CN113322048B - Carbon nano tube-based film material prepared at normal pressure and preparation method and application thereof - Google Patents
Carbon nano tube-based film material prepared at normal pressure and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a carbon nano tube-based film material prepared at normal pressure, a preparation method and application thereof, wherein the mass percentage of carbon nano tubes in the carbon nano tube-based film material is 50-100%, and the carbon nano tubes are arranged in the surface of the carbon nano tube-based film material and have orientation. The preparation method comprises the following steps: (1) Mixing the carbon nano tube with water, and dispersing to obtain an aqueous dispersion; (2) Extruding and printing the aqueous dispersion on a substrate placed in an organic solvent to obtain a pretreated sample; (3) And taking out the pretreated sample from the organic solvent, and drying the pretreated sample at normal pressure to obtain the carbon nanotube-based film material. The carbon nano tube-based film material has excellent electric conductivity, heat conductivity and electromagnetic shielding function, the preparation method is simple, the production energy consumption and the cost are low, and the large-scale industrialized application can be realized.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a carbon nano tube-based film material, a preparation method and application thereof.
Background
Nanomaterial refers to a material having at least one dimension in three dimensions in the nanoscale, the dimension of which is 0.1 to 100nm, or which is composed of unit types of these basic types. The nano material has special small-size effect and surface effect, excellent mechanical, electrical, optical and thermal properties, and the macroscopic material assembled by the nano material has a plurality of new and excellent functional characteristics, and has very wide application prospect in the fields of mechanics, electronics, optics, thermal and biology and the like. How to realize large-area and large-scale production of macroscopic aggregate materials assembled by nano materials by a flexible, low-cost and green preparation method has been a development focus and challenge in academic and industrial fields.
Carbon Nanotubes (CNT) are a novel carbonaceous nanomaterial, also known as bucky tubes, which can be regarded as one-dimensional hollow tubular nanostructures formed by crimping graphene sheets, and can be several nanometers to tens of nanometers in diameter, and can be several micrometers to several millimeters in length, and have very high aspect ratios and large specific surface areas. The carbon nanotubes can be classified into Single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes and Multi-walled carbon nanotubes (Multi-walled carbon nanotube, MWCNT) according to the number of carbon atom layers on the tube wall, and the Multi-walled carbon nanotubes can be regarded as being formed by coaxially nesting a plurality of Single-walled carbon nanotubes, and the interlayer spacing is 0.34nm. Because the carbon nano tube has excellent properties of force, electricity, heat and the like, the hot trend of researches on the carbon nano tube is initiated, a new chapter of carbon science development is opened up from now on, and people are brought into a new era of nano technology. Through development for twenty years, the carbon nano tube has great results in preparation, structure, performance, application and the like, and research of the carbon nano tube is more and more focused from small-scale preparation in an initial laboratory to current industrialized mass production. However, because the surfaces of these carbon nanomaterials are chemically inert and thus difficult to process or disperse, the construction, preparation and application of carbon nanotube-based macrostructure materials or films is difficult to achieve. Particularly, in order to effectively utilize the one-dimensional carbon nanotube structure, a flexible and scalable preparation technology is studied, so that the carbon nanotubes in the prepared macrostructure film are directionally arranged, and the carbon nanotubes and the carbon nanotube-based film with high performance are obtained.
CN105565295a discloses a preparation method of an oriented carbon nanotube film, which specifically comprises the following steps: A. firstly, polymer modification is carried out on the carboxylated multiwall carbon nanotube, and then magnetic particles are uniformly loaded by a chemical coprecipitation method, so that the multiwall carbon nanotube with magnetism is obtained; B. adding the magnetic carbon nanotubes obtained in the step A into a solvent for dispersion to obtain a carbon nanotube solution; C. pouring the magnetic carbon nanotube solution obtained in the step B into a vacuum filtration device by adopting a vacuum filtration method, and then applying a magnetic field and changing the direction of the magnetic field to obtain an in-plane vertical orientation film or an in-plane parallel orientation film; D. and removing the substrate film by utilizing liquid nitrogen to obtain the oriented carbon nanotube film. The film obtained by the method has uniform and complete structure, the strength of a magnetic field and the grafting rate of magnetic nano particles on the carbon nano tube are changed, and the controllability of the orientation degree can be realized. CN107119262a discloses a method for catalytic growth of carbon nanotube film on the surface of nickel metal matrix, which is a method for catalytic growth of carbon nanotube film based on chemical vapor deposition, and comprises the following main steps: placing the nickel metal matrix subjected to surface pretreatment in a tubular furnace, vacuumizing, introducing argon as carrier gas, heating, and introducing hydrogen to reduce the pretreated nickel metal matrix; continuously heating, introducing a carbon-hydrogen source, and growing a carbon nano tube film on the surface of the nickel metal matrix. The carbon nano tube film catalytically grown by the method is uniform and compact, and has high bonding strength with a nickel metal matrix.
In combination with the above prior art, researchers and industry now mainly prepare carbon nanotube-based films by suspension deposition (e.g., vacuum filtration) or Chemical Vapor Deposition (CVD). However, these production methods have a large limitation such as the former generally requiring an expensive support substrate (e.g., micro-nano cellulose, polytetrafluoroethylene, etc. commercial filtration membrane, etc.) and a low vacuum condition of high energy consumption, and at the same time, it is difficult to tear the self-supporting carbon nanotube or carbon nanotube-based film obtained from the substrate, and thus there are serious limitations in terms of production efficiency and product quality. The CVD method requires high energy consumption and expensive chemical vapor deposition equipment, requires a specific atmosphere (such as carbon dioxide or nitrogen), a specific gas pressure (such as low vacuum), and a specific temperature (ultra low temperature or high temperature), and not only has high energy consumption and long preparation time, but also the CVD synthesized CNT thin film has poor dimensional (thickness and width) controllability. These limitations limit to some extent the large-scale preparation of carbon nanotube-based materials, as well as their large-scale production and use.
