CN201910232174 A CN 201910232174A CN 109910329 B CN109910329 B CN 109910329B
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Abstract
The invention discloses a preparation method of a carbon nanotube interlayer reinforced resin matrix laminated composite material based on weak impregnation prepreg, which comprises the following steps: preparing a weak impregnation preforming body, determining a melting impregnation process interval, carrying out vacuum-assisted Z-direction melting impregnation, and carrying out mould pressing, curing and forming.
Description
Technical Field
The invention relates to the field of carbon nanotube reinforced resin matrix composite materials, in particular to a carbon nanotube interlayer reinforced resin matrix laminated composite material based on weak impregnation prepreg and a preparation method thereof.
Background
In recent years, fiber reinforced resin matrix composite materials have been rapidly increased in applications to high performance vehicles such as land, sea, air, sky and the like and sports by virtue of their characteristics of high specific strength, high specific modulus and strong material designability. With the continuous expansion of the application range, the defects of the application range are more and more obvious. Currently, the most widely used form of composite materials is primarily laminated composite (plywood). The laminated plate is an integral structural plate which is formed by laying a plurality of single-layer plates according to a specified laminating sequence and a laminating angle, bonding the single-layer plates by interlayer resin and then thermally curing the single-layer plates. In the traditional laminated composite material, fiber reinforcement is lacked among all layers, and the polymer matrix is only used for bearing and transferring load, so that the interlayer performance is weak, the interlayer performance is a weak link for bearing the laminated plate, and the full play of the advantageous performance and the weight reduction advantage of the laminated composite material is limited. The carbon nano tube is a large length-diameter ratio one-dimensional tubular nano reinforcing material with ultrahigh specific strength and ultrahigh specific modulus developed in recent years. After the carbon nano tube is introduced between the layers of the composite material, the rigidity, the strength and the fracture toughness of the interlayer matrix layer can be effectively improved, and the heat conduction and the electric conduction of the composite material along the thickness direction can be synchronously improved.
Generally, carbon nanotubes are generally added to composite materials by two methods, one is to transfer a carbon nanotube-containing liquid resin to a fiber preform by means of RTM, VIMP or the like after blending with the liquid resin in a liquid phase molding process, and heat-cure the resin. A significant disadvantage of this method is that when the carbon nanotube-containing resin impregnates the fiber preform, the carbon nanotubes are present in the glue inlet build-up phenomenon, which severely affects their distribution in the finally prepared composite material, since the carbon nanotubes are hindered by the fibers as the resin flows. In addition, because the viscosity of the resin used in the liquid phase forming process is low, the carbon nanotubes dispersed at the early stage are easy to re-agglomerate in the resin, and the performance of the carbon nanotubes is affected. And secondly, by a prepreg preparation method, the carbon nano tubes are mixed into high-viscosity prepreg resin in advance, then the resin containing the carbon nano tubes is uniformly coated on the fibers by a press-coating method, and the fibers are flattened to obtain the carbon nano tube-containing fiber prepreg. Although the method solves the problems of carbon nanotube distribution and agglomeration in the liquid phase forming of the carbon nanotubes, the method still has obvious defects. The carbon nano tubes of the prepreg prepared by the method are mainly distributed among fibers in the layers, and the relative content of the carbon nano tubes in the interlayer resin is less; the mass fraction of the carbon nano tube and the fiber is fixed and cannot be flexibly controlled; and the carbon nano tube has poor orientation degree along the thickness direction, and can not exert various advantageous properties along the axial direction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a carbon nanotube interlaminar reinforced resin matrix laminated composite material based on weak impregnation prepreg and a preparation method thereof, wherein carbon nanotubes are uniformly distributed in interlaminar layers and the mass fraction of the carbon nanotubes is controllable.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a carbon nanotube interlayer reinforced resin-based laminated composite material based on weak impregnation prepreg comprises the following steps:
