TWI377172B - Carbon nanotube composite material and method for making the same - Google Patents

Description

1377172 Modified on September 20, 2011, page 6, invention: [Technical Field] [0001] The present invention relates to a carbon nanotube composite material and a preparation method thereof, and more particularly to an electron emission source Nano carbon tube composite material and preparation method thereof. [Prior Art]

[0002] Carbon Nanotube (CNT), as a new type of carbon material, has excellent electrical conductivity, large aspect ratio and tip surface area close to the theoretical limit (the smaller the tip surface area, the higher the local electric field Concentrated), thus having good field emission properties. Field emission electron sources fabricated using carbon nanotubes have extremely low field emission voltages (less than 100 volts) and extremely high current densities, and are expected to be widely used in field emission displays, vacuum devices such as X-ray tubes and ionization gauges. However, in the prior art, a field emission electron source made of a carbon nanotube can maintain excellent field emission performance only under a high vacuum higher than 10_5 Torr, and an increase in the number of ions generated under a low vacuum such as 10_3 Torr. Its structure is easily damaged by ion bombardment. Therefore, the field emission electron source will have obvious current decay and cannot maintain stable operation. [0003] The field emission electron source fabricated by using the carbon nanotube is difficult to work stably under low vacuum, and Jihua Zhang et al. introduced a field emission electron source capable of stable operation under low vacuum, and the field emission electron source is The carbon nanotube composite material comprises a carbon nanotube and a layer of tantalum carbide coated on the outer surface of the carbon nanotube. See "Improvement of field emission of carbon nanotubes by hafnium coating and annealing" 0_05Bill No. A0101 Page 4/Total 40 Page 1013359402-0 1377172 101. September 20th Nuclear Replacement Page, Jihua Zhang et, Nanotechnology. 17, (2006) 257-260. The carbon nanotube composite material is prepared by forming a carbon nanotube array on a P-type ruthenium substrate by chemical vapor deposition; forming a metal ruthenium layer on the surface of the carbon nanotube array; Annealing at a temperature of 1200 degrees causes the metal ruthenium to react with carbon atoms in the carbon nanotubes to form lanthanum carbide, thereby forming an ion bombarded carbonized bell layer on the surface of the carbon nanotube. [0004] In the preparation process of the above carbon nanotube composite material, complicated heating equipment heating is required, and the annealing process is complicated. Therefore, the preparation method of the carbon nanotube composite material is complicated. SUMMARY OF THE INVENTION [0005] In view of the above, it is necessary to provide a method for preparing a carbon nanotube composite material having a simple method and a carbon nanotube composite material prepared by the preparation method. [0006] A method for preparing a carbon nanotube composite material, comprising the steps of: providing a carbon nanotube structure, the carbon nanotube structure comprising at least one carbon nanotube; forming a metal coating layer thereon An outer surface of at least one carbon nanotube in the carbon nanotube structure; energizing the carbon nanotube structure in a vacuum to melt the metal coating on the outer surface of the carbon nanotube and in the carbon nanotube The carbon atom reacts to form a plurality of metal carbide particles on the outer surface of the carbon nanotube. In this step, the carbon nanotube structure is heated to a first temperature after being energized in a vacuum, and the metal coating is Melting at the first temperature, the first temperature is greater than or equal to a reaction temperature of the metal coating layer and the carbon nanotubes. [0007] A method for preparing a carbon nanotube composite material, comprising the following steps: 1013359402-0 09810905^^'^^ A〇101 ^ 5 1 / ^ 40 1 1377172 September 20th, 2011 a nanocarbon carbon line-like structure comprising: a plurality of carbon nanotubes extending along an axial direction thereof; forming a metal coating layer of at least one carbon nanotube in the nanocarbon line structure An outer surface; the carbon carbon line-like structure is energized in a vacuum to heat the nanocarbon line-like structure to a first temperature, and the metal coating on the outer surface of the carbon nanotube is melted and the carbon nanotube a carbon atom reaction, forming a plurality of metal carbide particles on the outer surface of the carbon nanotube; energizing the nematic carbon line structure