CN109749107B - A kind of oriented carbon nanotube/resin film and preparation method thereof - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 117
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 117
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- 239000011347 resin Substances 0.000 title claims abstract description 108
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- 229920000647 polyepoxide Polymers 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
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- 239000005041 Mylar™ Substances 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 235000012239 silicon dioxide Nutrition 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 1
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Abstract
本发明公开了一种定向取向的碳纳米管/树脂膜，包括树脂膜和碳纳米管，所述碳纳米管呈阵列形式分布且自树脂膜内延伸至树脂膜外，所述碳纳米管的延伸方向与树脂膜的厚度方向之间的夹角为α，0°≤α≤15°，所述碳纳米管的长径比为500～5000，所述树脂膜的成分为热熔反应性树脂。本发明还公开了前述碳纳米管/树脂膜的制备方法包括以下步骤：树脂膜加热熔融，树脂膜垂直于阵列轻压粘带，冷冻降温成膜。本发明的制备工艺实施简单，碳纳米管取向度及形貌保持良好。
The invention discloses a carbon nanotube/resin film with directional orientation, comprising a resin film and carbon nanotubes. The carbon nanotubes are distributed in an array form and extend from the inside of the resin film to the outside of the resin film. The angle between the extending direction and the thickness direction of the resin film is α, 0°≤α≤15°, the aspect ratio of the carbon nanotubes is 500-5000, and the composition of the resin film is a hot melt reactive resin . The invention also discloses the preparation method of the carbon nanotube/resin film, which comprises the following steps: heating and melting the resin film, lightly pressing the adhesive tape perpendicular to the array, and freezing and cooling to form a film. The preparation process of the invention is simple to implement, and the orientation degree and morphology of the carbon nanotubes are kept well.
Description
Technical Field
The invention relates to the field of resin-based composite carbon nanotube macroscopic aggregates, in particular to a directionally oriented carbon nanotube/resin film and a preparation method thereof.
Background
A large number of researches show that the carbon nano tube is introduced between layers of the composite material, so that the capability of resisting layering damage of the FRP composite material can be effectively improved, and the heat conduction and the electric conduction of the resin between the layers can be obviously improved. Furthermore, when the carbon nano tubes are oriented along the thickness direction of the composite material between layers, the promotion effect is more obvious. The carbon nanotube array is prepared by adopting template catalyst CVD, the carbon nanotubes are perpendicular to a growth substrate and are periodically arranged along the in-plane direction, and the carbon nanotube macro aggregate has consistent orientation degree, appearance and height, and can adjust the length-diameter ratio and the surface density (tube-tube spacing) of the carbon tubes by controlling the growth conditions of the carbon nanotubes. The carbon nano tube array has the geometric characteristics and physical characteristics of uniform in-plane distribution, good vertical orientation degree and consistent and controllable appearance, well meets the requirements of traditional FRP composite material interlaminar toughening on the geometric appearance, distribution and process of the carbon nano tube, and is an effective composite material interlaminar functional modification and toughening phase.
The reason why the carbon nanotubes have such a high degree of orientation is that strong van der waals force exists between each carbon nanotube and the surrounding carbon nanotubes in the carbon nanotube array, so that the carbon nanotubes maintain their morphology and do not fall down. However, when the array is transferred or secondarily processed, the balance of van der waals forces therein is easily broken by external force due to lack of substrate support, and the array is broken or scattered. Furthermore, when the carbon nanotube array is independently inserted as an interlaminar reinforcement, the pressure between adjacent fiber lay-ups during the forming process can severely disrupt the orientation and distribution of the carbon nanotube array due to the lack of resin impregnation. The above problems have greatly limited their engineering applications, especially in the area of interlaminar toughening of composite materials.