s1, laminating the carbon nanotube-containing resin film serving as a substrate and a fiber fabric, and then performing pressure treatment to obtain a weak impregnation prepreg;
s2, respectively taking n pieces of the weakly impregnated prepreg obtained in the step S1, superposing the n pieces of weakly impregnated prepreg into two identical preformed bodies according to preset requirements, marking the two identical preformed bodies as a preformed body I and a preformed body II, placing temperature sensors between the 1 st layer and the 2 nd layer of the preformed body I, between the 2/n-1 st layer and the 2/n th layer, between the n-1 st layer and the n th layer and in one side surface of the resin film, leading the temperature sensors out of the preformed body I, and connecting the temperature sensors with a multichannel thermometer, wherein n is a positive integer greater than or equal to 2;
s3, coating resin on a rotational rheometer, wherein the resin components are the same as those of resin in a resin film containing carbon nano tubes, setting the test temperature input as the input of an external thermometer, placing the preformed body I obtained in the step S2 on a heating table top at the temperature of 60-200 ℃, recording the viscosity-time curve of the resin on the rotational rheometer and the temperature-time curve of a multi-channel thermometer after the resin in the preformed body I is completely cured, obtaining the viscosity-temperature-time curve of the preformed body II, determining a melting and dipping process interval, obtaining a vacuum pressure intervention time point, a vacuum pressure maintaining time length and a mould pressing time point;
s4, placing the preformed body II obtained in the step S2 on a mold, laying a flow guide net on the preformed body II, laying a vacuum bag film above the mold, and packaging to obtain a packaged mold;
the vacuum bag film is provided with an air outlet, a vacuum tube is inserted into the air outlet, and the air outlet is connected with a vacuum pump through the vacuum tube;
s5, heating the mould packaged in the step S4 to 60-200 ℃, preserving heat, opening a vacuum pump to vacuumize the vacuum bag film at the vacuum pressure intervention time point determined in the step S3 until the pressure in the vacuum bag film reaches a set value, maintaining pressure according to the vacuum pressure maintaining time determined in the step S3, closing the vacuum pump, and removing the vacuum bag film and the flow guide net to obtain a completely-impregnated preform II;
and S6, continuing to keep the temperature, closing the mold and pressurizing the fully-impregnated pre-forming body II obtained in the step S5 through the mold press at the pressurizing time point of the mold press determined in the step S3 until the resin is fully cured, cooling and demolding to obtain the fiber reinforced resin matrix laminated composite material.
As a further improvement to the above technical solution:
and a buffer tank is also connected between the gas outlet and the vacuum pump, and a pressure regulating valve is arranged on the buffer tank.
In the step S5, the negative pressure reduction rate of the vacuum-pumping treatment is 3.37-6.73 kPa/S, and the pressure set value is-101 kPa.
In the step S6, the pressure of the mold closing and pressing is 2 to 6 Mpa.
In step S1, the preparation method of the weakly impregnated prepreg specifically includes:
s1-1, mixing the resin, the solvent and the carbon nano tube powder, and uniformly stirring to obtain a mixed glue solution;
s1-2, coating the mixed glue solution obtained in the step S1 on a protective film, drying until the solvent is completely volatilized, and covering the protective film to obtain a carbon nanotube-containing resin film;
s1-3, cutting the carbon nanotube-containing resin film and the fiber fabric according to a preset size, removing the protective film on one side of the upper surface of the carbon nanotube-containing resin film obtained in the step S2, overlapping the fiber fabric on the upper surface of the carbon nanotube-containing resin film, and placing the carbon nanotube-containing resin film on a heating table;
s1-4, heating the heating table to 35-50 ℃, carrying out pressure treatment on the fiber fabric, releasing pressure, and cooling to obtain the weak impregnation prepreg.
The step S1-1 specifically includes:
a1, mixing the resin and the solvent, stirring uniformly, adding the carbon nanotube powder, and continuously stirring uniformly to obtain a carbon nanotube-containing resin glue solution;
a2, grinding the carbon nanotube-containing resin glue solution, and uniformly stirring to obtain a mixed glue solution.
The weak impregnation prepreg comprises a fiber fabric and a resin film substrate, wherein carbon nanotubes are distributed in the resin film substrate, the fiber fabric covers the resin film substrate, and the lower surface part of the fiber fabric is impregnated in the resin film substrate.