in a vacuum to heat the nanocarbon line structure to a second temperature, thereby The rice carbon line-like structure breaks and forms two tips at the break, and in this step, the second temperature is greater than the first temperature. [0008] A method for preparing a carbon nanotube composite material, comprising the steps of: providing a carbon nanotube film: the carbon nanotube film comprises a plurality of films extending in the same direction and connected end to end by van der Waals force a carbon nanotube; forming a metal coating on the outer surface of at least one of the carbon nanotubes in the carbon nanotube film; treating the carbon nanotube film with an organic solvent to shrink into a nano carbon line a structure in which the nanocarbon line-like structure is energized in a vacuum to heat the nanocarbon line-like structure to a first temperature, so that the metal coating on the outer surface of the at least one carbon nanotube is melted and bonded to the nano Reacting a carbon atom in the carbon tube to form a plurality of metal carbide particles on the outer surface of the carbon nanotube; energizing the nanocarbon line-like structure in a vacuum to heat the nanocarbon line structure to a second temperature The nanocarbon line-like structure breaks and forms two tips at the break, and in this step, the second temperature is greater than the first temperature. Page 6 of 40 [0009] - a carbon nanotube; material, the towel, the carbon nanotube composite material comprises a carbon nanotube structure, the surface of the carbon nanotube structure is formed with a plurality of 09810905# single No. 1010101 Page 6 of 40 Page 1013359402-0

Γ377172 101. September 20th, revised replacement page The metal carbide particles are separated by a gap of 1 nanometer to 100 nanometers between two adjacent metal carbide particles. [0010] A carbon nanotube composite material, wherein the carbon nanotube composite material comprises a carbon nanotube structure, wherein at least one carbon nanotube has at least one surface formed on the outer surface of the carbon nanotube structure The carbide particles have a gap of between 1 nm and 100 nm between two adjacent metal carbide particles. [0011] a carbon nanotube composite material, wherein the carbon nanotube composite material comprises a carbon nanotube, the surface of the carbon nanotube is formed with a plurality of spaced metal Φ carbide granules, two adjacent The metal carbide particles have a gap of between 1 nm and 100 nm. [0012] Compared with the prior art, the method for preparing the carbon nanotube composite material can heat the metal cladding layer to a first temperature to make the metal cladding layer by energizing the carbon nanotube structure in a vacuum. After melting, the molten metal coating reacts with carbon atoms in the carbon nanotube structure to form a plurality of metal carbide particles on the outer surface of the carbon nanotube structure. The method for preparing the carbon nanotube composite material has a simple heating method and does not require a complicated annealing process, thereby making the preparation method of the carbon nanotube composite material simpler. [Embodiment] The preparation method of the carbon nanotube composite material provided by the embodiment of the present invention and the carbon nanotube composite material prepared by the preparation method will be described in detail below with reference to the accompanying drawings. Referring to FIG. 1, a method for preparing a carbon nanotube composite material according to a first embodiment of the present invention includes the following steps. 09810905癸单号A0101 Page 7/Total 40 Page 1013359402-0 1377172 September 20th, 2011 Shuttle replacement page [0015] Step S101, providing a carbon nanotube structure, the carbon nanotube structure including at least one Carbon tube. The carbon nanotube structure is a carbon nanotube array, the carbon nanotube array is obtained by chemical vapor deposition, and the van der Waals force exists between the carbon nanotubes in the carbon nanotube array. . For the growth method of the carbon nanotube array, please refer to the patent application of No. 20040 72 59 published by Fan Shoushan et al. on November 5, 2002, published on May 15, 2004. The carbon nanotube structure may also be a single carbon nanotube or a self-supporting carbon nanotube structure, and the self-supporting carbon nanotube structure comprises a carbon nanotube composed of a plurality of carbon nanotubes. Membrane or nanocarbon line structure. Specifically, the single carbon nanotube comprises a conductive single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. The carbon nanotube membrane may comprise a carbon nanotube flocculation membrane, a carbon nanotube membrane or a