The ideal carbon nanotube for interlayer toughening should be a rigid needle with a relatively large long diameter, so in order to enhance the reinforcing effect as much as possible, the length-diameter ratio of the carbon nanotube should be as large as possible. However, the research shows that the intrinsic growth defects of the carbon nanotubes, such as 5-7-7-5 formed on the tube wall and carbon atom hole defects, increase along with the increase of the height of the carbon nanotube array. The defects not only influence the intrinsic comprehensive properties of the carbon nano tube, such as force, electricity, heat and the like, but also obviously influence the intrinsic appearance of the carbon nano tube, particularly the orientation degree (the orientation degree is reduced) and the waviness (the waviness is increased). In addition, the axial bending rigidity and the room temperature resistance of the excessively high carbon nanotube array are obviously reduced, when the array is operated in the thickness direction, the phenomena of bending and lodging are more easily caused due to the reduction of the axial rigidity, and in addition, the excessively high carbon nanotube array can increase the fiber layer spacing of the composite material, so that the total thickness of the final composite material is improved. The problem that the length-diameter ratio of the carbon nanotube array can be effectively reduced can be solved, but the mechanical property aspect can cause the carbon nanotube reinforcing and toughening efficiency to be reduced by excessively reducing the length-diameter ratio of the carbon nanotube array, and the process aspect can cause the cracking and the damage of the carbon nanotube array in the processes of transferring and secondary forming due to the fact that the height of the carbon nanotube array is reduced and the Van der Waals force between the carbon nanotubes is reduced. In conclusion, the carbon nanotube with a specific length-diameter ratio is selected as the interlayer reinforcing phase, which is significant.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a carbon nano tube/resin film which is easy to prepare and store, wide in application, simple in transfer operation, good in shape and orientation degree of the carbon nano tube and suitable for oriented orientation between composite material layers and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the carbon nano tube/resin film comprises a resin film and carbon nano tubes, wherein the carbon nano tubes are distributed in an array form and extend out of the resin film from the inside of the resin film, the included angle between the extending direction of the carbon nano tubes and the thickness direction of the resin film is alpha, alpha is more than or equal to 0 degrees and less than or equal to 15 degrees, the length-diameter ratio of the carbon nano tubes is 500-5000, and the component of the resin film is hot-melt reactive resin.
As a further improvement to the above technical solution:
the carbon nanotube comprises an embedded part and an extended part, wherein the embedded part is positioned in the resin film, the extended part is positioned outside the resin film, and the length of the embedded part is 5-50% of the total length of the carbon nanotube.
The height of the carbon nano tube is 1-150 mu m, the diameter of the carbon nano tube is 2-30 nm, and the duty ratio of the carbon nano tube on the resin film is 0.1-5%.
The hot-melt reactive resin is one or more of epoxy resin, unsaturated polyester resin, bismaleimide and thermosetting polyimide.
The gel time of the hot-melt reactive resin is more than 15 minutes at the temperature of 60-200 ℃.
As a general inventive concept, the present invention also provides a method of preparing an aligned carbon nanotube/resin film, comprising the steps of:
s1, adhering the back of the pretreated substrate loaded with the carbon nanotube array to a clamping device, wherein the thickness direction of the carbon nanotube array is vertical to the horizontal direction;
s2, adhering the lower surface of the resin film on a horizontal heating plate, and adjusting a clamping device and/or the horizontal heating plate to enable the carbon nanotube array to be positioned above the resin film and not to be in contact with the resin film;
s3, heating the horizontal heating plate until the temperature of the upper surface of the resin film reaches 35-50 ℃ so that the resin film is in a semi-molten state;
s4, moving the clamping device downwards along the vertical direction, applying positive pressure when the carbon nanotube array is in contact with the surface of the resin film, so that the end part of the carbon nanotube array is immersed in the resin film in a semi-molten state, and removing the positive pressure;
s5, cooling the horizontal heating plate to-10-5 ℃, lifting the clamping device to separate the carbon nanotube array from the substrate and completely transferring the carbon nanotube array to a base resin film to obtain the carbon nanotube/resin film.
As a further improvement to the above technical solution:
in the step S1, the pretreatment is a weak oxidation heat treatment, specifically: and (3) placing the substrate with the carbon nanotube array grown, prepared by the template method, in a reaction device, and heating at 450 ℃ for 5 minutes in a protective gas atmosphere to obtain the pretreated substrate loaded with the carbon nanotube array.
