JP5421183B2 - Hollow heat source - Google Patents

Description

  The present invention relates to a hollow heat source, and more particularly to a hollow heat source using carbon nanotubes.

  Heat sources play an important role in areas such as people's life and scientific research. For example, it is applied to an electric heater, an electric heater, an infrared therapy device, and the like. The hollow heat source is a kind of heat source and is a three-dimensional structure. The hollow heat source can simultaneously heat each part of the object to be heated, has a large heating area, good heating uniformity, and high efficiency.

  As a prior art, a hollow heat source includes a heating element and at least two electrodes. The at least two electrodes are disposed on the surface of the heating element and are electrically connected to the heating element. When a current is passed through the heating element by the at least two electrodes, heat is released from the heating element. A conventional hollow heat source converts electric energy into heat energy using a metal filament or carbon fiber as a heating element.

Kaili Jiang, Quung Li, Shuushan Fan, “Spinning continuous carbon nanotube yarns”, Nature, 2002, vol. 419, p. 801

  However, the metal filament or carbon fiber has poor strength, is easy to break, and is heavy. In particular, when the metal filament is bent at a predetermined angle, there is a drawback that the metal filament is more easily broken. In addition, since heat emitted from the metal filament or carbon fiber is radiated to the outside at a standard wavelength, there is a disadvantage that the efficiency of converting electric energy into heat energy is low and energy is wasted.

  Therefore, an object of the present invention is to provide a hollow heat source with high efficiency for converting electric energy into heat energy.

  The hollow heat source includes a heating element and at least two electrodes electrically connected to the heating element. The heating element has a hollow structure including a carbon nanotube composite structure, and the carbon nanotube composite structure includes at least one linear carbon nanotube composite structure. The linear carbon nanotube composite structure includes at least one carbon nanotube linear structure and a base material, and the carbon nanotube linear structure and the base material are combined. The carbon nanotube linear structure is composed of only a plurality of carbon nanotubes.

  In the carbon nanotube linear structure, a plurality of micropores are formed, and the base material penetrates into the plurality of micropores.

  Compared with the conventional hollow heat source, the hollow heat source of the present invention has the following excellent points.

  By directly combining the base material and the carbon nanotube structure having the self-supporting structure to form a heating element, the carbon nanotube retains the form of the carbon nanotube structure in the heating element. The carbon nanotubes in the heating element are uniformly distributed and can form a conductive path. Compared with the carbon nanotubes in the prior art limited to the concentration dispersed in the solution, the carbon nanotubes The content in the heating element can reach 99%. Therefore, the hollow heat source is highly efficient in converting electrical energy into heat energy, and can increase the heat radiation temperature of the hollow heat source.

  In the hollow heat source, the heating element includes a carbon nanotube structure, the carbon nanotubes in the carbon nanotube structure are uniformly arranged, and the heating element has a uniform thickness and resistance. Heat can be released. Since the carbon nanotube has a high efficiency of converting electric energy into heat energy, the hollow heat source has a high temperature rising rate, a high thermal response speed, and a high heat exchange rate.

  Since the carbon nanotube in the heating element has excellent mechanical performance, excellent toughness and excellent mechanical strength, the heating element has excellent mechanical performance, excellent toughness and mechanical strength, and has a long service life. Further, when the carbon nanotube structure and the flexible substrate are combined to form the heating element, a flexible hollow heat source can be manufactured using the heating element.

  Since the diameter of the carbon nanotube in the heating element is small, the heating element has a small thickness. Therefore, an extremely small hollow heat source can be manufactured, and a small element to be heated can be heated using the small hollow heat source.

  The material of the substrate is not limited to a polymer, and since the temperature range is wide, the hollow heat source can be more widely applied.

  When the carbon nanotube structure is made of a drone structure carbon nanotube film, the plurality of carbon nanotubes in the carbon nanotube film are connected to each other along the same direction, so that the carbon nanotube structure has excellent conductivity. Therefore, the hollow heat source has excellent heating performance. Further, since the carbon nanotube film has a predetermined transparency, a transparent hollow heat source can be manufactured.