carbon nanotube membrane, the nanocarbon pipeline structure comprising at least one nanocarbon pipeline. [0016] The carbon nanotube flocculation crucible is obtained by flocculation treatment on a carbon nanotube array, and the carbon nanotubes in the carbon nanotube flocculation membrane are intertwined or isotropically aligned. For the structure and preparation method of the carbon nanotube flocculation membrane, please refer to Taiwan Patent Application No. 0961 1 6824, which was filed on May 11, 2008, by Fan Shoushan et al., and published on November 16, 2008. The carbon nanotube rolled film can be obtained by extruding the carbon nanotube array in a direction perpendicular to the substrate grown by the array of carbon nanotubes by using a planar indenter, and the carbon nanotube film is pressed at this time. The carbon nanotube is isotropic; referring to Fig. 2, the carbon nanotube rolled film can also be obtained by rolling the carbon nanotube array in a fixed direction by using a roller-shaped indenter. The carbon nanotubes in the carbon nanotube rolled film are preferentially oriented in the fixed direction; the carbon nanotube rolled film can also be rolled in different directions by using a roller-shaped indenter. A〇101 Page 8 of 40 1013359402-0 Γ377172 ____________ 1101·September 20 is obtained by replacing the first carbon nanotube array, at this time, the carbon nanotubes in the carbon nanotube film Preferred orientation in different directions. For the structure and preparation method of the carbon nanotube rolled film, please refer to Taiwan Patent Application No. 096123694, which was filed on Jun. 29, 2007 by Fan Shoushan et al. [0017] The carbon nanotube film comprises a plurality of carbon nanotubes connected end to end by van der Waals force and arranged in a preferred orientation in the same direction. For the structure of the carbon nanotube film and the preparation method thereof, please refer to the patent application of CN101239712A, published on February 9, 2008 by Fan Shoushan et al., published on August 13, 2008. [0018] The nanocarbon line-like structure includes at least one nano carbon line, please refer to FIG. 3 and FIG. 4, the nano carbon line includes a plurality of carbon nanotubes extending or rotating in an axial direction thereof, preferably, The complex carbon nanotubes are connected end to end by Van der Valli. The nano-crushed line structure may comprise a bundle structure consisting of a plurality of nano-breaking pipelines side by side or a twisted wire structure composed of mutually twisted. The carbon nanotube structure may also be composed of a plurality of nano carbon line-like structures arranged in parallel, intertwined or interwoven. [0019] The nanocarbon pipeline can be obtained by subjecting a carbon nanotube membrane to organic solvent treatment or mechanical force twisting, and the nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by van der Waals force. The non-twisted nanocarbon pipeline obtained by the organic solvent treatment comprises a plurality of carbon nanotubes arranged in the length direction of the nanocarbon pipeline and connected end to end. The twisted nanocarbon pipeline known by mechanical force torsion includes a plurality of carbon nanotubes arranged in an axially spiral arrangement around the carbon nanotubes. The nano carbon line is not limited in length and has a diameter of 〇5 nm to 100 μm. The nano carbon pipeline obtained by the organic solvent treatment and the preparation method thereof can be found in Fan Shoushan et al. on December 16, 2005. 〇 _9〇 5# single number A0101 S 9 pages / total 40 pages 1013359402-0 1377172 [0020] Step S1 02', which forms a metal coating on the outer surface of at least one of the carbon nanotube structures in the carbon nanotube structure, is disclosed in Japanese Patent Application No. 094144790, which is incorporated by reference. Preferably, a metal cladding layer is formed on the outer surface of each of the carbon nanotube structures. The material of the metal coating layer is a transition metal, including ruthenium, osmium, titanium or ruthenium. The metal coating layer forming method comprises a magnetron sputtering method or an electron beam evaporation method, and the metal coating layer has a thickness of between 1 nm and 100 nm, and the metal coating layer is located by a particle diameter range. The metal particles between the nanometer and the nanometer are formed by joining each other. In the present embodiment, the metal clad layer is a 50 nm thick germanium layer formed by magnetron sputtering. _1] Step S103, energizing the carbon nanotube structure in the Qin air, melting the metal coating of the outer surface of the carbon carbon and reacting with the carbon atoms in the carbon nanotube, in the