Array carbon nanotube composite film, array carbon nanotube / polymer composite material and preparation method of array carbon nanotube composite film and array carbon nanotube / polymer composite material

Abstract

The invention belongs to the field of material compounding, and relates to an array carbon nanotube composite film, an array carbon nanotube / polymer composite material and a preparation method of the array carbon nanotube composite film and the array carbon nanotube / polymer composite material. The array carbon nanotube composite film comprises array carbon nanotubes and a low surface energy polymer. According to the preparation method, effective transfer and compounding of the array carbon nanotubes can be realized, the length-diameter ratio of the carbon nanotubes is not obviously reduced in the process, meanwhile, defect sites are not additionally introduced, the obtained array carbon nanotube / polymer composite material is better in enhancement and conductivity, the amount of the carbon nanotubes is reduced, and the cost is reduced.

Description

Technical Field

[0001] This invention belongs to the field of composite materials, specifically relating to an arrayed carbon nanotube composite film, a film-like material formed by stacking and hot-pressing arrayed carbon nanotube composite films, a composite material formed by combining the arrayed carbon nanotube composite film or the arrayed carbon nanotube film-like material with a polymer, and methods for preparing them. Background Technology

[0002] Carbon nanotubes, as a novel material with excellent performance at present, are due to the sp(s) of carbon atoms... 2 The hybridized π-π bonds and the one-dimensional linear spatial structure formed by the regular arrangement of carbon atoms endow carbon nanotubes with excellent mechanical, thermal, electrical properties and chemical stability. Therefore, carbon nanotubes have great application potential as additives in the field of composite materials and are commonly used as additives for reinforcing and conductive composite materials.

[0003] Carbon nanotubes can be specifically divided into powdered carbon nanotubes and arrayed carbon nanotubes. Due to their high aspect ratio, powdered carbon nanotubes tend to aggregate and are difficult to disperse uniformly in polymers, significantly reducing their effectiveness in reinforcing composite materials. In contrast, arrayed carbon nanotubes possess ordered directional arrangement and a perfect structure, resulting in physicochemical properties closer to their intrinsic characteristics. If effective composites of arrayed carbon nanotubes with polymer materials can be achieved, their aspect ratio advantage can construct multiple tightly bound network structures within the polymer, not only enhancing the mechanical properties of the composite material but also endowing the material with the inherent thermal, electrical, and chemical stability of carbon nanotubes. However, in current technologies, the preparation of arrayed carbon nanotubes requires a substrate, limiting their transfer and application, and hindering their integration with existing composite processes, thus greatly restricting the development of arrayed carbon nanotubes in the field of composite materials. Summary of the Invention

[0004] The purpose of this invention is to provide an arrayed carbon nanotube composite film and an arrayed carbon nanotube / polymer composite material and their preparation method, aiming to solve the problem of limited transfer and application of arrayed carbon nanotubes in the preparation process of existing technologies, and to achieve effective transfer and composite of arrayed carbon nanotubes.

[0005] A first aspect of the present invention provides an arrayed carbon nanotube composite film, the arrayed carbon nanotube composite film comprising arrayed carbon nanotubes and a low surface energy polymer.

[0006] A second aspect of the present invention provides a method for preparing the above-described arrayed carbon nanotube composite film, comprising the following steps:

[0007] (1) The arrayed carbon nanotubes were prepared by chemical vapor deposition.

[0008] (2) The arrayed carbon nanotubes are exfoliated using a low surface energy polymer to obtain an arrayed carbon nanotube composite film.

[0009] A third aspect of the present invention provides an arrayed carbon nanotube film material, which is prepared by hot pressing multiple layers of the above-mentioned arrayed carbon nanotube composite film.

[0010] The fourth aspect of the present invention provides the above-described arrayed carbon nanotube composite film, the method for preparing the above-described arrayed carbon nanotube composite film, or the application of the above-described arrayed carbon nanotube film material in the preparation of arrayed carbon nanotube composite materials.

[0011] A fifth aspect of the present invention provides an arrayed carbon nanotube / polymer composite material, comprising a polymeric substance and an arrayed carbon nanotube membrane, wherein the arrayed carbon nanotube membrane is the above-mentioned arrayed carbon nanotube composite membrane or the above-mentioned arrayed carbon nanotube membrane material.