Therefore, developing a carbon nanotube film with simple preparation method, low energy consumption, environmental protection and easy mass production is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon nano tube-based film material prepared at normal pressure, a preparation method and application thereof, wherein the carbon nano tube-based film material has an orientation structure, has excellent electric conductivity, heat conductivity and electromagnetic shielding function, is prepared under normal pressure, has a simple preparation method and low production energy consumption and cost, and can realize large-scale industrialized application.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a carbon nanotube-based thin film material prepared at normal pressure, wherein the mass percentage of carbon nanotubes in the carbon nanotube-based thin film material is 50-100%, and the carbon nanotubes are aligned in the plane of the carbon nanotube-based thin film material and have orientation.
The carbon nano tube-based film material provided by the invention takes the carbon nano tubes as a matrix, and the carbon nano tubes are arranged in an orientation mode, so that the excellent force, electricity, heat and other properties of the carbon nano tubes are fully combined, and the carbon nano tube-based film material has high electric conductivity, high heat conductivity and good electromagnetic shielding function.
The mass percentage of the carbon nanotubes in the carbon nanotube-based thin film material is 50-100%, for example, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 95%, 97% or 99%, and specific point values between the above point values, which are limited in space and for brevity, the present invention does not exhaustively list the specific point values included in the range.
In the present invention, the carbon nanotube-based thin film material may be composed of only carbon nanotubes, i.e., the content of carbon nanotubes is 100%; other components, such as functional fillers, polymers or adjuvants, etc., may also be included; the functional filler, polymer or auxiliary agent is uniformly dispersed in the matrix composed of the carbon nano-tubes.
Preferably, the thickness of the carbon nanotube-based thin film material is 0.5 to 900 μm, for example, 0.8 μm, 1.0 μm, 5.0 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, 220 μm, 250 μm, 280 μm, 300 μm, 320 μm, 350 μm, 380 μm, 400 μm, 420 μm, 450 μm, 480 μm, 500 μm, 550 μm, 600 μm, 700 μm, 800 μm or 850 μm, and a specific point value between the above point values is not limited to a range of more preferred range of from 80.8 to 100 μm, although the present invention is not limited to a range of more preferred from 1.80 μm to 80.80 μm.
Preferably, the density of the carbon nano tube-based film material is 100-5000 mg/cm 3 For example, it may be 120mg/cm 3 、150mg/cm 3 、180mg/cm 3 、200mg/cm 3 、250mg/cm 3 、300mg/cm 3 、350mg/cm 3 、400mg/cm 3 、450mg/cm 3 、500mg/cm 3 、550mg/cm 3 、600mg/cm 3 、650mg/cm 3 、700mg/cm 3 、750mg/cm 3 、800mg/cm 3 、900mg/cm 3 、1000mg/cm 3 、1200mg/cm 3 、1500mg/cm 3 、2000mg/cm 3 、2500mg/cm 3 、3000mg/cm 3 、3500mg/cm 3 、4000mg/cm 3 Or 4500mg/cm 3 And specific point values between the above point values, are not exhaustive of the specific point values included in the range, for reasons of space and brevity, and are more preferably 150 to 1500mg/cm 3 More preferably 300 to 1000mg/cm 3 。
Preferably, the carbon nanotubes comprise any one or a combination of at least two of single-walled carbon nanotubes, double-walled carbon nanotubes or multi-walled carbon nanotubes.
Preferably, the carbon nanotubes are surface-modified carbon nanotubes, and the surface modification includes modification of hydrophilic groups.
Preferably, the carbon nanotube-based thin film material further comprises a functional filler.
Preferably, the mass percentage of the functional filler in the carbon nanotube-based film material is 0.1-50%, for example, 0.2%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, and specific point values between the above point values, which are included in the range are not exhaustive for the sake of brevity and conciseness.
Preferably, the functional filler is a metallic filler and/or a nonmetallic filler.
Preferably, the functional filler comprises any one or a combination of at least two of silver nanowires, silver microwires, copper nanowires, copper microwires, gold nanowires, gold microwires, carbon fibers, graphene, aluminum oxide, iron oxide, manganese oxide, silicon carbide, carbon black or Mxenes, and further preferably any one or a combination of at least two of silver nanowires, silver microwires, graphene or Mxenes.
Wherein Mxenes is a carbide, nitride or carbonitride of a two-dimensional transition metal.
In the present invention, the functional filler includes, but is not limited to, nanoscale or microscale functional particles, and the functional characteristics of the functional filler include, but are not limited to, electrical, thermal, and mechanical properties. The introduction of the functional filler enables the carbon nano tube-based film material to have wider application in the fields of structural materials, electrotechnology and the like.
Preferably, the carbon nanotube-based thin film material further comprises a polymer.