The solvent is one of ethanol, acetone, tetrahydrofuran and methanol, and the resin is hot-melt reactive resin and is one or more of epoxy resin, unsaturated polyester resin, bismaleimide and thermosetting polyimide.
In the viscosity-temperature-time curve of the preform II, the vacuum pressure intervention time point is 1-15 minutes before the viscosity is transited from a low-viscosity platform to a viscosity rising section; the vacuum pressure maintaining time is the time from the intervention time point of the vacuum pressure to the initial point of the viscosity rising section; the press pressurization time point is the time point after the low viscosity plateau at which the viscosity begins to be greater than 10000mPa · s.
In the step S5, the vacuum bag film is translucent or transparent, and when the resin is observed to have penetrated uniformly from the top surface of the fiber fabric of the top layer of the preform II from the top of the vacuum bag film and the glue solution can be observed in the vacuum tube, the vacuum bag film and the flow guide net are removed.
The preparation steps of the vacuum bag film are as follows: and (3) defoaming the bag-film resin in vacuum, pouring the bag-film resin into a bag-film mold after defoaming, and curing to obtain the vacuum bag film.
The bag film resin comprises one or more of but not limited to silicon rubber, styrene-butadiene rubber and thermoplastic polyurethane.
The thickness of the vacuum bag film is 0.5-8 mm, the side length of the square cavity is 100-500 mm, the radius of the cross section is 0.1-2 mm, and the maximum elongation rate of the deformation of the vacuum bag film is 20-80% under the forming pressure of 0.1 Mpa.
The thickness of the flow guide net is 0.5-1.5 mm, and the compression ratio in the thickness direction after pressurization is 1-20%. Can be bent freely without deformation. Along the X and Y directions in the diversion net surface, the fluid permeability is equal.
The thickness of mould is 10 ~ 80mm, and the length of side is 115 ~ 560mm, and the inside 10mm equidistance of mould four sides is provided with the sealing washer that the width is 5 ~ 50 mm.
As a general inventive concept, the invention provides a carbon nanotube interlayer reinforced resin-based laminated composite material based on a weak impregnation prepreg, and the carbon nanotube interlayer reinforced resin-based laminated composite material is prepared by the preparation method.
Compared with the prior art, the invention has the advantages that:
the invention relates to a carbon nano tube interlayer reinforced resin matrix laminated composite material based on weak impregnation prepreg and a preparation method thereof, the weak impregnation pre-forming body is prepared by superposing the carbon nanotube-containing resin film and the fiber fabric, the natural barrier effect of the reinforced fiber fabric on the carbon nanotubes is utilized, on the basis of researching the macroscopic flow of resin during the forming of a preformed body and determining an impregnation process interval, the preparation method is matched with vacuum-assisted Z-direction melting impregnation and mould pressing solidification forming, the defects that carbon nanotubes are unevenly distributed in the composite material, the agglomeration phenomenon is severe, the orientation degree is poor, the relative content of the prepared carbon nanotubes between layers is less and the content of the prepared carbon nanotubes and the content of fibers is relatively uncontrollable in the traditional methods such as RTM (resin transfer molding) or VIMP (virmp) and the like are solved, a solid technical basis is laid for solving the application problem of the carbon nanotubes in the fiber reinforced resin matrix composite material, and the preparation method can be widely applied in the aspects of scientific research and technical popularization.
Drawings
FIG. 1 is a schematic process flow diagram in example 1 of the present invention.
FIG. 2 is a plot of viscosity versus temperature versus time for preform I of example 1.
FIG. 3 is an appearance photograph and an optical micrograph of a cross section of a fiber reinforced resin based laminated composite material containing carbon nanotubes in between in example 1.
Fig. 4 is a schematic diagram of the distribution of carbon nanotubes in the composite material under different molding processes.
Fig. 5 is an appearance photograph and an optical micrograph of a cross section of the fiber reinforced resin based laminated composite material in comparative example 1.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples. Unless otherwise indicated, all devices or materials used in the practice of the present invention are commercially available.