carbon nanotube The outer surface forms a plurality of metal carbide particles. Specifically, the carbon nanotube structure can be fixed and electrically connected between the two electrodes, and the carbon nanotube structure and the electrode are placed in a vacuum environment, and a voltage is applied between the electrodes to make the carbon nanotube. The structure is energized. [0022] In the present embodiment, the carbon nanotube structure is a carbon nanotube array, and the carbon nanotube array is generally formed on a substrate, and the carbon nanotube array can be covered and adhered by one of the electrodes. One end, the array of carbon nanotubes is detached from the substrate, and the other electrode is electrically connected to one end of the array of carbon nanotubes and the substrate. At this time, the plurality of carbon nanotubes in the array of carbon nanotubes extend along one of the electrodes to the other electrode, so that the array of carbon nanotubes forms a loop with the electrode and the power source. Since the carbon nanotube structure is a good conductor of electricity, the carbon nanotube structure is a conductive structure, so that 09810905^ is numbered Α0101, page 10/total 40 pages, 1013359402-0, Γ377172

[0023]

[0024] 101 years. September 20th nuclear replacement page The carbon nanotube array is heated when energized. Of course, a plurality of carbon nanotubes can be obtained from the carbon nanotube array by a tool such as tweezers to form a carbon nanotube structure electrically connected between the two electrodes. At this time, the nanometer between the two electrodes The resistance of the carbon tube structure is further increased than that of the carbon nanotube array, which is favorable for being heated. The carbon nanotube structure is heated in a relatively simple manner without the need for externally complicated heating equipment, and the heating method can control the heating temperature by controlling the magnitude of current or voltage. At the same time, the heating method does not require an external heat source and raises the ambient temperature around the carbon nanotube structure, which has high heating efficiency and saves energy. It will be understood by those skilled in the art that when the carbon nanotube structure is a flocculated film or an isotropic laminated film, the carbon nanotubes are disorderly arranged due to the arrangement of the carbon nanotubes in the carbon nanotube structure. The structure is electrically conductive in all directions, so the electrode can be anywhere in the structure of the carbon nanotube. When the carbon nanotube structure is a fixed direction oriented rolling film, a carbon nanotube film or a nano carbon line structure, the electrode should be disposed at both ends in the direction of arrangement of the carbon nanotubes, thereby The carbon nanotubes extend along one electrode to the other. Of course, the manner in which the carbon nanotube structure is energized in a vacuum is not limited to the use of two electrodes, and a plurality of electrodes may be employed. [0025] The carbon nanotube structure is heated to a first temperature after being energized in a vacuum, and the first temperature is a reaction temperature of the metal cladding layer and the carbon nanotube. In this embodiment, the first temperature is 1 600K. When the carbon nanotube structure is heat-treated at 1 600 K, the metal particles in the metal coating layer are at a nanometer level, and the melting point is remarkably lowered, so that the metal particles are melted at a temperature of 1 600 K, and the metal The carbon atoms in contact with the cladding layer are dispersed in the metal coating layer to form a metal carbide. Since the molten surface _1_5# single number is deleted 1 page 11 / total 40 pages 1013359402-0 1377172 On September 20, 2010, the effect of the replacement sheet tension is corrected, and the generated metal carbide exists in the form of particles, and the particle size range thereof It is located between 1 nm and 100 nm, and a plurality of metal carbide particles are formed at a certain distance, and the distance between two adjacent metal carbide particles is between 1 nm and 100 nm. [0026] In the method for preparing a carbon nanotube composite material provided by the embodiment of the present invention, the molten metal coating layer reacts with carbon atoms in the carbon nanotube structure to form an outer surface of the carbon nanotube structure. A plurality of metal carbide particles are formed. The carbon nanotube composite material can be obtained without a complicated annealing process, thereby simplifying the preparation method of the carbon nanotube composite material. The carbon nanotube structure is also very simple to heat. The