Preferably, the mass percentage of the polymer in the carbon nanotube-based thin film material is 0.01-50%, for example, may be 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, and specific point values between the above point values, which are limited in length and for brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the polymer comprises any one or a combination of at least two of cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, lignin, starch, hydroxymethyl starch, starch acetate, vegetable gum, animal glue, polyacrylamide, polyvinylpyrrolidone, aqueous polyurethane, polyacrylic acid, polyacrylate, polyvinyl alcohol (PVA), polyaniline, polylactic acid, polymaleic anhydride or polyethylene glycol, and further preferably any one or a combination of at least two of cellulose, polyvinyl alcohol or aqueous polyurethane.
Preferably, the carbon nanotube-based thin film material further comprises an auxiliary agent.
Preferably, the auxiliary agent comprises any one or a combination of at least two of an antibacterial agent, a reinforcing agent, a flame retardant, a thickener, a compatibilizer, an antioxidant or a tackifier.
Preferably, the mass percentage of the auxiliary agent in the carbon nanotube-based thin film material is 0.01-50%, for example, may be 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 3%, 5%, 7% or 9%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, and specific point values between the above point values, which are limited to a spread and for simplicity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the antibacterial agent comprises chlorhexidine and/or polyhexamethylene biguanide hydrochloride (PHMB).
In the present invention, the morphology and composition of the auxiliary agent include, but are not limited to, inorganic nanoparticles, inorganic microparticles, synthetic small molecules, polymers or biomolecules, etc., and are applied as flame retardants, thickeners, compatibilizers, antioxidants or adhesion promoters to the carbon nanotube-based film material.
In a second aspect, the present invention provides a method for preparing the carbon nanotube-based thin film material according to the first aspect, the method comprising the steps of:
(1) Mixing the carbon nano tube with water, and dispersing to obtain an aqueous dispersion;
(2) Extruding and printing the aqueous dispersion obtained in the step (1) on a substrate placed in an organic solvent to obtain a pretreated sample;
(3) And (3) taking out the pretreated sample obtained in the step (2) from the organic solvent, and drying the pretreated sample at normal pressure to obtain the carbon nanotube-based film material.
In the preparation method provided by the invention, firstly, carbon nano tubes are mixed with water and uniformly dispersed to form aqueous dispersion, then the aqueous dispersion is extruded by a wet method and printed on a substrate placed in an organic solvent, water in the aqueous dispersion is dispersed (or mutually dissolved) in the organic solvent, and dispersoids in the aqueous dispersion are deposited on the substrate to form a film, so that a pretreatment sample is obtained; and taking the pretreated sample out of the organic solvent, and drying the pretreated sample at normal pressure to obtain the carbon nanotube-based film material with the orientation structure. The preparation method has simple process, does not need special atmosphere, pressure or temperature or complicated instrument and equipment, greatly reduces energy consumption and equipment cost, and provides a brand new idea for large-scale industrial production of the carbon nanotube-based film material with an orientation structure.
Preferably, the mass percentage of the carbon nanotubes in the aqueous dispersion in step (1) is 0.01-20%, for example, 0.02%, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15% or 18%, and the specific values between the above values are limited in space and for brevity, and the invention is not intended to be exhaustive list of the specific values included in the range.
Preferably, the carbon nanotubes are hydrophilically modified carbon nanotubes.
Preferably, the hydrophilic modification comprises covalent hydrophilic modification and/or non-covalent hydrophilic modification.
Preferably, the covalent hydrophilic modifying agent comprises any one or a combination of at least two of ozone, sulfuric acid, nitric acid, hydrochloric acid or aqua regia; after the hydrophilic modification reagent is modified, the surface of the carbon nano tube contains hydrophilic groups such as carboxyl and the like, which is beneficial to improving the dispersibility of the carbon nano tube in water.
Preferably, the non-covalent hydrophilic modification is by adding a surfactant to the aqueous dispersion.
Preferably, the surfactant is an ionic surfactant, and more preferably sodium dodecyl sulfate.
Preferably, the aqueous dispersion contains 0.01 to 10% by mass of surfactant, for example 0.03%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 7%, 9% or 9.5%, and the specific values between the above values are limited in length and for simplicity, the invention is not intended to be exhaustive list of the specific values included in the range.
Preferably, the aqueous dispersion further comprises any one or a combination of at least two of functional fillers, polymers or adjuvants.
Wherein the polymer comprises any one or a combination of at least two of cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, lignin, starch, hydroxymethyl starch, starch acetate, vegetable gum, animal glue, polyacrylamide, polyvinylpyrrolidone, aqueous polyurethane, polyacrylic acid, polyacrylate, polyvinyl alcohol, polyaniline, polylactic acid, polymaleic anhydride or polyethylene glycol, and more preferably any one or a combination of at least two of cellulose, polyvinyl alcohol or aqueous polyurethane.
As a preferable embodiment of the present invention, the polymer such as polyvinyl alcohol and cellulose is a hydrophilic polymer, and thus the dispersibility of the carbon nanotubes in water can be improved.
Preferably, the mass percentage of the dispersoids in the aqueous dispersion is 0.1 to 50%, for example, 0.2%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, and the specific point values between the above point values are limited to the extent and for the sake of brevity, the invention is not intended to be exhaustive list of the specific point values included in the range.
In the present invention, the term "dispersoid" means a component other than water in an aqueous dispersion.
In the invention, the dispersion in the step (1) can be assisted by magnetic stirring, ultrasonic and/or other modes, so that each component is uniformly dispersed in water.
Preferably, the organic solvent in step (2) comprises any one or a combination of at least two of ethanol, isopropanol, ethylene glycol, acetone, dichloromethane, chloroform, tetrachloromethane or methyl pyrrolidone, and further preferably acetone and/or isopropanol.