The shielding gas is 98% volume fraction argon and 2% volume fraction oxygen.
The step S2 specifically includes:
s2-1, pressing epoxy resin into an epoxy resin film with the thickness of 0.05-0.3 mm at the temperature of 40-130 ℃, and covering polyester films easy to uncover the film on the upper surface and the lower surface of the epoxy resin film to obtain a resin film;
s2-2, processing the resin film into a preset size at 0-35 ℃, and pasting the lower surface of the resin film on a horizontal heating plate;
s2-3, adjusting a clamping device and/or a horizontal heating plate to enable the carbon nanotube array to be positioned above the resin film and not to be in contact with the resin film.
The step S2-3 is followed by removing the mylar film from the upper surface of the resin film.
Preferably, in the step S4, the pressure is applied for 4 to 20kPa for 30 to 120S.
Compared with the prior art, the invention has the advantages that:
the carbon nanotube/resin film effectively combines a carbon nanotube array and a resin film, the carbon nanotube is a carbon nanotube macroscopic aggregate with consistent appearance, controllable array height, high orientation degree and excellent mechanical and electrical properties, the resin film is a hot-melt reactive resin, is suitable for forming fiber composite materials, and has the advantages of good film forming property, mechanical properties after curing and the like. The carbon nano tube/resin film is easy to shape and process at normal temperature, can be melted and dipped when heated, and is well adapted to the composite material forming process.
The carbon nano tube/resin film and the preparation method thereof adopt the resin film as the substrate, effectively overcome the problem that the carbon nano tube with small length-diameter ratio is easy to damage in the processes of transfer and secondary forming, and have simple implementation process, high carbon nano tube orientation degree and orderly and intact arrangement of the carbon nano tubes. Meanwhile, the resin film is a resin which can be kept in a solid state at normal temperature but can be bent at will and can be melted and flow at high temperature and has curing activity, the application range of the carbon nano tube array in the field of fiber reinforced resin matrix composite materials is widened, particularly the resin film can be applied to a resin film melting and dipping process and a glue film for gluing the composite materials, the adjustable and directional reinforcing and toughening can be carried out on the interlayer or the joint of the composite material layers, after the carbon nano tube/the resin film is inserted between the composite material layers, the good infiltration and the good bonding can be formed between the layers, the orientation degree and the appearance of the carbon nano tube are kept good, meanwhile, certain thermal and electrical functional characteristics can be endowed to the composite materials, and the carbon nano tube/resin film composite material has wide application prospect.
Drawings
FIG. 1 is a graph of viscosity versus time for a resin film in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph showing the appearance of a carbon nanotube array in example 1 of the present invention.
Fig. 3 is a schematic view of a flow of manufacturing a carbon nanotube/resin film according to example 1 of the present invention.
Fig. 4 is a schematic view of a structural model of a carbon nanotube/resin film according to example 1 of the present invention.
Fig. 5 is a photograph of the carbon nanotube/resin film of example 1 of the present invention.
Fig. 6 is an SEM picture and a frequency histogram of the distribution of degree of orientation of the carbon nanotube/resin film of example 1 of the present invention.
FIG. 7 is a graph of viscosity versus time for a resin film in example 2 of the present invention.
Fig. 8 is an SEM picture and a frequency histogram of the distribution of degree of orientation of the carbon nanotube/resin film of example 2 of the present invention.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples.
Example 1
The resin film of this example was a 0.3mm thick, externally milky-white high viscosity epoxy film having a viscosity of 10.9 pas at 80 ℃ and 1.1 pas at 120 ℃ and a thickness of 0.3mm, and the viscosity-time curve at 120 ℃ is shown in FIG. 1. The resin film of the embodiment has certain flexibility at 0-35 ℃, can be bent freely without deformation and flow, and has gradually reduced viscosity along with temperature rise.
In other embodiments, the resin film may be made of one or more of unsaturated polyester resin, bismaleimide and thermosetting polyimide, and the same or similar technical effects can be obtained.
The carbon nanotubes of this example are carbon nanotube arrays with a height of 30 μm, a carbon nanotube diameter of 10nm, an aspect ratio of 3000, and a duty cycle on the resin film of 1%, as shown in FIG. 2.