[0012] A sixth aspect of the present invention provides a method for preparing the above-described arrayed carbon nanotube / polymer composite material, comprising the following steps:

[0013] The arrayed carbon nanotube membrane is combined with the polymer material to obtain the arrayed carbon nanotube / polymer composite material.

[0014] The beneficial effects of this invention are as follows:

[0015] (1) The carbon nanotubes used in the present invention are arrayed carbon nanotubes. The preparation method of the present invention can effectively exfoliate the arrayed carbon nanotubes and then combine them well with polymer materials. During the process, the aspect ratio of the carbon nanotubes is not significantly reduced and no additional defect sites are introduced. As a result, the arrayed carbon nanotube / polymer composite material provided by the present invention has better reinforcement and conductivity, and the amount of carbon nanotubes used is reduced, thus reducing costs.

[0016] (2) The present invention introduces carbon nanotubes into polymer composite materials by hot pressing film and processing with polymer materials. Compared with the existing technology of dispersing carbon nanotubes in liquid and then using them, the method of the present invention avoids solution mixing and dispersion, which can save solvent costs and has a good environmental protection effect.

[0017] (3) The steps of the method of the present invention are highly independent, the products are independent, and it is easy to apply to industrial production lines for continuous and large-scale assembly line processing operations, and can effectively reduce costs.

[0018] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0019] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0020] In related technologies, the preparation of arrayed carbon nanotubes requires a substrate, which limits their transfer and application. Furthermore, they do not integrate well with current composite processes, greatly restricting the development of arrayed carbon nanotubes in the field of material composites.

[0021] In view of this, the present invention proposes an arrayed carbon nanotube composite film and an arrayed carbon nanotube / polymer composite material and their preparation method. The arrayed carbon nanotubes on the substrate are exfoliated by using a low surface energy polymer and then composited with a polymer to obtain the arrayed carbon nanotube / polymer composite material. This solves the problem of limited transfer and application of arrayed carbon nanotubes in the preparation process of the prior art, and realizes the effective transfer and composite of arrayed carbon nanotubes.

[0022] The present invention provides an arrayed carbon nanotube composite film, wherein the arrayed carbon nanotube composite film comprises arrayed carbon nanotubes and a low surface energy polymer.

[0023] Low surface energy polymers can be used to achieve the exfoliation and composite of arrayed carbon nanotubes. Preferably, the surface energy of the low surface energy polymer is less than 30 mN / m, more preferably less than 25 mN / m.

[0024] This invention can use any polymer that meets the above-mentioned surface energy standard. Preferably, the low surface energy polymer is selected from at least one of fluorocarbon resins, silicone resins, and polyolefins; more preferably, it is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, copolymers of ethylene and trifluoroethylene, copolymers of ethylene and tetrafluoroethylene, copolymers of ethylene and chlorotrifluoroethylene, perfluoroethylene propylene, polyfluoroacrylates, polysiloxanes, polystyrene, polyethylene, and polypropylene. Considering all aspects of performance and ease of application, polytetrafluoroethylene is a preferred choice.

[0025] According to the present invention, from an application perspective, the low surface energy polymer is in the form of a micro powder with a particle size of 0.01–30 μm, preferably 0.02–20 μm. The particle size can be any one of 0.01 μm, 0.02 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm, or a value within a range of any two of the above.

[0026] According to the present invention, the relative contents of arrayed carbon nanotubes and low surface energy polymers can be adjusted within a wide range. To obtain a better exfoliation effect, based on the weight of the arrayed carbon nanotube composite film, the content of the arrayed carbon nanotubes is 0.1 to 50% by weight, and the content of the low surface energy polymer is 50 to 99.9% by weight.

[0027] Specifically, the content of the arrayed carbon nanotubes can be listed as any one of the following values ​​or a range of any two of the above: 0.1 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 15 wt%, 18 wt%, 20 wt%, 23 wt%, 25 wt%, 28 wt%, 30 wt%, 33 wt%, 35 wt%, 38 wt%, 40 wt%, 43 wt%, 45 wt%, 48 wt%, and 50 wt%. The content of the low surface energy polymer can be listed as any one of the following values, or a range of any two of the above values: 50 wt%, 52 wt%, 55 wt%, 57 wt%, 60 wt%, 62 wt%, 65 wt%, 67 wt%, 70 wt%, 72 wt%, 75 wt%, 77 wt%, 80 wt%, 82 wt%, 85 wt%, 87 wt%, 90 wt%, 92 wt%, 95 wt%, 97 wt%, 99 wt%, 99.5 wt%, 99.9 wt%.