Preferably, the substrate of step (2) comprises any one of a silicone rubber substrate, a polyimide substrate, a polytetrafluoroethylene substrate, or a cellulose fiber substrate.
Preferably, the temperature of the extrusion and printing in the step (2) is 15 to 40 ℃, for example, 16 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, or the like, and more preferably, room temperature.
Preferably, the temperature of the atmospheric drying in the step (3) is 15 to 180 ℃, for example, 18 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 175 ℃, and specific point values between the above point values are possible, and the present invention is not limited to the extent and for the sake of brevity, but more preferably, the specific point values included in the range are not exhaustive.
Preferably, the time of the normal pressure drying in the step (3) is 0.1-24 h, for example, may be 0.3h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h or 22h, and specific point values between the above point values, which are limited in length and for simplicity, the present invention is not exhaustive, and the specific point values included in the range are more preferably 0.5-6 h.
Preferably, the step (3) further comprises a step of peeling the carbon nanotube-based thin film material from the substrate after the atmospheric drying.
Preferably, the aqueous dispersion in the step (1) comprises a surfactant, and the step (3) further comprises a step of removing the surfactant after the drying under normal pressure.
Preferably, the method of removing the surfactant comprises: and (3) placing the sample dried under normal pressure into water for soaking for 1-16 h (for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h or 15h and the like), and drying to obtain the carbon nanotube-based film material.
Preferably, the preparation method specifically comprises the following steps:
(1) Mixing carbon nano tube, water, optional functional filler, optional polymer and optional auxiliary agent, and dispersing uniformly to obtain aqueous dispersion; the mass percentage of the carbon nano tube in the aqueous dispersion is 0.01-20%;
(2) Extruding and printing the aqueous dispersion obtained in the step (1) on a substrate placed in an organic solvent to obtain a pretreated sample; the organic solvent is acetone and/or isopropanol;
(3) And (3) taking out the pretreated sample obtained in the step (2) from the organic solvent, and drying the pretreated sample at 20-100 ℃ under normal pressure for 0.5-6 h to obtain the carbon nanotube-based film material.
In a third aspect, the present invention provides the use of a carbon nanotube-based film material according to the first aspect in an electromagnetic shielding material, an electrothermal material, a fireproof material, a heat conducting material, a filtering material, a sensing material, an electrode material, a building material, a packaging material, a biomedical material, an antibacterial material or a support material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The carbon nano tube-based film material provided by the invention takes the carbon nano tubes which are arranged in an orientation way as a matrix, has controllable thickness, low density, high mechanical strength and flexibility, excellent electric conductivity and heat conductivity, good hydrophobic and waterproof characteristics, solvent resistance, high and low temperature stability, good electric heating performance and high electromagnetic shielding performance, has shielding effectiveness exceeding 50dB under an X wave band, has a proper micropore structure, and can realize a good ventilation function.
(2) The carbon nano tube-based film material also comprises functional filler, polymer and auxiliary agent, the content of which can be adjusted according to the application requirement, so that the carbon nano tube-based film material has wider application in the fields of mechanics, electricity, heat or biological medicine and the like.
(3) The carbon nanotube-based film material provided by the invention is prepared in normal pressure, a low vacuum suction filtration device is not required, special atmosphere, pressure and temperature are not required, complex instruments and equipment are not required, the preparation process is simple, the operation cost is low, the energy consumption and the equipment cost are reduced, large-area production can be realized, and the carbon nanotube-based film material is suitable for large-scale industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of the carbon nanotube-based thin film material provided in example 1;
FIG. 2 is an optical image of the carbon nanotube-based thin film material provided in example 1;
FIG. 3 is a cross-sectional scanning electron microscope image of the carbon nanotube-based thin film material provided in example 1;
FIG. 4 is a graph showing the conductivity test results of the carbon nanotube-based thin film material provided in example 3;
FIG. 5 is a graph showing the results of conducting performance test of the carbon nanotube-based thin film material provided in example 3;
FIG. 6 is a graph showing the results of the flexibility test of the carbon nanotube-based thin film material provided in example 5;
FIG. 7 is a graph showing the low temperature resistance of the carbon nanotube-based thin film material according to example 5;
FIG. 8 is a graph showing the results of solvent resistance testing of the carbon nanotube-based thin film material provided in example 6;
FIG. 9 is a graph showing the surface contact angle of the carbon nanotube-based thin film material according to example 6;
FIG. 10 is a graph showing the results of thermal conductivity testing of the carbon nanotube-based thin film material provided in example 6;
FIG. 11 is a graph showing the pressure drop test results of the carbon nanotube-based thin film material provided in example 8;
FIG. 12 is a graph showing the results of an electro-thermal test of the carbon nanotube-based thin film material provided in example 8;
fig. 13 is an electromagnetic shielding effectiveness chart of the carbon nanotube-based thin film material provided in example 8.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The mass percentage of carbon nano tubes in the carbon nano tube-based film material is 100%, and the carbon nano tubes are single-wall carbon nano tubes which are arranged in the surface of the carbon nano tube-based film material and have orientation.