Example 1
As shown in fig. 1, the preparation method of the fiber reinforced resin based laminated composite material containing carbon nanotubes between layers of the embodiment includes the following steps:
preparing a carbon nanotube-containing weak impregnation prepreg:
1. in this embodiment, the weakly impregnated prepreg includes a fiber fabric and a resin film substrate, carbon nanotubes are distributed in the resin film substrate, the fiber fabric covers the resin film substrate, and a lower surface portion of the fiber fabric is impregnated in the resin film substrate. The number of the weakly-impregnated prepregs is 32, the size of the weakly-impregnated prepregs is 200mm multiplied by 200mm, the mass fraction of the carbon nano tubes is 0.1%, the main component of the resin film is epoxy resin, and the fiber fabric is 6K carbon fiber unidirectional non-woven fabric or 1K carbon fiber plain fabric.
In other embodiments, the resin film is a hot-melt reactive resin, and comprises one or more of epoxy resin, unsaturated polyester resin, bismaleimide and thermosetting polyimide, the fiber fabric is one of unidirectional non-woven fabric, plain weave fabric, satin weave fabric, three-dimensional woven fabric and chopped strand mat, the fiber type is one or more of carbon fiber, glass fiber, kevlar fiber, PBO fiber and ultra-high molecular weight polyethylene fiber, and the same or similar technical effects can be obtained.
The preparation method of the weakly impregnated prepreg of the embodiment comprises the following steps:
a) 5g of carbon nanotube powder and 1000g of an epoxy resin with the trade name EP-3121 were weighed at room temperature. And adding the weighed epoxy resin into a beaker, adding 500g of ethanol into the beaker, mechanically stirring the mixture for 50 minutes at the rotating speed of 1000 rpm, adding carbon nanotube powder after stirring, and continuously stirring for 50 minutes while keeping the rotating speed unchanged to obtain carbon nanotube-containing resin glue solution.
b) Pouring the carbon nanotube-containing resin glue solution into a three-roller grinding machine, and repeatedly grinding for three times, wherein the roller clearance of a feeding roller is as follows in sequence when grinding for three times: 20 μm, 10 μm and 8 μm, the discharge roll gap being in the order: 10 mu m, 5 mu m and 2 mu m, the rotating speed ratio of the feeding roller, the middle roller and the discharging roller is 1:3:9, the rotating speed of the feeding roller is adjusted to 400 r/m, the mixture is poured into a mechanical stirrer after being ground for three times, and the mixture is stirred for 10 minutes at the rotating speed of 1000 r/m to obtain mixed glue solution.
c) Adjusting the gap of a glue spreader, uniformly coating the mixed glue solution obtained in the step b) on release paper to form a film with the thickness of 0.45mm, placing the film in a forced air drying oven at 60 ℃, drying for 5 minutes until the solvent is completely volatilized, and covering the release paper on the upper surface of the dried film to obtain the carbon nanotube-containing resin film.
d) Cutting the carbon nanotube-containing resin film obtained in the step c) into 1 square with the size of 200mm multiplied by 200mm, uncovering release paper on one side of the cut carbon nanotube-containing resin film, overlapping the carbon nanotube-containing resin film with 6K carbon fiber unidirectional non-woven cloth with the same size, and placing the resin film on a horizontal heating table in a downward direction after overlapping.
e) And (3) heating a horizontal heating table to 35 ℃, pressing a rigid flat plate on the upper surface of the 6K carbon fiber unidirectional weftless fabric, applying a positive pressure of 15kPa to the flat plate, keeping for 5 minutes, removing the positive pressure, removing the flat plate, and cooling the horizontal heating table to room temperature to obtain the weak impregnated prepreg.
In this example, a weakly impregnated prepreg in which the fiber fabric was a 1k carbon fiber plain fabric was also prepared.
In the embodiment, the direction components in the surface of the weakly impregnated prepreg are uniform and the thickness is consistent, the number of the carbon nanotube-containing resin films is 1, and the thickness of the carbon nanotube-containing resin film is 0.3mm, in other embodiments, the number of the carbon nanotube-containing resin films can be any integer value from 1 to 10, and the thickness of a single carbon nanotube-containing resin film is 0.05 to 0.3 mm.