[0028] The carbon nanotubes used in this invention for composites are arrayed carbon nanotubes. Preferably, the arrayed carbon nanotubes are horizontally arrayed carbon nanotubes. The arrayed carbon nanotubes can be single-walled or multi-walled. The length of the arrayed carbon nanotubes is preferably in the range of 1 μm to 1 m. The length of the arrayed carbon nanotubes can be any one of the following values: 1 μm, 10 μm, 50 μm, 100 μm, 500 μm, 800 μm, 1 mm, 5 mm, 1 cm, 10 cm, 50 cm, and 1 m, or a value within the range of any two of the above values.

[0029] According to the present invention, the arrayed carbon nanotube composite film is obtained by directly peeling arrayed carbon nanotubes on a substrate using a low surface energy polymer.

[0030] The present invention also provides a method for preparing the above-mentioned arrayed carbon nanotube composite film, comprising the following steps:

[0031] (1) The array of carbon nanotubes was prepared on a substrate by chemical vapor deposition.

[0032] (2) The arrayed carbon nanotubes are peeled off from the substrate using low surface energy polymer powder to obtain the arrayed carbon nanotube composite film.

[0033] The array of carbon nanotubes can be prepared by chemical vapor deposition using methods known in the art. Specifically, step (1) includes: placing a substrate in a horizontal resistance furnace, introducing a carbon source and a carrier gas, and having the carbon source react on the substrate to prepare the array of carbon nanotubes.

[0034] Preferably, the carbon source is a mixture of C1-C in any proportion. 10 Alkanes, C2-C 10 Olefins and C2-C 10 One or more alkynes; the carrier gas is one or more of hydrogen, nitrogen and argon mixed in any proportion; the substrate is a silicon substrate, a silicon oxide substrate or a silicon / silicon oxide substrate; the reaction temperature is 800-1200℃ and the pressure is 0.1-1MPa.

[0035] The key to the exfoliation of arrayed carbon nanotubes in this invention lies in the second step. According to one specific embodiment, step (2) includes:

[0036] Low surface energy polymer powder is sprinkled onto the substrate on which the array of carbon nanotubes is prepared;

[0037] The substrate containing the arrayed carbon nanotubes, which is sprinkled with the low surface energy polymer powder, is heated, and the arrayed carbon nanotubes and the low surface energy polymer are initially combined to obtain the arrayed carbon nanotube composite film.

[0038] The arrayed carbon nanotube composite film is peeled off from the surface of the substrate.

[0039] The heating can be infrared heating, and preferably, the parameter settings for infrared heating include:

[0040] The power of the infrared heating is 200-2000W;

[0041] The infrared heating time is 0.5 to 10 hours.

[0042] The present invention further provides an arrayed carbon nanotube film material, which is obtained by hot pressing after stacking multiple layers of the arrayed carbon nanotube composite film.

[0043] According to the method of the present invention, the multilayer arrayed carbon nanotube composite film is first stacked to obtain a shaped body, and then the shaped body is hot-pressed to obtain a film material.

[0044] This invention does not specifically limit the number of stacked layers; the number of layers can be determined according to the required thickness. Generally, the number of stacked arrayed carbon nanotube composite films is 2 to 20 layers. The thickness of the film material is 200 nm to 5 mm, preferably 100 μm to 5 mm. The thickness of the film material can be any value from 200 nm, 500 nm, 1 μm, 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, or a value within the range of any two of the above values.

[0045] The present invention does not particularly limit the specific form of stacking, but from the perspective of increasing strength, the stacking is preferably cross-stacking.

[0046] The purpose of hot pressing is to integrate the multilayer array carbon nanotube composite film into a single unit. The present invention can adopt suitable hot pressing conditions according to different exfoliated components. Specifically, the hot pressing conditions include: temperature of 50-500℃, preferably 140-450℃; pressure of 0.1-30MPa, preferably 0.5-20MPa; and heat preservation and pressurization time of 0.1-10h, preferably 0.2-5h.

[0047] This invention provides a novel method for exfoliating arrayed carbon nanotubes. The resulting exfoliated arrayed carbon nanotubes, as well as the derived arrayed carbon nanotube molded bodies and arrayed carbon nanotube film materials, can be used to further prepare carbon nanotube composite materials. The composite materials include, but are not limited to, polymeric substances.