The preparation method comprises the following steps:
(1) Mixing powdery single-walled carbon nanotubes (diameter distribution is 1-2 nm, average length is 5 μm), sodium Dodecyl Sulfate (SDS) and water to make the mass percent of the single-walled carbon nanotubes in the mixed system be 0.5% and the mass percent of the SDS be 1%, dispersing the single-walled carbon nanotubes by ultrasonic assistance, and further stirring the mixture for 2 hours by using a magnetic stirrer to obtain an aqueous dispersion;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing on a silicon rubber substrate placed in acetone, dissolving water in the aqueous dispersion in the acetone, and depositing dispersoids on the silicon rubber substrate to obtain a pretreated sample;
(3) Taking out the pretreated sample obtained in the step (2) from acetone, drying at 80 ℃ and normal pressure for 4 hours, peeling off the silicon rubber substrate, soaking the obtained material in water overnight, removing small molecular SDS, and fully drying to obtain the carbon nanotube-based film material.
The microscopic morphology test was performed on the carbon nanotube-based thin film material provided in this embodiment by a scanning electron microscope (SEM, JSM-7600F), and the obtained scanning electron microscope is shown in fig. 1, which shows that the arrangement of the single-walled carbon nanotubes has an orientation, and the carbon nanotube-based thin film material has an orientation structure.
The optical image of the carbon nanotube-based thin film material is shown in fig. 2, the scanning electron microscope image of the cross section is shown in fig. 3, and the average thickness of the carbon nanotube-based thin film material is 7 μm as can be seen from fig. 3.
Example 2
The mass percentage of carbon nano tubes in the carbon nano tube-based film material is 100%, and the carbon nano tubes are multi-wall carbon nano tubes which are arranged in the surface of the carbon nano tube-based film material and have orientation.
The preparation method comprises the following steps:
(1) Mixing powdery multi-wall carbon nano-tubes (purchased by Chengdu organic chemistry, with the diameter of about 50nm and the length of 10-20 mu m), SDS and water to ensure that the mass percent of the multi-wall carbon nano-tubes in a mixed system is 10 percent and the mass percent of the SDS is 5 percent, dispersing the multi-wall carbon nano-tubes by ultrasonic assistance, and further stirring the mixture for 3 hours by using a magnetic stirrer to obtain an aqueous dispersion;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing the aqueous dispersion on a silicone rubber substrate placed in isopropanol, dissolving water in the aqueous dispersion in isopropanol, and depositing dispersoids on the silicone rubber substrate to obtain a pretreated sample;
(3) And (3) taking out the pretreated sample obtained in the step (2) from isopropanol, drying at 60 ℃ and normal pressure for 6 hours, stripping the silicon rubber substrate, soaking the obtained film in water overnight, removing SDS, and fully drying to obtain the carbon nanotube-based film material.
Example 3
The mass percentage of carbon nano tubes in the carbon nano tube-based film material is 100%, and the carbon nano tubes are single-wall carbon nano tubes which are arranged in the surface of the carbon nano tube-based film material and have orientation.
The preparation method comprises the following steps:
(1) Mixing powdery single-walled carbon nanotubes, SDS (sodium dodecyl sulfate) and water to ensure that the mass percent of the single-walled carbon nanotubes in a mixed system is 0.5 percent and the mass percent of the SDS is 1 percent, dispersing the single-walled carbon nanotubes by ultrasonic assistance, and further stirring the mixture for 2 hours by using a magnetic stirrer to obtain a dispersion liquid I; mixing the dispersion liquid I with water according to a mass ratio of 1:4, magnetically stirring and dispersing for 2 hours, and uniformly dispersing to obtain an aqueous dispersion liquid;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing the aqueous dispersion on a silicone rubber substrate placed in isopropanol, dissolving water in the aqueous dispersion in isopropanol, and depositing dispersoids on the silicone rubber substrate to obtain a pretreated sample;
(3) And (3) taking out the pretreated sample obtained in the step (2) from isopropanol, drying at 60 ℃ and normal pressure for 6 hours, stripping the silicon rubber substrate, soaking the obtained film in water overnight, removing SDS, and fully drying to obtain the carbon nanotube-based film material.
The conductivity of the carbon nanotube-based thin film material provided in this example was measured by a four-probe method using a Keithley 4200SCS semiconductor parameter analysis system, and the conductivity test chart obtained was shown in fig. 4, wherein the conductivity of the carbon nanotube-based thin film material in the orientation parallel direction reached 2400S/cm, and the conductivity in the orientation perpendicular direction was 1400S/cm.
The carbon nanotube-based thin film material provided in this embodiment was tested for conductivity by the following method: the carbon nano tube-based film material is connected with the LED lamp and the battery (1.5V) in series, after a circuit is connected, the LED lamp emits light, and a graph of a conductive performance test result is shown in fig. 5, which further illustrates that the carbon nano tube-based film material has high conductivity and can drive the LED lamp.
Example 4
The mass percentage of carbon nano tubes in the carbon nano tube-based film material is 100%, and the carbon nano tubes are single-wall carbon nano tubes which are arranged in the surface of the carbon nano tube-based film material and have orientation.
The preparation method comprises the following steps:
(1) Placing the powdery single-walled carbon nanotubes in 98% concentrated sulfuric acid for acidizing treatment to ensure that the surfaces of the powdery single-walled carbon nanotubes are provided with hydrophilic groups (carboxyl and the like); then mixing the mixture with water to enable the mass percentage of the single-walled carbon nano-tube in the mixed system to be 0.2%, dispersing the single-walled carbon nano-tube by ultrasonic assistance, and further stirring the mixture for 2 hours by using a magnetic stirrer, wherein the dispersion is uniform, so as to obtain aqueous dispersion;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing the aqueous dispersion on a silicone rubber substrate placed in isopropanol, dissolving water in the aqueous dispersion in isopropanol, and depositing dispersoids on the silicone rubber substrate to obtain a pretreated sample;
(3) And (3) taking out the pretreated sample obtained in the step (2) from isopropanol, drying at 80 ℃ and normal pressure for 4 hours, and stripping the silicon rubber substrate to obtain the carbon nanotube-based film material.