The weak impregnation in the weak impregnation prepreg specifically means that the lower surface of the fiber fabric is impregnated with the bottom of the resin film substrate, the thickness of the partial impregnation is D, the thickness of the weak impregnation prepreg is D, and D = 1-10% of D. In this example, the thickness of the fiber fabric was 0.2mm, and the thickness of the partial impregnation was 0.05 mm.
The carbon nano-tube is a single-walled carbon nano-tube or a multi-walled carbon nano-fiber with the same length-diameter ratio of 50-5000 and the diameter of 1-90 nm.
In this example, the mass fraction of the carbon nanotubes was 0.1%, and the carbon nanotubes were uniformly distributed in the resin film and well dispersed. In other embodiments, the carbon nanotubes have a mass fraction of 0.01% to 5%, and can achieve the same or similar technical effects.
Preparation of weakly impregnated preforms:
2. dividing the weakly-impregnated prepreg in the step 1 into two equal parts, wherein each group comprises 16 pieces of (12 pieces of 6k carbon fiber unidirectional weakly-impregnated prepreg and 4 pieces of 1k carbon fiber plain fabric) according to the formula of (fabric)2/0°7]sThe method comprises the following steps of (1) sequentially overlapping, wherein one side of a carbon nanotube-containing resin film of a weakly-impregnated prepreg is overlapped with one side of a fiber fabric of another weakly-impregnated prepreg during overlapping to obtain two identical weakly-impregnated preforms, which are marked as a preform I and a preform II, 1 temperature thermocouples are respectively attached to the interface centers of the 1 st layer, the 2 nd layer, the 8 th layer, the 9 th layer, the 15 th layer and the 16 th layer of the preform I and in one side face of the resin film, and are led out of the preform I in a centralized manner to be connected with a multichannel thermometer, and the preform II is not provided with the temperature thermocouples for standby.
In this example, in the weakly impregnated preform, the surfaces of the laminated fiber fabrics and the resin are weakly impregnated and adhered to each other, and are flat and free of air inclusions.
Determining a melt impregnation process interval:
3. and (3) uniformly coating 2g of resin, namely epoxy resin, with the same components as the carbon nanotube-containing resin film in the step (1) on a rotational rheometer, and setting the test temperature input as the input of an external thermodetector.
4. The heating table was raised to 120 ℃ and held for 10 minutes, placing preform I on the heating table.
5. Keeping the temperature of the heating table surface unchanged until the resin in the preforming body I is completely solidified, recording a viscosity-time curve of a resin system on the rotational rheometer at the temperature of the preforming body I and a temperature-time curve of a multi-channel thermodetector by using a computer to obtain the viscosity-temperature-time curve of the preforming body I shown in figure 2, and determining a melting and dipping process interval.
As can be seen from fig. 2, the graph consists of three curves, a temperature/time curve of the lower bottom surface of the mold, i.e., a temperature/time curve of the heating table; a temperature/time curve of the middle layer of the preformed body I, namely an average temperature/time curve in the preformed body I; the viscosity-time temperature change curve of the resin in the preform I is the viscosity-time temperature change curve measured by a rheometer which obeys the change of the internal temperature of the preform I. When the resin containing the curing agent is heated, the combination of the gradual increase of the internal temperature of the resin and the reduction of the viscosity (physical reason) and the initiation of curing of the curing agent (chemical reason) caused by the increase of the temperature forms a relatively stable and low viscosity platform with low viscosity, wherein the viscosity of 4000mPa · s or less is defined as the low viscosity platform in the embodiment. The vacuum pressure intervention time point is the lowest viscosity position in the low-viscosity platform in the viscosity-time variable temperature curve, and is generally 1-15 minutes before the viscosity is transited from the low-viscosity platform to the viscosity rising section; the vacuum pressure maintaining time is the time from the vacuum pressure intervention time point to the viscosity rising section starting point, and is generally 1-10 minutes after the vacuum pressure intervention time point; and the pressurizing time point of the mould press is the time point that the viscosity begins to be more than 10000mPa.s after passing through a low viscosity platform in the viscosity-time variable temperature curve, the vacuum pressure intervention time point is determined to be 30 minutes (calculated from the time point of the mould temperature to 120 ℃), the vacuum pressure maintaining time period is 5 minutes, the heat preservation time period is 8 minutes, and the pressurizing time point of the mould press is 43 minutes after the flow guide net covering the vacuum bag film and the preformed surface is removed.