[0048] Furthermore, the present invention provides an arrayed carbon nanotube / polymer composite material, comprising a polymer material and an arrayed carbon nanotube membrane composited together, wherein the arrayed carbon nanotube membrane is either the aforementioned arrayed carbon nanotube composite membrane or the aforementioned arrayed carbon nanotube film material. That is, the arrayed carbon nanotube composite membrane obtained by exfoliation can be directly composited with the polymer material, or a multilayer arrayed carbon nanotube composite membrane can be hot-pressed into a film material and then composited with the polymer material. A suitable method can be selected according to the properties of the desired composite material.

[0049] When combining with polymeric materials, the amount of arrayed carbon nanotubes added should be such that it does not affect other properties of the polymeric material itself. Preferably, based on the weight of the composite material, the content of arrayed carbon nanotubes in the composite material is 0.01-20% by weight. Specifically, it can be any one of the following values, or a range of any two of the above values: 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, and 20% by weight. Because the carbon nanotubes are uniformly dispersed in the composite material, adding only 0.01% by weight is sufficient to achieve a reinforcing effect.

[0050] This invention does not have special requirements for the polymeric material used in the composite; it can be one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, nylon, polyester, acrylic, vinylon, styrene-butadiene rubber, butadiene rubber, isoprene rubber, and ethylene propylene rubber mixed in any proportion. Any polymeric material can achieve a reinforcing effect by being composited with the arrayed carbon nanotube film material of this invention.

[0051] Experimental tests showed that, compared with the polymer material, the arrayed carbon nanotube / polymer composite material can increase the strength by 15-300% and the volume conductivity by 10%. 6 above.

[0052] The present invention also provides a method for preparing the above-mentioned arrayed carbon nanotube / polymer composite material, comprising the following steps:

[0053] The arrayed carbon nanotube membrane is combined with the polymer material to obtain the arrayed carbon nanotube / polymer composite material.

[0054] Various composite methods in the art can be employed based on the phase state of the polymer to achieve the composite of the arrayed carbon nanotube film and the polymer. According to one specific embodiment, the preparation method includes the following steps:

[0055] The arrayed carbon nanotube membrane and the polymer material are processed and shaped to obtain the arrayed carbon nanotube / polymer composite material; the processing and shaping are carried out under certain temperature and pressure conditions; preferably, the processing and shaping temperature is 40-500℃, more preferably 50-350℃; the processing and shaping pressure is 0.05-20MPa, more preferably 0.1-10MPa; the processing and shaping time is 0.5min-10h, more preferably 1min-3h.

[0056] According to a specific embodiment of the present invention, the arrayed carbon nanotube / polymer composite material is obtained by exfoliating the arrayed carbon nanotubes with polytetrafluoroethylene (PTFE), further preparing an arrayed carbon nanotube-PTFE macrostructure, and then compounding it with a polymer. Specifically, the preparation method includes the following steps:

[0057] The arrayed carbon nanotubes were prepared using chemical vapor deposition.

[0058] The arrayed carbon nanotubes were exfoliated using the PTFE to obtain an arrayed carbon nanotube-PTFE composite film;

[0059] The arrayed carbon nanotube-PTFE composite film is prepared into an arrayed carbon nanotube-PTFE macrobody, and the arrayed carbon nanotube-PTFE macrobody is formed into a film material by hot pressing.

[0060] The membrane material is combined with the polymer to obtain the arrayed carbon nanotube / polymer composite material.

[0061] The steps for forming the film-like material include:

[0062] The stripped arrayed carbon nanotube-PTFE composite film is cross-stacked in multiple layers to form the arrayed carbon nanotube-PTFE macrostructure;

[0063] The arrayed carbon nanotube-PTFE macrostructure is hot-pressed to obtain the film material.

[0064] The present invention will be further described below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0065] Specific experimental steps or conditions are not specified in the examples; however, they can be performed according to the conventional experimental steps or conditions described in the prior art. Reagents and other instruments used, unless otherwise specified, are all commercially available conventional reagent products.

[0066] In the following embodiments,

[0067] The strength is the tensile strength tested according to the method of GB / T 1040.3-2006.

[0068] Volumetric conductivity was measured according to ASTM-D638 using an RTS 4 four-probe resistivity meter.

[0069] PTFE micro powder: TPD-515H from Taipuda New Materials, surface energy 20-22 mN / m, particle size distribution: D50 < 15.0 μm.