Example 5
The carbon nano tube-based film material comprises carbon nano tubes and graphene, wherein the mass percentage of the carbon nano tubes is 80%, and the mass percentage of the graphene is 20%; the carbon nanotubes are single-walled carbon nanotubes which are aligned in the plane of the carbon nanotube-based thin film material and have orientation.
The preparation method comprises the following steps:
(1) Mixing powdery single-walled carbon nanotubes, graphene, SDS and water to enable the mass percentage of the single-walled carbon nanotubes in a mixed system to be 2%, the mass percentage of the graphene to be 0.5% and the mass percentage of the SDS to be 0.3%, dispersing the single-walled carbon nanotubes and the graphene by ultrasonic assistance, and further stirring for 2 hours by using a magnetic stirrer, wherein the dispersion is uniform, so as to obtain aqueous dispersion;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing the aqueous dispersion on a silicone rubber substrate placed in isopropanol, dissolving water in the aqueous dispersion in isopropanol, and depositing dispersoids on the silicone rubber substrate to obtain a pretreated sample;
(3) Taking out the pretreated sample obtained in the step (2) from isopropanol, drying at 80 ℃ and normal pressure for 4 hours, stripping a silicon rubber substrate, soaking the obtained material in water overnight, removing small molecular SDS, and fully drying to obtain the carbon nanotube-based film material.
The mechanical properties of the carbon nanotube-based thin film material provided in this embodiment are tested, and the graph of the flexibility test result is shown in fig. 6, where the carbon nanotube-based thin film material can be curled and wound, and the carbon nanotube-based thin film material is free from fracture and has excellent flexibility.
The carbon nanotube-based film material provided in this embodiment is tested for low temperature resistance (liquid nitrogen), and the test result graph is shown in fig. 7, and the carbon nanotube-based film material is bent in liquid nitrogen, so that the carbon nanotube-based film material does not break or crack during bending, and can maintain excellent stability and flexibility in a low-temperature environment.
Example 6
The carbon nano tube-based film material comprises carbon nano tubes and silver nano wires, wherein the mass percent of the carbon nano tubes is 70%, and the mass percent of the silver nano wires is 30%; the carbon nanotubes are single-walled carbon nanotubes which are aligned in the plane of the carbon nanotube-based thin film material and have orientation.
The preparation method comprises the following steps:
(1) Mixing powdery single-walled carbon nanotubes, silver nanowires, SDS and water to ensure that the mass percent of the single-walled carbon nanotubes in a mixed system is 1.4%, the mass percent of the silver nanowires is 0.6%, and the mass percent of the SDS is 0.5%, dispersing the single-walled carbon nanotubes and the silver nanowires by ultrasonic assistance, and further stirring for 2 hours by using a magnetic stirrer, wherein the dispersion is uniform, thus obtaining aqueous dispersion;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing on a silicon rubber substrate placed in acetone, dissolving water in the aqueous dispersion in the acetone, and depositing dispersoids on the silicon rubber substrate to obtain a pretreated sample;
(3) Taking out the pretreated sample obtained in the step (2) from acetone, drying at 80 ℃ and normal pressure for 4 hours, stripping a silicon rubber substrate, soaking the obtained material in water overnight, removing micromolecular SDS, and fully drying to obtain the carbon nanotube-based film material.
The solvent resistance of the carbon nanotube-based thin film material provided in this embodiment was tested, the experimental solvents were ethanol and acetone, and the test results are shown in fig. 8, and the carbon nanotube-based thin film material can maintain excellent stability after being immersed in ethanol and acetone for 30 days.
The contact angle measuring instrument is used for measuring the surface water contact angle of the carbon nanotube-based film material provided by the embodiment, the test chart is shown in fig. 9, the water contact angle is about 120 degrees, and the carbon nanotube-based film material has higher hydrophobic performance.
The thermal conductivity of the carbon nanotube-based thin film material provided in this example was tested with a commercial TDTR thin film thermal conductivity meter (Femto-TDTR) and compared with silver, and the resulting graph of thermal conductivity test results is shown in fig. 10, and the carbon nanotube-based thin film material has anisotropic thermal conductivity, particularly, has high thermal conductivity similar to that of metal (silver) when parallel to the direction in which the carbon nanotubes are oriented.
Example 7
The carbon nano tube-based film material comprises carbon nano tubes and polyvinyl alcohol (PVA), wherein the mass percentage of the carbon nano tubes is 90%, and the mass percentage of the PVA is 10%; the carbon nanotubes are single-walled carbon nanotubes which are aligned in the plane of the carbon nanotube-based thin film material and have orientation.
The preparation method comprises the following steps:
(1) Mixing powdery single-walled carbon nanotubes, PVA, SDS and water to ensure that the mass percent of the single-walled carbon nanotubes in a mixed system is 4.5%, the mass percent of the PVA is 0.5%, the mass percent of the SDS is 0.5%, dispersing the single-walled carbon nanotubes by ultrasonic assistance, and further stirring the mixture for 2 hours by using a magnetic stirrer to obtain an aqueous dispersion;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing the aqueous dispersion on a silicone rubber substrate placed in isopropanol, dissolving water in the aqueous dispersion in isopropanol, and depositing dispersoids on the silicone rubber substrate to obtain a pretreated sample;
(3) Taking out the pretreated sample obtained in the step (2) from isopropanol, drying at 80 ℃ and normal pressure for 3 hours, stripping a silicon rubber substrate, soaking the obtained material in water for 5 hours (changing water every 0.5 hour), removing small molecular SDS, and fully drying to obtain the carbon nano tube-based film material.