Vacuum assisted Z-direction melt impregnation:
6. placing the preformed body II in the middle of a forming mold, laying a flow guide net with the same area and size on the preformed body II, laying a vacuum bag film on the mold, ensuring that the vacuum bag film is in good contact with a sealing ring on the surface of the mold and has no dust inclusion, inserting a vacuum tube into an air outlet above the vacuum bag film, and connecting the other end of the vacuum tube with a buffer tank and a vacuum pump.
In this embodiment, in other embodiments, the thickness of the flow guide net is 1mm, the compression ratio in the thickness direction after pressurization is 10, the flow guide net can be bent at will without deformation, and the fluid permeability is equal in the X and Y directions in the flow guide net surface. The thickness of the vacuum bag film is 4mm, a square cavity with the side length of 200mm is prefabricated in the vacuum bag film, the air outlet is a cross-shaped air guide groove with a semicircular section, the radius of the section is 2mm, and the maximum elongation rate of the deformation of the vacuum bag film is 60% under the forming pressure of 0.1 Mpa.
In this embodiment, the preparation steps of the vacuum bag film are specifically: weighing 150g of polydimethylsiloxane and 15g of sylgard-184 silicone rubber curing agent, mixing, mechanically stirring at room temperature for 20 minutes, placing in a vacuum defoaming barrel for full defoaming, slowly pouring the silicone rubber into a bag film mold after defoaming, and curing at 60 ℃ for 2 hours to obtain a silicone bag film, namely a vacuum bag film.
In other embodiments, the bag film resin includes one or more of but not limited to silicone rubber, styrene-butadiene rubber, thermoplastic polyurethane, and the same or similar technical effects can be achieved.
In other embodiments, the thickness of the flow guiding net is 0.5-1.5 mm, the compression ratio in the thickness direction after pressurization is 1-20%, the thickness of the vacuum bag film is 0.5-8 mm, the side length of the square cavity is 100-500 mm, the section radius is 0.1-2 mm, and the maximum elongation rate of the deformation of the vacuum bag film is 20-80% under the molding pressure of 0.1 Mpa.
7. And (4) placing the molding die packaged in the step 6 under a molding press, and heating the molding die to 120 ℃.
When the forming die is heated for 30 minutes, introducing vacuum pressure, sealing the buffer tank, opening the vacuum pump, slowly opening a pressure regulating valve of the buffer tank, controlling the reduction rate of the average negative pressure within 5kPa/s and 20s, reducing the pressure in the vacuum bag to-101 kPa, maintaining the pressure for 5 minutes until the resin is uniformly discharged from the surface of the top layer fiber fabric of the forming body II from the top of the vacuum bag film, observing a glue solution by the vacuum tube, completely impregnating the resin and the fiber fabric of the forming body II, closing the vacuum pump, removing a flow guide net on the surfaces of the vacuum bag film and the forming body II, keeping the temperature of a die press and the die at 120 ℃, preserving the temperature for 8 minutes, enabling the resin to be close to a gel point, and increasing the viscosity of the resin to obtain the completely impregnated forming body II.
In this embodiment, the thickness of the mold is 30mm, the side length is 380mm, and the four sides of the mold are provided with 10 mm-wide sealing rings inwards by 10mm at equal intervals.
In other embodiments, the thickness of the mold is 10-80 mm, the side length is 115-560 mm, and the sealing rings with the width of 5-50 mm are arranged at the same distance of 10mm inwards on the four sides of the mold, all of which can achieve the same or similar technical effects.
And (3) mould pressing, curing and forming:
9. placing 3mm cushion blocks at four corners of a forming mold, closing the mold by a molding press, pressurizing to 2Mpa, preserving heat until the resin is completely cured, naturally cooling the mold to room temperature, demolding, and polishing the flash of the composite material by using abrasive paper to obtain the fiber reinforced resin matrix laminated composite material.