  A method of directly combining the base material and the carbon nanotube structure having the self-supporting structure to form a heating element is simple. In addition, the content of the carbon nanotubes in the heating element can be easily controlled. After the carbon nanotube structure having the self-standing structure and the base material are directly combined, the carbon nanotube structure can maintain the conventional state. Therefore, the heating element can release almost the same heat as the heating element made of a pure carbon nanotube structure.

It is a cross-sectional enlarged view of the heating element of the hollow heat source which concerns on the Example of this invention. It is a cross-sectional enlarged view of the heating element of the hollow heat source which concerns on the Example of this invention. It is a SEM photograph of the drone structure carbon nanotube film in the hollow heat source concerning the example of the present invention. It is a figure which shows the structure of the carbon nanotube segment in a drone structure carbon nanotube film. It is a sketch drawing which draws out the drone structure carbon nanotube film in FIG. It is a SEM photograph of the carbon nanotube film in which the carbon nanotube in the precision structure carbon nanotube film isotropically arranged in the hollow heat source concerning the example of the present invention. It is a SEM photograph of the carbon nanotube film in which the carbon nanotube in the precision structure carbon nanotube film in the hollow heat source concerning the example of the present invention was arranged along the same direction. It is a SEM photograph of the carbon nanotube film of a fluff structure in the hollow heat source concerning the example of the present invention. It is a photograph of the carbon nanotube film of fluff structure in the hollow heat source concerning the example of the present invention. It is the photograph of the carbon nanotube structure of the filtered fluff structure. It is a SEM photograph of the ultra-long structure carbon nanotube film in the hollow heat source concerning the example of the present invention. It is a SEM photograph of the non-twisted carbon nanotube wire concerning the example of the present invention. It is a SEM photograph of the twisted carbon nanotube wire concerning the example of the present invention. It is a flowchart of the manufacturing method of the hollow heat source which concerns on the Example of this invention. It is a figure which shows the structure of the 1st kind of hollow heat source which concerns on Example 1 of this invention. It is sectional drawing cut | disconnected along the XVI-XVI line | wire shown in FIG. 15 of the 1st kind of hollow heat source which concerns on Example 1 of this invention. It is the photograph of the cross section formed by cut | disconnecting the said carbon nanotube composite structure along the arrangement direction of the carbon nanotube in the drone structure carbon nanotube film of the 1st kind of hollow heat source concerning Example 1 of this invention. It is a figure which shows the structure of the 2nd type | mold hollow heat source which concerns on Example 1 of this invention. It is a figure which shows the structure of the 3rd type | mold hollow heat source which concerns on Example 1 of this invention. It is a figure which shows the structure of the hollow heat source which concerns on Example 2 of this invention. It is sectional drawing which cuts the hollow heat source which concerns on Example 2 of this invention along the XXI-XXI line | wire shown in FIG. It is sectional drawing which cuts the hollow heat source which concerns on Example 2 of this invention along the XXII-XXII line | wire shown in FIG. It is a figure which shows the structure of the hollow heat source which concerns on Example 3 of this invention. It is sectional drawing which cuts the hollow heat source which concerns on Example 3 of this invention along the XXIV-XXIV line | wire shown in FIG.

  Embodiments of the present invention will be described below with reference to the drawings.

  The present invention provides a three-dimensional hollow heat source. The hollow heat source includes a hollow three-dimensional support, a heating element, a first electrode, and a second electrode. The heating element is installed on the surface of the hollow three-dimensional support. The first electrode and the second electrode are each electrically connected to the heating element, and are used to electrically connect the heating element to a power source.

  The hollow three-dimensional support is used for supporting the heating element and forming the heating element into a hollow three-dimensional structure. The heating element can heat the hollow space from a plurality of directions to increase the heating efficiency of the heating element. The material of the hollow three-dimensional support may be a hard material such as ceramics, glass, resin, or quartz, or may be a flexible material such as plastic or soft fiber. When the hollow three-dimensional support employs a flexible material, the hollow three-dimensional support can be curved into an arbitrary shape depending on the actual application. The hollow three-dimensional support has a hollow structure. The hollow structure can be changed depending on the shape of the object to be heated. The shape of the hollow three-dimensional support is a tube shape, a spherical shape, or a hollow rectangular parallelepiped shape.