Example 8
The carbon nano tube-based film material comprises 67 mass percent of carbon nano tubes and 33 mass percent of cellulose; the carbon nanotubes are single-walled carbon nanotubes which are aligned in the plane of the carbon nanotube-based thin film material and have orientation.
The preparation method comprises the following steps:
(1) Mixing powdery single-walled carbon nanotubes, cellulose nanofibers and water to make the mass percent of the single-walled carbon nanotubes in a mixed system be 1% and the mass percent of the cellulose nanofibers be 0.5%, dispersing the single-walled carbon nanotubes by ultrasonic assistance, and further stirring the mixture for 2 hours by using a magnetic stirrer to obtain an aqueous dispersion;
(2) Placing the aqueous dispersion obtained in the step (1) in a syringe, controlling the syringe to move through a motor, extruding the aqueous dispersion from a syringe needle, printing the aqueous dispersion on a silicone rubber substrate placed in isopropanol, dissolving water in the aqueous dispersion in isopropanol, and depositing dispersoids on the silicone rubber substrate to obtain a pretreated sample;
(3) And (3) taking out the pretreated sample obtained in the step (2) from isopropanol, drying at 80 ℃ and normal pressure for 5 hours, and stripping the silicon rubber substrate to obtain the carbon nanotube-based film material.
The carbon nanotube-based film material provided in this embodiment was tested for air permeability, and compared with a commercial N95 mask, the specific method was as follows:
the pressure sensor (PC 409, omega, inc.) is used to measure the pressure drop at two ends of the sample under different air flow rates, and the graph of the obtained pressure drop test result is shown in fig. 11, and as can be seen from fig. 11, the pressure drop of the carbon nanotube-based film material is lower than that of the commercial N95 mask, which proves that the film material has a microporous structure, and can realize a good ventilation function.
The carbon nanotube-based film material provided by the embodiment is adhered to the electrodes through silver colloid, and the electrode spacing is 30mm; the voltage (1.0V, 1.5V, 1.8V, 2.2V, respectively) was applied between the electrodes, the temperature and time were measured at the surface using a thermocouple, and the resulting graph of the results of the electric heating test was plotted as shown in fig. 12, and it was found from fig. 12 that the carbon nanotube-based thin film material was able to rise to different temperatures and remain stable at different voltages, and had an electric heating function at a lower voltage.
The electromagnetic shielding performance of the carbon nanotube-based thin film material provided in this embodiment was measured using a vector network analyzer (VNA, agilent 8517A), and the obtained electromagnetic shielding performance graph is shown in fig. 13, where the carbon nanotube-based thin film material can have a shielding performance exceeding 50dB in the X-band (8.2-12.4 GHz), and can attenuate electromagnetic waves by more than 99.999%, which is far exceeding the requirement of 20dB for commercial use.
By combining the above embodiments, the carbon nanotube-based film material provided by the invention has an orientation structure, and the preparation method is simple, the operation cost is low, the equipment cost is greatly saved, and the energy consumption is reduced. The carbon nano tube-based film material has high conductivity, good heat conduction performance, excellent mechanical strength, flexibility, solvent resistance, low-temperature stability and air permeability, has hydrophobic surface, waterproof effect, can generate heat electrically, has good electric heating performance, excellent electromagnetic shielding performance, has shielding efficiency exceeding 50dB under an X wave band, and can have wide application prospect in a plurality of fields such as mechanics, electricity, thermal or biological medicine.
The applicant states that the present invention is illustrated by the above examples for the atmospheric-pressure-prepared carbon nanotube-based thin film material of the present invention, and the preparation method and application thereof, but the present invention is not limited to the above process steps, i.e., it does not mean that the present invention must be carried out depending on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (40)
1. The preparation method of the carbon nano tube-based film material prepared at normal pressure is characterized in that the mass percentage of the carbon nano tubes in the carbon nano tube-based film material is 50-100%, and the carbon nano tubes are arranged in the surface of the carbon nano tube-based film material and have orientation;
the preparation method comprises the following steps:
(1) Mixing the hydrophilically modified carbon nanotubes with water, and dispersing to obtain an aqueous dispersion;
(2) Extruding and printing the aqueous dispersion obtained in the step (1) on a substrate placed in an organic solvent to obtain a pretreated sample; the organic solvent is selected from any one or a combination of at least two of ethanol, isopropanol and acetone;
(3) And (3) taking out the pretreated sample obtained in the step (2) from the organic solvent, and drying the pretreated sample at normal pressure to obtain the carbon nanotube-based film material.
2. The method of claim 1, wherein the carbon nanotube-based thin film material has a thickness of 0.5 to 900 μm.
3. The method according to claim 1, wherein the thickness of the carbon nanotube-based thin film material is 0.8 to 100 μm.
4. The method of claim 1, wherein the carbon nanotube-based thin film material has a thickness of 1 to 80 μm.
5. The method according to claim 1, wherein the density of the carbon nanotube-based thin film material is 100 to 5000mg/cm 3 。
6. The method according to claim 1, wherein the density of the carbon nanotube-based thin film material is 150 to 1500mg/cm 3 。
7. The method according to claim 1, wherein the density of the carbon nanotube-based thin film material is 300 to 1000mg/cm 3 。
8. The method of claim 1, wherein the carbon nanotubes comprise any one or a combination of at least two of single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes.