An appearance photograph and an optical micrograph of a cross section of the fiber reinforced resin based laminated composite material prepared in this example are shown in fig. 3, in which fig. 3a is the appearance photograph and fig. 3b is the optical micrograph of the cross section. As can be seen from fig. 3, the composite material prepared in this example has a flat surface, no obvious buckling of the surface fabric layer, regular fiber arrangement, no resin enrichment in the transition region of the two different fiber fabric layers, a straight and clear interlayer interface, and low porosity.
Fig. 4 is a schematic diagram of the distribution of carbon nanotubes in the composite material under different molding processes. Fig. 4a is a conventional VIMP/RIM process, fig. 4b is a conventional prepreg process, and fig. 4c is a weak impregnation prepreg-based molding process of the present invention. As can be seen from the figure, in the composite material prepared by the forming mode, the carbon nano tubes are uniformly distributed along the whole thickness direction, the interlayer content is high, and the composite material has certain Z-direction orientation degree.
Comparative example 1
The fiber reinforced resin based laminate composite of this comparative example was prepared in substantially the same manner as in example 1, except that:
1. in the step of vacuum-assisted Z-direction melting impregnation, after the vacuum pressure is introduced from a vacuum pressure introduction point, keeping the temperature and the vacuum pressure at 120 ℃ until the resin is completely cured, and removing the vacuum bag film and the flow guide net covered on the preformed surface, namely removing the film to obtain the composite material.
2. Not including the molding, curing and forming steps. Solidification is complete after vacuum assisted Z-direction melt impregnation.
Fig. 5 shows an appearance photograph and a cross-sectional optical micrograph of the fiber reinforced resin based laminate composite prepared in this comparative example, wherein fig. 5a is an appearance photograph and fig. 5b is a cross-sectional optical micrograph. It can be seen from the figure that using exactly the same composite preform as in example 1, the composite prepared by this comparative example has a rough surface topography and severe in-plane buckling of the orthogonal fabric of the surface. In addition, as the vacuum pressure maintaining time of the process of the comparative example is too long and no mould pressing pressure is applied near the gel point, the prepared composite material has the phenomena of excessive extraction of resin among fibers, increased porosity, disordered fiber arrangement and excessive enrichment of resin among layers, and the performance of the composite material is greatly reduced.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments to equivalent variations, without departing from the scope of the invention, using the teachings disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (9)
1. A preparation method of a carbon nanotube interlayer reinforced resin-based laminated composite material based on weak impregnation prepreg is characterized by comprising the following steps: the method comprises the following steps:
s1, laminating the carbon nanotube-containing resin film serving as a substrate and a fiber fabric, and then performing pressure treatment to obtain a weak impregnation prepreg; the resin in the carbon nanotube-containing resin film is one or more of epoxy resin, unsaturated polyester resin, bismaleimide and thermosetting polyimide; the fiber type of the fiber fabric is one or more of carbon fiber, glass fiber, Kevlar fiber, PBO fiber and ultrahigh molecular weight polyethylene fiber;
s2, respectively taking 16 pieces of the weakly impregnated prepreg obtained in the step S1, superposing the pieces of the weakly impregnated prepreg into two identical preformed bodies according to preset requirements, marking the two identical preformed bodies as a preformed body I and a preformed body II, placing temperature sensors in one side surface of the resin film between the 1 st layer and the 2 nd layer, between the 8 th layer and the 9 th layer, and between the 15 th layer and the 16 th layer of the preformed body I, leading the temperature sensors out of the preformed body I, and connecting the temperature sensors with a multichannel thermometer;
s3, coating resin on a rotational rheometer, wherein the resin components are the same as those of resin in a resin film containing carbon nano tubes, setting the test temperature input as the input of an external thermometer, placing the preformed body I obtained in the step S2 on a heating table top at the temperature of 60-200 ℃, recording the viscosity-time curve of the resin on the rotational rheometer and the temperature-time curve of a multi-channel thermometer after the resin in the preformed body I is completely cured, obtaining the viscosity-temperature-time curve of the preformed body II, determining a melting and dipping process interval, obtaining a vacuum pressure intervention time point, a vacuum pressure maintaining time length and a mould pressing time point;