  The heating element is installed on the back surface or the outer surface of the hollow three-dimensional support. The back surface of the hollow three-dimensional support is a surface of the hollow three-dimensional support facing the hollow space. The outer surface of the hollow three-dimensional support is an opposite surface facing the back surface of the hollow three-dimensional support. The heating element is a carbon nanotube composite structure. The carbon nanotube composite structure can be installed on the surface of the hollow three-dimensional support using an adhesive or a mechanical system.

  The heating element is a carbon nanotube composite structure. The carbon nanotube composite structure includes a carbon nanotube structure and a substrate. The carbon nanotube structure and the substrate are combined. Specifically, since the carbon nanotube structure includes a plurality of micropores, the base material is immersed in the micropores of the carbon nanotube structure, thereby forming a carbon nanotube composite structure. When the volume of the substrate is large, the carbon nanotube structure is placed in the substrate and covered with the substrate.

  The carbon nanotube structure has a self-supporting structure. Here, the self-supporting structure is a form in which the carbon nanotube structure can be used independently without using a support material. That is, it means that the carbon nanotube structure can be suspended by supporting the carbon nanotube structure from opposite sides without changing the structure of the carbon nanotube structure. The carbon nanotube structure includes a plurality of carbon nanotubes, and the plurality of carbon nanotubes are connected by an intermolecular force and are uniformly distributed. Therefore, the carbon nanotube structure has a predetermined shape. The carbon nanotube structure has a film-like structure or a linear structure. Since there are a plurality of gaps between adjacent carbon nanotubes in the carbon nanotube structure, a plurality of micropores are formed in the carbon nanotube structure, and the diameter of the micropores is 10 micrometers or less. Accordingly, the base material is immersed in the micropores in the carbon nanotube structure and is closely bonded to the carbon nanotube structure.

  The carbon nanotube composite structure includes a film-like carbon nanotube composite structure or at least one linear carbon nanotube composite structure. The membrane-like carbon nanotube composite structure or at least one linear carbon nanotube composite structure is placed on the surface of the hollow three-dimensional support.

  As an example, the film-like carbon nanotube composite structure is a two-dimensional structure. In this case, the membrane-like carbon nanotube composite structure can be coated on or wound around the outer surface of the hollow three-dimensional support, or the hollow three-dimensional support can be formed by an adhesive or a mechanical method. It can also be fixed to the back surface of the. The specific structure of the film-like carbon nanotube composite structure is classified into the following two types depending on the method of combining the carbon nanotube structure and the base material.

  In the first type, referring to FIG. 1, the heating element is the film-like carbon nanotube composite structure. The film-like carbon nanotube composite structure, the film-like carbon nanotube structure 2044 and the substrate 2042 are included. Since the film-like carbon nanotube structure 2044 has a plurality of micropores, the material of the base body 2042 can be immersed in the micropores of the film-like carbon nanotube structure 2044. The film-like carbon nanotube structure 2044 is added as a base material, and the material of the base 2042 is added as an additive material into the micropores of the film-like carbon nanotube structure 2044 as a base material. When the film-like carbon nanotube structure 2044 includes a plurality of carbon nanotube films, the plurality of carbon nanotube films are stacked and installed. When the film-like carbon nanotube structure 2044 includes one carbon nanotube linear structure, the carbon nanotube linear structure is formed into a film-like free-standing structure. When the film-like carbon nanotube structure 2044 includes a plurality of carbon nanotube linear structures, the plurality of carbon nanotube linear structures are installed in parallel, crossed, or knitted together. A film-like self-supporting structure can be formed. When the film-like carbon nanotube structure 2044 includes a carbon nanotube film and a carbon nanotube linear structure, the carbon nanotube linear structure is disposed on at least one surface of the carbon nanotube film.

  In the second type, referring to FIG. 2, the film-like carbon nanotube composite structure includes a carbon nanotube structure 2044 and a substrate 2042. The base body 2042 has a film-like structure, and the carbon nanotube structures 2044 are distributed in the base body 2042. Further, the carbon nanotube structures 2044 are preferably distributed uniformly in the base body 2042. The base body 2042 can completely cover the carbon nanotube structure 2044. Alternatively, at least part of the material of the base body 2042 is immersed in the carbon nanotube structure 2044. When the carbon nanotube structure 2044 includes a plurality of carbon nanotube linear structures arranged in parallel and spaced apart, the carbon nanotube linear structure extends from the first electrode to the second electrode. .