[0070] PTFE ultrafine powder: TPD-603S from Taipuda New Materials, surface energy 20-25 mN / m, particle size distribution: D50 < 3.0 μm.

[0071] Polypropylene powder: Zhongyuan Petrochemical polypropylene FC03, surface energy 28-30 mN / m, sieve particle size 15-20 μm.

[0072] Polysiloxane powder: Shenzhen Xinyongsheng XYS-9223, surface energy 20~25mN / m, particle size 1~2μm.

[0073] Poly(fluoroethylene propylene) powder: Daikin NC-1500, Japan, surface energy 23-27 mN / m, particle size 30 μm.

[0074] Example 1

[0075] This embodiment illustrates an arrayed carbon nanotube composite film and its preparation method according to the present invention, including the following steps:

[0076] (1) Arrayed carbon nanotubes were prepared by chemical vapor deposition.

[0077] In the specific implementation, a silicon substrate was placed in a horizontal resistance furnace, and methane and hydrogen were introduced. The reaction was carried out on the silicon substrate in a hydrogen atmosphere. The reaction temperature was set to 1200℃, and the reaction pressure was set to 0.1MPa. Multi-walled horizontal array carbon nanotubes with a length of 1m were prepared.

[0078] (2) PTFE micro powder was sprinkled on the arrayed carbon nanotubes and infrared heating was performed to obtain an arrayed carbon nanotube-PTFE composite film.

[0079] In practice, a certain proportion of PTFE micropowder is sprinkled onto a silicon substrate on which the aforementioned arrayed carbon nanotubes are prepared. Then, the substrate with the PTFE micropowder and arrayed carbon nanotubes is subjected to infrared heating, with the infrared heating power controlled at 2000W and the heating time at 0.5h, allowing the arrayed carbon nanotubes and PTFE to initially bond, resulting in an arrayed carbon nanotube-PTFE composite film. The obtained arrayed carbon nanotube-PTFE composite film is then peeled off from the substrate surface.

[0080] Example 2

[0081] This embodiment illustrates an arrayed carbon nanotube film material and its preparation method according to the present invention, including the following steps:

[0082] The arrayed carbon nanotube-PTFE composite film peeled off in Example 1 was cross-stacked with 20 layers to form an arrayed carbon nanotube-PTFE macrostructure. The formed arrayed carbon nanotube-PTFE macrostructure was fed into a hot press to obtain a film material with a thickness of 5 mm. The hot pressing conditions included: temperature of 365°C, pressure of 20 MPa, and holding time of 3 hours.

[0083] Example 3

[0084] This embodiment illustrates an arrayed carbon nanotube / polymer composite material and its preparation method according to the present invention, including the following steps:

[0085] The film material obtained in Example 2 was processed and molded with polyethylene material at a temperature of 150°C, a pressure of 5 MPa, and a time of 0.5 h to obtain a uniformly distributed array of carbon nanotubes / polymer composite material.

[0086] In the composite material, the mass fraction of carbon nanotubes is 0.1%, and the mass fraction of PTFE is 1%. The composite material has a 17% higher strength and a 3.8*10⁻⁶ higher volume conductivity compared to pure polyethylene. 7 Tests showed that the aspect ratio of carbon nanotubes did not decrease significantly.

[0087] Example 4

[0088] This embodiment illustrates an arrayed carbon nanotube composite film and its preparation method according to the present invention, including the following steps:

[0089] (1) Arrayed carbon nanotubes were prepared by chemical vapor deposition.

[0090] In the specific implementation, a silicon substrate was placed in a horizontal resistance furnace, and a mixture of C2-C5 alkanes and olefins (ethane, 1-butene, and n-pentane mixed in equal weight ratios) and a mixed carrier gas of hydrogen and argon (1:1, v / v) was introduced. The reaction was carried out on the silicon substrate in the mixed carrier atmosphere of hydrogen and argon, with the reaction temperature set at 800℃ and the reaction pressure set at 0.1 MPa. Single-walled horizontal array carbon nanotubes with a length of 1 μm were prepared.

[0091] (2) PTFE micro powder was sprinkled on the arrayed carbon nanotubes and infrared heating was performed to obtain an arrayed carbon nanotube-PTFE composite film.