The method for preparing the carbon nanotube/resin film according to the embodiment, as shown in fig. 3, includes heating and melting the resin film, lightly pressing the adhesive tape perpendicular to the carbon nanotube array, and freezing and cooling the adhesive tape to form the film, and specifically includes the following steps:
1. the carbon nanotube array prepared by the template CVD method and the substrate are horizontally placed in a quartz tube furnace to be subjected to weak oxidation heat treatment, 98% of argon and 2% of oxygen in volume fraction are introduced into a hearth, the temperature of the hearth is set at 450 ℃, and the heating time is 5 minutes, so that the binding force between the carbon nanotube array and the substrate is reduced.
2. The temperature of a resin hopper is controlled to be 80 ℃, the gap between opposite compression rollers is adjusted to be 0.3mm, epoxy resin is pressed into an epoxy resin film with the thickness of 0.3mm by adopting a calendering method, the thickness is uniform and complete, no convex wrinkles exist, and the upper surface and the lower surface of the epoxy resin film are covered with film paper (in the embodiment, release paper is used for finishing the protection and packaging of the epoxy resin film, so that the resin film is obtained, and the subsequent transportation and use are facilitated.
3. And adhering the back surface of the silicon dioxide substrate on which the carbon nanotube array grows to the clamp, and after the silicon dioxide substrate containing the carbon nanotube array is positioned and installed, the thickness direction of the carbon nanotube array is vertical to the horizontal direction. The clamp holder has the functions of positioning in the horizontal direction and moving up and down in the vertical (namely vertical) direction; and the holder is placed along a horizontal plane.
4. Cutting the resin film in the step 2 to 20mm × 20mm at 25 ℃, adhering the lower surface of the resin film on a horizontal heating flat plate, and simultaneously, vertically placing a holder above the resin film precisely and keeping the carbon nanotube array from contacting the resin film.
5. Tearing off the film paper on the upper surface of the resin film, controlling the temperature of the horizontal heating plate to be 40 ℃, keeping for 2mins, applying 10kPa downward pressure to the holder when the temperature of the upper surface of the resin film reaches 40 ℃ and the resin film is in a semi-molten state, slowly moving the holder downwards along the vertical direction to enable the carbon nanotube array to be in contact with the surface of the resin film, keeping for 60s, enabling the end part of the array to be immersed in the semi-molten resin, and removing the pressure.
In other embodiments, the pressure is 4 to 20kPa, and the holding time is 30 to 120s, all of which can achieve the same or similar technical effects.
6. The horizontal heating plate is cooled to-10 deg.C, the holder is slowly raised, the carbon nanotube array is separated from the substrate, and the carbon nanotubes are completely transferred to the resin film, to obtain the carbon nanotube/resin film, as shown in FIGS. 4 and 5.
Fig. 6 is an SEM picture and a frequency histogram of the distribution of degree of orientation of the carbon nanotube/resin film of example 1 of the present invention. Wherein, fig. 6a is an SEM photograph, fig. 6b is an orientation degree distribution frequency histogram, and it can be seen from the figure that the resin and the carbon nano tube are well impregnated without pore defects, the morphology of the carbon nano tube is kept intact after impregnation, and the orientation degree along the Z direction is high.
Example 2:
the carbon nanotube/resin film of this example was prepared in substantially the same manner as in example 1, except that:
(1) the resin film of this example was an epoxy resin film having a pale yellow appearance, a viscosity of 5.8 pas at 80 ℃ and a viscosity of 0.6 pas at 120 ℃, a thickness of 0.15mm, and a viscosity-time curve at 120 ℃ as shown in FIG. 7.
(2) In step 2, the thickness of the resin film was 0.15 mm.
(3) In step 5, the cutting temperature of the resin film was 10 ℃.
(4) In step 6, the temperature of the horizontal heating plate was controlled to 35 ℃.
(5) In step 7, the temperature of the horizontal heating plate is reduced to 5 ℃.