  As another example, the linear carbon nanotube composite structure is a one-dimensional structure. In this case, the linear carbon nanotube composite structure is classified into the following two types.

  In the first type, the linear carbon nanotube composite structure includes a carbon nanotube linear structure and a substrate. Since the carbon nanotube linear structure has many micropores, the base material is immersed in the micropores of the carbon nanotube linear structure.

  In the second type, the linear carbon nanotube composite structure includes a carbon nanotube linear structure and a substrate. The carbon nanotube linear structure is composited in the substrate.

  The carbon nanotube structure includes a plurality of carbon nanotubes, and the plurality of carbon nanotubes are connected by an intermolecular force and are uniformly distributed. In the carbon nanotube structure, the plurality of carbon nanotubes are arranged with or without orientation. According to the arrangement method of the plurality of carbon nanotubes, the carbon nanotube structure is classified into two types: a non-oriented carbon nanotube structure and an oriented carbon nanotube structure. In the non-oriented carbon nanotube structure, the carbon nanotubes are arranged or entangled along different directions. In the oriented carbon nanotube structure, the plurality of carbon nanotubes are arranged along the same direction. Alternatively, in the oriented carbon nanotube structure, when the oriented carbon nanotube structure is divided into two or more regions, a plurality of carbon nanotubes in each region are arranged along the same direction. In this case, the arrangement directions of the carbon nanotubes in different regions are different. The carbon nanotube structure has a thickness of 0.5 nanometer to 1.0 millimeter. The carbon nanotube is a single-walled carbon nanotube, a double-walled carbon nanotube, or a multi-walled carbon nanotube. When the carbon nanotube is a single-walled carbon nanotube, the diameter is set to 0.5 nm to 50 nm. When the carbon nanotube is a double-walled carbon nanotube, the diameter is set to 1 nm to 50 nm. In the case of a nanotube, the diameter is set to 1.5 nm to 50 nm. The carbon nanotube structure is preferably an oriented carbon nanotube structure.

The thermal response speed of the carbon nanotube structure is related to the thickness of the carbon nanotube structure. When the carbon nanotube structures have the same surface area, the thermal response speed is slow if the thickness is large, and the thermal response speed is fast if the thickness is thin. Since the purity of the carbon nanotube structure is high and the carbon nanotube structure has a large specific surface area (for example, 100 m ² / g or more), the heat capacity per unit area of the carbon nanotube structure is 0 (0 is included) 1) to 2 × 10 ⁻⁴ J / cm ² · K, preferably 0 (not including 0) to 1.7 × 10 ⁻⁶ J / cm ² · K. Since the heat capacity per unit area of the carbon nanotube structure is very low, the heating element can be quickly heated. That is, the carbon nanotube structure has a high thermal response speed. Since the density of the carbon nanotube structure is low and reaches about 1.35 g / cm ³ , the light transmittance of the carbon nanotube structure is high.

  Specifically, the carbon nanotube structure includes at least one carbon nanotube film, a carbon nanotube linear structure, or a combination of a carbon nanotube film and a carbon nanotube linear structure. When the carbon nanotube structure includes a plurality of carbon nanotube films, the plurality of carbon nanotube films are stacked and installed. When the carbon nanotube structure includes a plurality of carbon nanotube linear structures, the plurality of carbon nanotube linear structures are installed in parallel, crossed, or knitted to form a two-dimensional carbon nanotube structure. The body can be formed. The carbon nanotube structure can form a two-dimensional carbon nanotube structure by winding the carbon nanotube linear structure.

Examples of the carbon nanotube film of the present invention include the following (1) to (4).
(1) Drone structure carbon nanotube film The carbon nanotube structure includes at least one drone structure carbon nanotube film. Referring to FIG. 3, the single drone-structured carbon nanotube film 143a is obtained by pulling from a super-aligned carbon nanotube array (see Superaligned array of carbon nanotubes, Non-Patent Document 1), and has a self-supporting structure. is there. In the single carbon nanotube film 143a, most of the plurality of carbon nanotubes are arranged in parallel to the surface of the carbon nanotube film, along the direction of drawing out the carbon nanotube film, and along the same direction. Yes. The ends of the plurality of carbon nanotubes are connected by an intermolecular force.