s4, placing the preformed body II obtained in the step S2 on a mold, laying a flow guide net on the preformed body II, laying a vacuum bag film above the mold, and packaging to obtain a packaged mold;
the vacuum bag film is provided with an air outlet, a vacuum tube is inserted into the air outlet, and the air outlet is connected with a vacuum pump through the vacuum tube;
s5, heating the mould packaged in the step S4 to 60-200 ℃, preserving heat, opening a vacuum pump to vacuumize the vacuum bag film at the vacuum pressure intervention time point determined in the step S3 until the pressure in the vacuum bag film reaches a set value, maintaining pressure according to the vacuum pressure maintaining time determined in the step S3, closing the vacuum pump, and removing the vacuum bag film and the flow guide net to obtain a completely-impregnated preform II;
and S6, continuing to keep the temperature, closing the mold and pressurizing the fully-impregnated pre-forming body II obtained in the step S5 through the mold press at the pressurizing time point of the mold press determined in the step S3 until the resin is fully cured, cooling and demolding to obtain the fiber reinforced resin matrix laminated composite material.
2. The method of claim 1, wherein: and a buffer tank is also connected between the gas outlet and the vacuum pump, and a pressure regulating valve is arranged on the buffer tank.
3. The method of claim 2, wherein: in the step S5, the negative pressure reduction rate of the vacuum-pumping treatment is 3.37-6.73 kPa/S, and the pressure set value is-101 kPa.
4. The method of claim 1, wherein: in the step S6, the pressure of the mold closing and pressing is 2 to 6 Mpa.
5. The production method according to any one of claims 1 to 4, characterized in that: in step S1, the preparation method of the weakly impregnated prepreg specifically includes:
s1-1, mixing the resin, the solvent and the carbon nano tube powder, and uniformly stirring to obtain a mixed glue solution;
s1-2, coating the mixed glue solution obtained in the step S1 on a protective film, drying until the solvent is completely volatilized, and covering the protective film to obtain a carbon nanotube-containing resin film;
s1-3, cutting the carbon nanotube-containing resin film and the fiber fabric according to a preset size, removing the protective film on one side of the upper surface of the carbon nanotube-containing resin film obtained in the step S2, overlapping the fiber fabric on the upper surface of the carbon nanotube-containing resin film, and placing the carbon nanotube-containing resin film on a heating table;
s1-4, heating the heating table to 35-50 ℃, carrying out pressure treatment on the fiber fabric, releasing pressure, and cooling to obtain the weak impregnation prepreg.
6. The method of claim 5, wherein: the step S1-1 specifically includes:
a1, mixing the resin and the solvent, stirring uniformly, adding the carbon nanotube powder, and continuously stirring uniformly to obtain a carbon nanotube-containing resin glue solution;
a2, grinding the carbon nanotube-containing resin glue solution, and uniformly stirring to obtain a mixed glue solution.
7. The method of claim 5, wherein: the weak impregnation prepreg comprises a fiber fabric and a resin film substrate, wherein carbon nanotubes are distributed in the resin film substrate, the fiber fabric covers the resin film substrate, and the lower surface part of the fiber fabric is impregnated in the resin film substrate.
8. The method of claim 5, wherein: the solvent is one of ethanol, acetone, tetrahydrofuran and methanol.
9. The production method according to any one of claims 1 to 4, characterized in that: in the viscosity-temperature-time curve of the preform II, the vacuum pressure intervention time point is 1-15 minutes before the viscosity is transited from a low-viscosity platform to a viscosity rising section; the vacuum pressure maintaining time is the time from the intervention time point of the vacuum pressure to the initial point of the viscosity rising section; the press pressurization time point is the time point after the low viscosity plateau at which the viscosity begins to be greater than 10000mPa · s.
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| CN103182784A (en) * | 2013-03-26 | 2013-07-03 | 中材科技风电叶片股份有限公司 | Vacuum infusion forming method for carbon fiber composite structure member |
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