carbon nanotube structure can be heated in a vacuum to heat the metal coating to a first temperature to melt the metal coating without complicated heating. The temperature range of the carbon nanotube structure can be controlled by controlling the range of energization current or voltage of the carbon nanotube structure; and the electric energy is converted into heat energy through the inner resistance of the carbon nanotube, from the inside of the carbon nanotube The heat is heated to the outer metal layer of the coating, and the energy utilization rate is high. [0027] Referring to FIG. 5, a method for preparing a carbon nanotube composite material according to a second embodiment of the present invention includes the following steps. [0028] Step S201, providing a nanocarbon pipeline structure, the nanocarbon pipeline structure including a plurality of carbon nanotubes extending along the axial direction thereof. Preferably, the plurality of carbon nanotubes are connected end to end by van der Waals force. [0029] Step S202, forming a metal coating layer on the outer surface of at least one of the carbon nanotubes in the nanocarbon line structure. [0030] Step S203, energizing the nanocarbon line-like structure in a vacuum to make the nanometer 09_5癸 single number A〇101 page 12/total 40 pages 1013359402-0 Γ377172 [0031] • 1101. September 20 Repairing the carbon pipeline structure to a first temperature, melting a metal coating on the outer surface of the carbon nanotube and reacting with carbon atoms in the carbon nanotube to form a plurality of metals on the outer surface of the carbon nanotube Carbide particles. The first temperature is the reaction temperature of the carbon nanotubes and the metal coating. Step S204' energizes the nanocarbon line-like structure in a vacuum to heat the carbon nanotube structure to a second temperature, causing the nanocarbon line-like structure to break and form a tip at the fracture end. The nanocarbon line-like structure is heated at a different temperature due to uneven heat or heat dissipation, and a portion where the temperature rises rapidly breaks and contracts, thereby forming a tip at one end of the fracture. For example, when the nanocarbon line-like structure is fixed at opposite ends and electrically connected between the two electrodes, the nanocarbon line-like structure is fixed on the electrode or near the electrode when heated, and the heat dissipation is faster. The heat away from the electrode is relatively slow, so when heated to the second temperature, a certain section of the nanocarbon line-like structure breaks and contracts, thereby forming a tip at one end of the fracture. The tip is a bundle structure formed by connecting a plurality of carbon nanotubes through a van der Waals force, and a carbon nanotube is extended at the end of the tip and the carbon nanotube is passed through the adjacent carbon nanotube Devalli fixed. [0032] With respect to the method of preparing the carbon nanotube composite material in the first embodiment, the carbon nanotube composite material in the embodiment of the present invention has a tip end having a smaller diameter at the end. Therefore, when the nano carbon camp wire structure is applied to the field emission electron emission source, the required field emission voltage is lower. [0033] Please refer to FIG. 6 'the third embodiment of the present invention - the carbon nanotube A method of preparing a retanning material, comprising the following steps. 09810905^单号A01〇l Page 13/Total 40 Page 1013359402-0 [0034] [0037] [0037] On September 20, 101, the shuttle replacement page provides two electrodes and a carbon nanotube For the membrane, please refer to Figure 7. The carbon tube (4) includes a plurality of carbon nanotubes extending in the same direction and connected end to end. = S3G2 domain - a metal coating on the outer surface of at least the naphthalene tube in the carbon nanotube film. Preferably, the carbon nanotubes in the nanotubes are formed with a metal coating. Please refer to _9. In the present embodiment, the metal coating layer is a 5Q nanometer thick layer. The carbon nanotube film is treated with an organic solvent to shrink the carbon nanotube-like structure. After the carbon nanotube film is treated by an organic solvent, the outer surface area is reduced, and the heat resistance is improved. In this implementation, the carbon nanotube is treated with an organic solvent to form a straight H wire. 34 micron Na H line structure. Of course, the carbon nanotube film can also be mechanically twisted to reduce the outer surface area, and the organic solvent is reversed after the mechanical force is reversed, or the carbon nanotube is The film is subjected to an organic solvent treatment and then mechanically twisted.