[0092] In practice, a certain proportion of PTFE micropowder is sprinkled onto a silicon substrate on which the aforementioned arrayed carbon nanotubes are prepared. Then, the substrate with the PTFE micropowder and arrayed carbon nanotubes is subjected to infrared heating. The infrared heating power is controlled at 200W, and the infrared heating time is 10 hours, allowing the arrayed carbon nanotubes and PTFE to initially bond, resulting in an arrayed carbon nanotube-PTFE composite film. The obtained arrayed carbon nanotube-PTFE composite film is then peeled off from the substrate surface.

[0093] Example 5

[0094] This embodiment illustrates an arrayed carbon nanotube film material and its preparation method according to the present invention, including the following steps:

[0095] The arrayed carbon nanotube-PTFE composite film exfoliated in Example 4 was cross-stacked in two layers to form an arrayed carbon nanotube-PTFE macrostructure. The formed arrayed carbon nanotube-PTFE macrostructure was fed into a hot press to obtain a film material with a thickness of 200 μm. The hot pressing conditions included: temperature of 365°C, pressure of 10 MPa, and holding time of 1 hour.

[0096] Example 6

[0097] This embodiment illustrates an arrayed carbon nanotube / polymer composite material and its preparation method according to the present invention. It includes the following steps:

[0098] The film material obtained in Example 5 was processed and molded with a mixture of polypropylene and polyethylene at a temperature of 200°C, a pressure of 5 MPa, and a time of 0.5 h to obtain a uniformly distributed array of carbon nanotubes / polymer composite material.

[0099] In the composite material, the mass fraction of carbon nanotubes is 10%, the mass fraction of PTFE is 10%, and the strength of the composite material is increased by 245% compared with pure polyethylene, and the volume conductivity is increased by 9.0*10 compared with pure polyethylene. 15 Tests showed that the aspect ratio of carbon nanotubes did not decrease significantly.

[0100] Example 7

[0101] This embodiment illustrates an arrayed carbon nanotube composite film and its preparation method according to the present invention, including the following steps:

[0102] (1) Arrayed carbon nanotubes were prepared by chemical vapor deposition.

[0103] In the specific implementation, a silicon substrate was placed in a horizontal resistance furnace, and methane and hydrogen were introduced. The reaction was carried out on the silicon substrate in a hydrogen atmosphere. The reaction temperature was set to 1000℃, and the reaction pressure was set to 0.1MPa. Multi-walled horizontal array carbon nanotubes with a length of 0.5m were prepared.

[0104] (2) PTFE micro powder was sprinkled on the arrayed carbon nanotubes and infrared heating was performed to obtain an arrayed carbon nanotube-PTFE composite film.

[0105] In practice, a certain proportion of PTFE micropowder is sprinkled onto a silicon substrate on which the aforementioned arrayed carbon nanotubes are prepared. Then, the substrate with the PTFE micropowder and arrayed carbon nanotubes is subjected to infrared heating. The infrared heating power is controlled at 1000W, and the infrared heating time is 5 hours, allowing the arrayed carbon nanotubes and PTFE to initially bond, resulting in an arrayed carbon nanotube-PTFE composite film. The obtained arrayed carbon nanotube-PTFE composite film is then peeled off from the substrate surface.

[0106] Example 8

[0107] This embodiment illustrates an arrayed carbon nanotube film material and its preparation method according to the present invention, including the following steps:

[0108] The arrayed carbon nanotube-PTFE composite film peeled off in Example 7 was cross-stacked with 8 layers to form an arrayed carbon nanotube-PTFE macrostructure. The formed arrayed carbon nanotube-PTFE macrostructure was fed into a hot press to obtain a film material with a thickness of 1 mm. The hot pressing conditions included: temperature of 350°C, pressure of 20 MPa, and holding time of 3 hours.

[0109] Example 9

[0110] This embodiment illustrates an arrayed carbon nanotube / polymer composite material and its preparation method according to the present invention, including the following steps:

[0111] The film material obtained in Example 8 was processed and molded with styrene-butadiene rubber material at a temperature of 130°C, a pressure of 4 MPa, and a time of 1 hour to obtain a uniformly distributed array of carbon nanotubes / polymer composite material.

[0112] In the composite material, the mass fraction of carbon nanotubes is 1%, and the mass fraction of PTFE is 4%. The strength of the composite material is increased by 32% compared to pure styrene-butadiene rubber, and the volume conductivity is increased by 8*10 compared to pure styrene-butadiene rubber. 6 Tests showed that the aspect ratio of carbon nanotubes did not decrease significantly.