  Microscopically, in the carbon nanotube film 143a, in addition to the plurality of carbon nanotubes arranged along the same direction, there are carbon nanotubes which are not along the same direction but are oriented in a random direction. . Here, the proportion of the carbon nanotubes oriented in the random direction is smaller than that of the plurality of carbon nanotubes arranged along the same direction.

Referring to FIG. 4, the single carbon nanotube film 143a includes a plurality of carbon nanotube segments 143b. The plurality of carbon nanotube segments 143b are connected to each other by an intermolecular force along the length direction. Each carbon nanotube segment 143b includes a plurality of carbon nanotubes 145 connected in parallel to each other by intermolecular force. In the single carbon nanotube segment 143b, the lengths of the plurality of carbon nanotubes 145 are substantially the same. By soaking the carbon nanotube film 143a in an organic solvent, the toughness and mechanical strength of the carbon nanotube film 143a can be increased. When the thickness of the carbon nanotube film 143a is 10 micrometers or less, the transmissivity of the carbon nanotube film 143a reaches about 96% or more, and therefore it can be used as a transparent heat source. The heat capacity per unit area of the single carbon nanotube film 143a is 1.7 × 10 ⁻⁶ J / cm ² · K or less.

  When the carbon nanotube structure includes a plurality of stacked carbon nanotube films 143a, the adjacent carbon nanotube films 143a are bonded by intermolecular force. The carbon nanotubes 145 in the adjacent carbon nanotube films 143a intersect each other at an angle of 0 ° to 90 °. When the carbon nanotubes 145 in the adjacent carbon nanotube film 143a intersect at an angle of 0 ° or more, a plurality of micropores are formed in the carbon nanotube structure, and the diameter of the micropores is 10 micrometers or less. Alternatively, the plurality of carbon nanotube films 143a may be juxtaposed on the same plane without a gap.

  The method for manufacturing the carbon nanotube film includes the following steps.

  In the first step, a carbon nanotube array is provided. The carbon nanotube array is a super aligned carbon nanotube array (see Superaligned array of carbon nanotubes, Non-Patent Document 1), and a chemical vapor deposition method is employed as a method of manufacturing the super aligned carbon nanotube array. The manufacturing method includes the following steps. In step (a), a flat substrate is provided, and the substrate is any one of a P-type silicon substrate, an N-type silicon substrate, and a silicon substrate on which an oxide layer is formed. In this embodiment, it is preferable to select a 4-inch silicon substrate. In step (b), a catalyst layer is uniformly formed on the surface of the substrate. The material of the catalyst layer is any one of iron, cobalt, nickel and two or more alloys thereof. In step (c), the substrate on which the catalyst layer has been formed is annealed with air at 700 ° C. to 900 ° C. for 30 minutes to 90 minutes. In step (d), the annealed substrate is placed in a reaction furnace, heated with a protective gas at a temperature of 500 ° C. to 740 ° C., and then a carbon-containing gas is introduced to react for 5 to 30 minutes. Thus, it is possible to grow a super aligned carbon nanotube array (Superaligned array of carbon nanotubes, Non-Patent Document 1). The carbon nanotube array has a height of 100 micrometers or more. The carbon nanotube array is composed of a plurality of carbon nanotubes that are parallel to each other and grow perpendicular to the substrate. Since the carbon nanotubes are long, the carbon nanotubes are partially entangled with each other. By controlling the growth conditions, the carbon nanotube array does not contain impurities such as amorphous carbon and remaining metal particles as a catalyst.

  In this embodiment, as the gas containing carbon, for example, active hydrocarbons such as acetylene, ethylene, and methane are selected, and it is preferable to select ethylene. The protective gas is nitrogen gas or inert gas, preferably argon gas.

  The carbon nanotube array provided by the present embodiment is not limited to being manufactured by the above manufacturing method, and may be manufactured by an arc discharge method or a laser evaporation method.