Step S304, energizing the nanocarbon line-like structure in a vacuum to heat the nanocarbon line-like structure to a first temperature, so that the metal coating on the outer surface of the at least one carbon carbon camp is melted and reacted with the nanometer. The carbon atoms in the carbon tube react to form a plurality of metal carbide particles on the outer surface of the carbon nanotube. The first temperature of β Hai is the reaction temperature of the metal coating layer and the nano tube. In this embodiment, the first temperature is 16〇〇1 (the heating voltage is 1〇2〇)

Between the special. Referring to Fig. 11, the diameter or wire diameter of the nanocarbon line-like structure having a plurality of metal carbide particles is reduced, resulting in an increase in density. However, the diameter or diameter of the nanocarbon pipeline structure can be increased, and the field increase can be increased. 09810905#单号Α0101 Page 14/40 pages 1013359402-0 λ factor 'increased_nano carbon tube·structure field Emission effect „ See Figure 12 to Figure 14 for details, the metal carbide particles have a particle size ranging from 1 nm to 10 G nm, which is distributed outside each nanocarbon officer in the nanocarbon line structure. The surface is wire-bonded to the outer wall of the carbon nanotube. The metal carbide particles distributed on the outer surface of the same-nanocarbon tube also have a distance between the i nanometer and the 1GG nanoparticle. The metal carbide particles are When carbonization is given, it exists in the form of a crystal of a face-centered cubic lattice. _] #STEPS3G5, the carbon-carbon line-like structure is passed through a vacuum, and the carbon nanotube-like structure is heated to a second temperature, so that The nano carbon line structure is broken, and the nano carbon line structure forms a tip end at the end of the fracture. In the embodiment, the second temperature at which the nano carbon line structure is broken is above 2136K. The heating voltage is above 2 volts. Please refer to Figure 15 to Figure 17, the nanocarbon. After the pipeline structure is melted, it has a tip at the break, and the wire diameter of the tip is much smaller than the wire diameter of the nanocarbon pipeline structure, further enhancing the field emission of the Nylon carbon pipeline structure. Compared with the preparation method of the carbon nanotube composite material in the second embodiment of the present invention, the carbon nanotube structure in the embodiment of the present invention adopts a carbon nanotube film. The majority of the carbon nanotube film is drawn. The carbon nanotubes overlap in the normal direction of the carbon nanotube pulling, and the different carbon nanotubes have a gap, so the metal coating is more easily formed in the carbon nanotube film. The outer surface of each of the carbon nanotubes, thereby enabling the metal carbide to be uniformly distributed on the surface of the carbon nanotube structure. 3 The carbon nanotubes prepared by the preparation method of the carbon nanotube composite material Coffee (10) a single material, which includes a carbon nanotube structure and is formed on the carbon nanotube junction 1 page 15 / total 40 pages 1013359402-0 1377172 September 20, the shuttle is replacing the plural of the surface of the page Metal carbide particles. The metal carbide particles can be formed Part of the surface or the entire surface of the carbon nanotube structure, specifically, the metal may be distributed on the outer surface of the plurality of carbon nanotubes in the carbon nanotube structure, or may be decorated on the carbon nanotube structure An outer surface. Preferably, the metal carbide particles are uniformly dispersed on the outer surface of each of the carbon nanotube structures or the carbon nanotube structure. The particle size range of the metal carbide particles Located between 1 nanometer and 〇〇 nanometer, it is distributed on the outer surface of each of the carbon nanotubes in the carbon nanotube and linear structure and is deposited on the outer wall of the carbon nanotube. The metal carbon 4 compound particles on the outer surface of the rice pipe have a distance between the nanometer and the nanometer. When the metal carbide particle is tantalum carbide, it exists in the form of a crystal of the face-centered cubic lattice [_ The nai tube structure comprises a nano carbon-, a nano carbon line structure, a carbon nanotube array or a single carbon nanotube, and the nano carbon line structure or the carbon nanotube film may have at least a tip. The tip is a bundle structure formed by connecting a plurality of carbon nanotubes through a van der Waals force. A carbon nanotube is extended at the end of the tip and the carbon nanotube is fixed by a van der Waals force to the adjacent 4 4 tube. The ceramsite carbon nanotube composite is formed by forming a plurality of metal carbide particles on the surface of the nanotube structure, and has an ion bombardment resistance. Therefore, the electron source prepared by using the nano-tube composite can work stably under low vacuum. [_] In summary, the mesocarbon nanotube structure table (4) is a plurality of metal carbide particles resistant to ion bombardment, which can increase the life of the carbon nanotube composite under low vacuum. In addition, since the metal broken particles 09810905# single number A0101 page 16 / total 40 pages 1013359402-0 Γ 377172 101. September 20 modified