[0113] Example 10

[0114] An arrayed carbon nanotube composite film was prepared according to the method of Example 4, except that an equal mass of PTFE ultrafine powder was used instead of PTFE micro powder for the exfoliation of the arrayed carbon nanotubes, resulting in an arrayed carbon nanotube composite film with a thickness of 10 μm. This arrayed carbon nanotube composite film was then directly compounded with a polymer material, and the composite material was prepared according to the method of Example 6. The composite material exhibited a 229% increase in strength and a 4.8 × 10⁻⁶ increase in volume conductivity compared to pure polyethylene. 15 Tests showed that the aspect ratio of carbon nanotubes did not decrease significantly.

[0115] Example 11

[0116] Arrayed carbon nanotube composite films were prepared according to the method of Example 1, except that an equal mass of polypropylene micropowder was used instead of PTFE micropowder for the exfoliation of the arrayed carbon nanotubes. The composite materials were then prepared according to the methods of Examples 2 and 3. The strength of the composite material was increased by 12% compared to pure polyethylene, and the volume conductivity was increased by 5.7 × 10⁻⁶ compared to pure polyethylene. 5 Tests showed that the aspect ratio of carbon nanotubes did not decrease significantly.

[0117] Example 12

[0118] An arrayed carbon nanotube composite film was prepared according to the method of Example 1, except that an equal mass of polysiloxane powder was used instead of PTFE micropowder for the exfoliation of the arrayed carbon nanotubes. The composite material was then prepared according to the methods of Examples 2 and 3. The strength of the composite material was increased by 13.5% compared to pure polyethylene, and the volume conductivity was increased by 2.2 × 10⁻⁶ compared to pure polyethylene. 6 Tests showed that the aspect ratio of carbon nanotubes did not decrease significantly.

[0119] Example 13

[0120] Arrayed carbon nanotube composite films were prepared according to the method of Example 1, except that an equal mass of perfluoroethylene propylene powder was used instead of PTFE micropowder for the exfoliation of the arrayed carbon nanotubes. The composite materials were then prepared according to the methods of Examples 2 and 3. The strength of the composite material was increased by 15.7% compared to pure polyethylene, and the volume conductivity was increased by 8.9 × 10⁻⁶ compared to pure polyethylene. 5 Tests showed that the aspect ratio of carbon nanotubes did not decrease significantly.

[0121] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0122] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. An arrayed carbon nanotube composite film, characterized in that, The arrayed carbon nanotube composite film comprises arrayed carbon nanotubes and a low surface energy polymer.

2. The arrayed carbon nanotube composite film according to claim 1, characterized in that, The surface energy of the low surface energy polymer is less than 30 mN / m, preferably less than 25 mN / m.

3. The arrayed carbon nanotube composite film according to claim 2, characterized in that, The low surface energy polymer is selected from at least one of fluorocarbon resins, silicone resins, and polyolefins; preferably, it is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, copolymers of ethylene and trifluoroethylene, copolymers of ethylene and tetrafluoroethylene, copolymers of ethylene and chlorotrifluoroethylene, perfluoroethylene propylene, polyfluoroacrylate, polysiloxane, polystyrene, polyethylene, and polypropylene.

4. The arrayed carbon nanotube composite film according to claim 1, characterized in that, The low surface energy polymer is in the form of micro powder with a particle size of 0.01–30 μm, preferably 0.02–20 μm.

5. The arrayed carbon nanotube composite film according to claim 1, characterized in that, Based on the weight of the arrayed carbon nanotube composite film, the content of the arrayed carbon nanotubes is 0.1-50% by weight, and the content of the low surface energy polymer is 50-99.9% by weight.

6. The arrayed carbon nanotube composite film according to claim 1, characterized in that, The arrayed carbon nanotubes are horizontally arrayed carbon nanotubes; the arrayed carbon nanotubes are single-walled or multi-walled; the length of the arrayed carbon nanotubes ranges from 1 μm to 1 m.

7. The arrayed carbon nanotube composite film according to any one of claims 1-6, characterized in that, The arrayed carbon nanotube composite film is obtained by directly peeling the arrayed carbon nanotubes off the substrate using a low surface energy polymer.

8. A method for preparing the arrayed carbon nanotube composite film according to any one of claims 1-7, comprising the following steps: (1) The array of carbon nanotubes was prepared on a substrate by chemical vapor deposition. (2) The arrayed carbon nanotubes are peeled off from the substrate using a low surface energy polymer to obtain the arrayed carbon nanotube composite film.