Fig. 8 is an SEM picture and a frequency histogram of the distribution of degree of orientation of the carbon nanotube/resin film of example 2 of the present invention. Wherein, fig. 8a is an SEM photograph, fig. 8b is an orientation degree distribution frequency histogram, and it can be seen from the figure that for a resin with a slightly low viscosity, the impregnation of the resin and the carbon nanotubes is still good without void defects, the morphology of the impregnated carbon nanotubes remains intact, and the orientation degree in the Z direction is high.
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 (5)
1. A method for preparing a carbon nanotube/resin film having an orientation, characterized by: the method comprises the following steps:
s1, adhering the back of the pretreated substrate loaded with the carbon nanotube array to a clamping device, wherein the thickness direction of the carbon nanotube array is vertical to the horizontal direction;
s2, adhering the lower surface of the resin film on a horizontal heating plate, and adjusting a clamping device and/or the horizontal heating plate to enable the carbon nanotube array to be positioned above the resin film and not to be in contact with the resin film;
s3, heating the horizontal heating plate until the temperature of the upper surface of the resin film reaches 35-50 ℃ so that the resin film is in a semi-molten state;
s4, moving the clamping device downwards along the vertical direction, applying positive pressure when the carbon nanotube array is in contact with the surface of the resin film, so that the end part of the carbon nanotube array is immersed in the resin film in a semi-molten state, and removing the positive pressure;
s5, cooling the horizontal heating plate to-10-5 ℃, lifting the clamping device to separate the carbon nanotube array from the substrate and completely transferring the carbon nanotube array to a resin film to obtain the carbon nanotube/resin film.
2. The method of claim 1, wherein: in the step S1, the pretreatment is a weak oxidation heat treatment, specifically: and (3) placing the substrate with the carbon nanotube array grown, prepared by the template method, in a reaction device, and heating at 450 ℃ for 5 minutes in a protective gas atmosphere to obtain the pretreated substrate loaded with the carbon nanotube array.
3. The method of claim 2, wherein: the shielding gas is 98% volume fraction argon and 2% volume fraction oxygen.
4. The production method according to any one of claims 1 to 3, characterized in that: the step S2 specifically includes:
s2-1, pressing epoxy resin into an epoxy resin film with the thickness of 0.05-0.3 mm at the temperature of 40-130 ℃, and covering polyester films easy to uncover the film on the upper surface and the lower surface of the epoxy resin film to obtain a resin film;
s2-2, processing the resin film into a preset size at 0-35 ℃, and pasting the lower surface of the resin film on a horizontal heating plate;
s2-3, adjusting a clamping device and/or a horizontal heating plate to enable the carbon nanotube array to be positioned above the resin film and not to be in contact with the resin film.
5. The method of claim 4, wherein: the step S2-3 is followed by removing the mylar film from the upper surface of the resin film.
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| WO2002076724A1 (en) * | 2001-03-26 | 2002-10-03 | Eikos, Inc. | Coatings containing carbon nanotubes |
| CN1699452A (en) * | 2004-05-19 | 2005-11-23 | 中国航空工业第一集团公司北京航空材料研究院 | High volume fraction carbon nanotube array-resin matrix composite material and preparation method |
| CN101054467A (en) * | 2006-04-14 | 2007-10-17 | 清华大学 | Carbon nano-tube composite material and preparation method thereof |
| CN108473312A (en) * | 2015-12-28 | 2018-08-31 | 日立造船株式会社 | Carbon nanotube composite material and method for producing carbon nanotube composite material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002076724A1 (en) * | 2001-03-26 | 2002-10-03 | Eikos, Inc. | Coatings containing carbon nanotubes |
| CN1699452A (en) * | 2004-05-19 | 2005-11-23 | 中国航空工业第一集团公司北京航空材料研究院 | High volume fraction carbon nanotube array-resin matrix composite material and preparation method |
| CN101054467A (en) * | 2006-04-14 | 2007-10-17 | 清华大学 | Carbon nano-tube composite material and preparation method thereof |
| CN108473312A (en) * | 2015-12-28 | 2018-08-31 | 日立造船株式会社 | Carbon nanotube composite material and method for producing carbon nanotube composite material |
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