replacement pages are spaced apart from each other and are embedded in the surface of the carbon nanotube structure The diameter of the carbon nanotube structure can be kept small, and when applied to an electron emission source, the carbon nanotube composite can maintain a large field enhancement factor, thereby enabling excellent field emission. effect. [0044] The method for preparing the carbon nanotube composite material, the metal cladding layer is heated to a first temperature to melt the metal cladding layer by energizing the carbon nanotube structure, and the molten metal layer is melted. The metal coating reacts with the carbon atoms in the carbon nanotube structure to form reticular metal carbide particles on the outer surface of the carbon nanotube structure. The preparation method of the carbon nanotube composite material has a simple heating method and does not require a complicated annealing process, thereby making the preparation method of the carbon nanotube composite material simpler. The embodiment of the invention further provides a carbon nanotube composite material prepared by the method for preparing the carbon nanotube composite material, wherein the carbon nanotube composite material forms a plurality of metal carbides on the surface of the carbon nanotube structure. The particles are resistant to ion bombardment. [0045] • In summary, the present invention has indeed met the requirements of the invention patent and has filed a patent application in accordance with the law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of preparing a carbon nanotube composite material according to a first embodiment of the present invention. 2 is a scanning electron micrograph of a preferred orientation carbon nanotube rolled film of the first embodiment of the present invention as a carbon nanotube structure. _1_5Bill No. Α〇101 $ Π page/Total 40 pages 1013359402-0 1377172 September 20th, 2010 Nuclear replacement page [0048] FIG. 3 is a non-twisting naf of the first embodiment of the present invention as a carbon nanotube structure Scanning electron micrograph of the carbon carbon pipeline. 4 is a scanning electron micrograph of a twisted nanocarbon line as a carbon nanotube structure according to a first embodiment of the present invention. 5 is a schematic flow chart showing a method for preparing a carbon nanotube composite material according to a second embodiment of the present invention. 6 is a schematic flow chart showing a method of preparing a carbon nanotube composite material according to a third embodiment of the present invention. 7 is a scanning electron micrograph of a carbon nanotube film drawn by a third embodiment of the present invention. [0053] FIG. 8 is a scanning electron micrograph of the carbon nanotube film of FIG. 7 at 2 micrometers. [0054] FIG. 9 is a drawing of the carbon nanotube film of FIG. Scanning electron micrographs of the ruler at 2 microns. [0055] FIG. 10 is a scanning electron micrograph of a carbon nanotube-like structure formed by the carbon nanotube film of FIG. 9 after being treated with an organic solvent. [0056] FIG. 11 is a scanning electron micrograph of a reaction between a carbon nanotube in a nanocarbon line-like structure of FIG. 10 and a metal coating layer. 12 is a transmission electron micrograph of the nanocarbon line-like structure of FIG. 10. [0058] FIG. 13 is a transmission electron micrograph of the nanocarbon line structure of FIG. 14 is a transmission electron micrograph of carbonized buckle particles in the nanocarbon line-like structure of FIG. [0060] FIG. 15 is a diagram showing the nano carbon line structure of FIG. 11 after heat treatment fracture 1013359402-0 __5 production order number A0101 page 18 / total 40 page 1377172 101 years. September 20th nuclear replacement page A scanning electron micrograph of the tip. 16 is a partially enlarged scanning electron micrograph of the tip end of the nanocarbon line structure of FIG. 15. [0062] FIG. 17 is a scanning electron micrograph of the tip ruler of FIG. 16 at 2 micrometers. [Main component symbol description] [0063] None

Single No. A0101 Page 19 of 40 1013359402-0

Claims (1)

1377172 t September 20, 101 Nuclear replacement page VII. Patent application scope: 1. A method for preparing a carbon nanotube composite material, comprising the steps of: providing a carbon nanotube structure, the carbon nanotube structure Including at least one carbon nanotube; forming a metal coating on at least one outer surface of the carbon nanotube in the carbon nanotube structure; energizing the carbon nanotube structure in a vacuum to make the carbon nanotube The metal coating of the outer surface is melted and reacts with carbon atoms in the carbon nanotube to form a plurality of metal carbide particles on the outer surface of the carbon nanotube. In this step, the carbon nanotube structure is After being energized in a vacuum, it is heated to a first temperature, and the metal coating layer is melted at the first temperature, and the first temperature is greater than or equal to a reaction temperature of the metal coating layer and the carbon nanotube. 2. The method for preparing a carbon nanotube composite material according to claim 1, wherein the carbon nanotube structure is energized in a vacuum by fixing and electrically connecting the carbon nanotube structure to Between the two electrodes, placed in a vacuum and a voltage is applied between the two electrodes. 