9. The method of claim 1, wherein the carbon nanotube-based thin film material further comprises a functional filler.
10. The preparation method according to claim 9, wherein the functional filler in the carbon nanotube-based film material is 0.1-50% by mass.
11. The method of claim 9, wherein the functional filler is a metallic filler and/or a non-metallic filler.
12. The method of claim 9, wherein the functional filler comprises any one or a combination of at least two of silver nanowires, silver microwires, copper nanowires, copper microwires, gold nanowires, gold microwires, carbon fibers, graphene, alumina, iron oxide, manganese oxide, silicon carbide, carbon black, or Mxenes.
13. The method of claim 9, wherein the functional filler is any one or a combination of at least two of silver nanowires, silver microwires, graphene, or Mxenes.
14. The method of claim 1, wherein the carbon nanotube-based thin film material further comprises a polymer.
15. The method of claim 14, wherein the mass percentage of polymer in the carbon nanotube-based film material is 0.01-50%.
16. The method of claim 14, wherein the polymer comprises any one or a combination of at least two of cellulose, lignin, starch, vegetable gums, animal gums, polyacrylamides, polyvinylpyrrolidone, aqueous polyurethanes, polyacrylic acid, polyacrylates, polyvinyl alcohol, polyaniline, polylactic acid, polymaleic anhydride, or polyethylene glycol.
17. The method of claim 14, wherein the polymer comprises any one or a combination of at least two of hydroxymethyl cellulose, carboxymethyl cellulose, hydroxymethyl starch, and starch acetate.
18. The method of claim 1, wherein the carbon nanotube-based thin film material further comprises an additive.
19. The method of claim 18, wherein the auxiliary agent comprises any one or a combination of at least two of an antimicrobial agent, a reinforcing agent, a flame retardant, a thickener, a compatibilizer, an antioxidant, or a tackifier.
20. The method according to claim 18, wherein the mass percentage of the auxiliary agent in the carbon nanotube-based thin film material is 0.001-50%.
21. The method of preparation of claim 19, wherein the antimicrobial agent comprises chlorhexidine and/or polyhexamethylene biguanide hydrochloride.
22. The method according to claim 1, wherein the mass percentage of the carbon nanotubes in the aqueous dispersion in the step (1) is 0.01 to 20%.
23. The method of claim 1, wherein the hydrophilic modification comprises covalent hydrophilic modification and/or non-covalent hydrophilic modification.
24. The method of claim 23, wherein the covalently hydrophilically modified reagent comprises any one or a combination of at least two of ozone, sulfuric acid, nitric acid, hydrochloric acid, or aqua regia.
25. The method of claim 23, wherein the non-covalent hydrophilic modification is by adding a surfactant to the aqueous dispersion.
26. The method according to claim 25, wherein the mass percentage of the surfactant in the aqueous dispersion is 0.01 to 10%.
27. The method of claim 1, wherein the aqueous dispersion further comprises any one or a combination of at least two of a functional filler, a polymer, or an auxiliary agent.
28. The method according to claim 1, wherein the mass percentage of the dispersoid in the aqueous dispersion is 0.1 to 50%, and the dispersoid refers to the other components than water in the aqueous dispersion.
29. The preparation method according to claim 1, wherein the organic solvent in the step (2) is acetone and/or isopropanol.
30. The method of claim 1, wherein the substrate of step (2) comprises any one of a silicone rubber substrate, a polyimide substrate, a polytetrafluoroethylene substrate, or a cellulose fiber substrate.
31. The method according to claim 1, wherein the temperature of the atmospheric drying in the step (3) is 15 to 180 ℃.
32. The method according to claim 1, wherein the temperature of the atmospheric drying in the step (3) is 20 to 100 ℃.
33. The method according to claim 1, wherein the time for the normal pressure drying in the step (3) is 0.1 to 24 hours.
34. The method according to claim 1, wherein the time for the normal pressure drying in the step (3) is 0.5 to 6 hours.
35. The method according to claim 1, wherein the step (3) further comprises a step of peeling the carbon nanotube-based thin film material from the substrate after the atmospheric drying.
36. The method according to claim 1, wherein the aqueous dispersion in step (1) contains a surfactant, and the step (3) further comprises a step of removing the surfactant after the drying at normal pressure.
37. The method of claim 36, wherein the method of removing surfactant comprises: and (3) soaking the sample dried under normal pressure in water for 1-16 h, and drying to obtain the carbon nanotube-based film material.
38. The preparation method according to claim 1, characterized in that it comprises the following steps:
(1) Mixing the hydrophilically modified carbon nano tube, water, optional functional filler, optional polymer and optional auxiliary agent, and uniformly dispersing to obtain aqueous dispersion; the mass percentage of the carbon nano tube in the aqueous dispersion is 0.01-20%;
(2) Extruding and printing the aqueous dispersion obtained in the step (1) on a substrate placed in an organic solvent to obtain a pretreated sample; the organic solvent is acetone and/or isopropanol;
(3) And (3) taking out the pretreated sample obtained in the step (2) from the organic solvent, and drying the pretreated sample at 20-100 ℃ under normal pressure for 0.5-6 h to obtain the carbon nanotube-based film material.
39. A carbon nanotube-based thin film material prepared by the preparation method according to any one of claims 1 to 38.
40. The use of the carbon nanotube-based film material of claim 39 in electromagnetic shielding material, electrothermal material or heat conducting material.
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