9. The method for preparing the arrayed carbon nanotube composite film according to claim 8, characterized in that, Step (1) includes: placing a substrate in a horizontal resistance furnace, introducing a carbon source and a carrier gas, wherein the carbon source reacts on the substrate to prepare the array of carbon nanotubes; Preferably, the carbon source is a mixture of C1-C in any proportion. 10 Alkanes, C2-C 10 Olefins and C2-C 10 One or more alkynes; the carrier gas is one or more of hydrogen, nitrogen and argon mixed in any proportion; the substrate is a silicon substrate, a silicon oxide substrate or a silicon / silicon oxide substrate; the reaction temperature is 800-1200℃ and the pressure is 0.1-1MPa.

10. The method for preparing the arrayed carbon nanotube composite film according to claim 8, characterized in that, Step (2) includes: Low surface energy polymer powder is sprinkled onto the substrate on which the array of carbon nanotubes is prepared; The substrate containing the arrayed carbon nanotubes, which is sprinkled with the low surface energy polymer powder, is heated, and the arrayed carbon nanotubes and the low surface energy polymer are initially combined to obtain the arrayed carbon nanotube composite film. The arrayed carbon nanotube composite film is peeled off from the surface of the substrate.

11. The method for preparing the arrayed carbon nanotube composite film according to claim 10, characterized in that, The heating is infrared heating, and preferably, the parameter settings for the infrared heating include: The power of the infrared heating is 200-2000W; The infrared heating time is 0.5 to 10 hours.

12. An arrayed carbon nanotube film material, characterized in that, The arrayed carbon nanotube film material is obtained by hot pressing after stacking multiple arrayed carbon nanotube composite films, and the arrayed carbon nanotube composite film is the arrayed carbon nanotube composite film according to any one of claims 1-7.

13. The arrayed carbon nanotube film material according to claim 12, characterized in that, The number of layers in the stacked array of carbon nanotube composite film is 2 to 20; the stacking is preferably cross-stacking.

14. The arrayed carbon nanotube film material according to claim 12, characterized in that, The thickness of the film material is 200 nm to 5 mm, preferably 100 μm to 5 mm.

15. The arrayed carbon nanotube film material according to claim 12, characterized in that, The hot pressing conditions include: a temperature of 50–500℃, preferably 140–450℃; a pressure of 0.1–30 MPa, preferably 0.5–20 MPa; and a heat preservation and pressurization time of 0.1–10 h, preferably 0.2–5 h.

16. The arrayed carbon nanotube composite film according to any one of claims 1-7, the method for preparing the arrayed carbon nanotube composite film according to any one of claims 8-11, or the application of the arrayed carbon nanotube film material according to any one of claims 12-15 in the preparation of arrayed carbon nanotube composite materials.

17. An arrayed carbon nanotube / polymer composite material, characterized in that, It includes a polymeric material and an arrayed carbon nanotube membrane, wherein the arrayed carbon nanotube membrane is the arrayed carbon nanotube composite membrane according to any one of claims 1-7 or the arrayed carbon nanotube membrane material according to any one of claims 12-15.

18. The arrayed carbon nanotube / polymer composite material according to claim 17, characterized in that, Based on the weight of the composite material, the content of arrayed carbon nanotubes in the composite material is 0.01–20% by weight.

19. The arrayed carbon nanotube / polymer composite material according to claim 17, characterized in that, The polymeric material is one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, nylon, polyester, acrylic, vinylon, styrene-butadiene rubber, butadiene rubber, isoprene rubber, and ethylene propylene rubber, mixed in any proportion.

20. The method for preparing the arrayed carbon nanotube / polymer composite material according to any one of claims 17-19, characterized in that, Includes the following steps: The arrayed carbon nanotube membrane is combined with the polymer material to obtain the arrayed carbon nanotube / polymer composite material.

21. The method for preparing arrayed carbon nanotube / polymer composite material according to claim 20, characterized in that, Includes the following steps: The arrayed carbon nanotube membrane and the polymer material are processed and shaped to obtain the arrayed carbon nanotube / polymer composite material; preferably, the processing temperature is 40-500℃, more preferably 50-350℃; the processing pressure is 0.05-20MPa, more preferably 0.1-10MPa; the processing time is 0.5min-10h, more preferably 1min-3h.