3. The method for preparing a carbon nanotube composite material according to claim 1, wherein the carbon nanotube structure comprises a carbon nanotube film, a carbon nanotube line, a c> A carbon nanotube array or a single carbon nanotube. 4. The method of preparing a carbon nanotube composite material according to claim 1, wherein the material of the metal coating layer is any one or more of ruthenium, knob, titanium and zirconium. 5. The method of preparing a carbon nanotube composite according to claim 1, wherein the metal coating has a thickness of between 1 nm and 100 nm. 6. The preparation method of the carbon nanotube composite material as described in claim 1 of the patent scope 09810905#单号 A〇101 Page 20 of 40 1013359402-0 1377172 101. The method of forming a metal cladding layer includes a magnetron sputtering method or an electron beam evaporation method. 7. A method of preparing a carbon nanotube composite material, comprising the steps of: providing a nanocarbon line-like structure comprising a plurality of carbon nanotubes extending along an axial direction thereof; forming a metal Coating a surface of the at least one carbon nanotube in the nanocarbon line-like structure; energizing the nanocarbon line-like structure in a vacuum to heat the nanocarbon line-like structure to a first temperature, a metal coating on the outer surface of the carbon nanotube is melted and reacts with carbon atoms in the carbon nanotube to form a plurality of metal carbide particles on the outer surface of the carbon nanotube; the carbon nanotube-like structure is vacuumed The medium energization heats the nanocarbon line-like structure to a second temperature, causing the nanocarbon line-like structure to break and form two tips at the fracture, and in the step, the second temperature is greater than the first temperature 8 . A method for preparing a carbon nanotube composite material, comprising the steps of: providing a carbon nanotube film, the carbon nanotube film comprising a plurality of carbon nanotubes extending in the same direction and connected end to end by van der Waals force Forming a metal coating on the outer surface of at least one of the carbon nanotubes in the carbon nanotube film; treating the carbon nanotube film with an organic solvent to shrink into a nano carbon line structure; The nanocarbon line-like structure is energized in a vacuum to heat the nanocarbon line-like structure to a first temperature, so that the metal coating on the outer surface of the at least one carbon nanotube is melted and formed in the carbon nanotube Carbon atom reaction, forming a plurality of metal carbide particles on the outer surface of the carbon nanotube; 1013359402-0 0981_5 more than a single number A〇101 page / a total of 40 pages 1377172 101 September 20 revised replacement page to the nano The carbon line-like structure is energized in a vacuum to heat the nanocarbon line-like structure to a second temperature, causing the nanocarbon line-like structure to break and form two tips at the fracture. In this step, the second temperature is greater than the The first temperature is 9. A carbon nanotube composite material, the improvement is that the carbon nanotube composite material comprises a carbon nanotube structure, and the surface of the carbon nanotube structure is formed with a plurality of spaced metal carbide particles, the phase Neighbor two Attachment between the carbide particles have a gap of 1 nm ~ 100 nm. 10 . The nano carbon tube composite material is improved in that the carbon nanotube composite material comprises a carbon nanotube structure, and at least one carbon nanotube outer surface of the carbon nanotube structure is formed with a plurality of intervals The metal carbide particles have a gap of between 1 nm and 100 nm between two adjacent metal carbide particles. 11. The carbon nanotube composite material according to claim 10, wherein the carbon nanotube structure comprises a carbon nanotube membrane, a nanocarbon pipeline structure, a carbon nanotube array or a single root. Carbon tube. 12. The carbon nanotube composite of claim 11, wherein the nanocarbon line structure or the carbon nanotube film has at least one tip. The carbon nanotube composite material according to claim 10, wherein the metal carbide material is any one or more of niobium carbide, carbonized niobium, titanium carbide, and carbonization. The carbon nanotube composite material according to claim 13, wherein the metal carbide particles are carbonized in the presence of a face-centered cubic lattice crystal structure. The carbon nanotube composite material according to claim 13, wherein the metal carbide particles are embedded in the outer wall of the carbon nanotube. 16. The carbon nanotube composite material according to claim 15 of the patent application, wherein __5 癸 single number A0101 $ 22 pages / total 4 pages 1013359402-0 1.377172 17 . 18 . 101. September 20 Mistaken replacement page The metal carbide particles have a particle size ranging from 1 nm to 1 nm. The carbon nanotube composite material according to claim 15, wherein two adjacent metal carbide particles are spaced apart on the surface of the same carbon nanotube. A carbon nanotube composite material, which is improved in that it comprises a carbon nanotube having a plurality of spaced apart metal carbide particles formed on the surface thereof, and 1 nm between two adjacent metal carbide particles ~100 nm gap. 09810905^^^^ A0101 Page 23 of 40 1013359402-0