  In the second step, at least one carbon nanotube film is stretched from the carbon nanotube array. First, using a tool such as tweezers, a plurality of carbon nanotube ends are provided. For example, a plurality of carbon nanotube ends are used by using a tape having a certain width. Next, the plurality of carbon nanotubes are pulled out at a predetermined speed to form a continuous carbon nanotube film composed of a plurality of carbon nanotube bundles.

  In the step of pulling out the plurality of carbon nanotubes, when the plurality of carbon nanotubes are detached from the base material, the carbon nanotube bundles are joined to each other by an intermolecular force to form a continuous carbon nanotube film. (See FIG. 5).

(2) Precise structure carbon nanotube film The carbon nanotube structure includes at least one pressed structure carbon nanotube film. Referring to FIG. 6 or FIG. 7, the plurality of carbon nanotubes in the carbon nanotube film are arranged isotropically, arranged along a predetermined direction, or arranged along a plurality of different directions. Has been. The carbon nanotube film has a sheet-like self-supporting structure formed by pressing the carbon nanotube array by applying a predetermined pressure by using a pushing tool and depressing the carbon nanotube array with the pressure. is there. The arrangement direction of the carbon nanotubes in the carbon nanotube film is determined by the shape of the pushing device and the pushing direction of the carbon nanotube array.

  Referring to FIG. 6, the carbon nanotubes in a single carbon nanotube film are arranged without being oriented. The carbon nanotube film includes a plurality of carbon nanotubes arranged isotropically. Adjacent carbon nanotubes attract each other by intermolecular force and connect. The carbon nanotube structure has planar isotropy. The carbon nanotube film is formed by pressing the carbon nanotube array along a direction perpendicular to the substrate on which the carbon nanotube array is grown using a pressing device having a flat surface.

  Referring to FIG. 7, the carbon nanotubes in a single carbon nanotube film are aligned and arranged. The carbon nanotube film includes a plurality of carbon nanotubes arranged along the same direction. When the carbon nanotube array is simultaneously pressed along the same direction using a pressing device having a roller shape, a carbon nanotube film including carbon nanotubes arranged in the same direction is formed. In addition, when the carbon nanotube array is simultaneously pressed along different directions using a pressing device having a roller shape, a carbon nanotube film including carbon nanotubes arranged in a selective direction along the different directions Is formed.

  The degree of inclination of the carbon nanotubes in the carbon nanotube film is related to the pressure applied to the carbon nanotube array. The carbon nanotubes in the carbon nanotube film and the surface of the carbon nanotube film form an angle α, and the angle α is not less than 0 ° and not more than 15 °. Preferably, the carbon nanotubes in the carbon nanotube film are parallel to the surface of the carbon nanotube film. The greater the pressure, the greater the degree of tilt. The thickness of the carbon nanotube film is related to the height of the carbon nanotube array and the pressure applied to the carbon nanotube array. That is, as the height of the carbon nanotube array increases and the pressure applied to the carbon nanotube array decreases, the thickness of the carbon nanotube film increases. On the contrary, as the height of the carbon nanotube array becomes smaller and the pressure applied to the carbon nanotube array becomes larger, the thickness of the carbon nanotube film becomes smaller. Since there is a gap between adjacent carbon nanotubes in the carbon nanotube film, a plurality of micropores are formed in the carbon nanotube film, and the diameter of the micropores is 10 micrometers or less.

(3) Fluff-structured carbon nanotube film The carbon nanotube structure includes at least one fluff-structured carbon nanotube film (flocculated carbon nanotube film). 8 and 9, in the single carbon nanotube film, a plurality of carbon nanotubes are entangled with each other and isotropically arranged. In the carbon nanotube structure, the plurality of carbon nanotubes are uniformly distributed and parallel to the surface of the fluff structure carbon nanotube film. The plurality of carbon nanotubes are arranged without being oriented. The length of the single said carbon nanotube is 10 micrometers or more, and it is preferable in it being 200 micrometers-900 micrometers. The carbon nanotube structure is formed in the shape of a self-supporting thin film. Here, the self-supporting structure is a form in which the carbon nanotube structure can be used independently without using a support material. The plurality of carbon nanotubes are close to each other by intermolecular force and entangled with each other to form a carbon nanotube net. The plurality of carbon nanotubes are arranged without being oriented to form a plurality of minute holes. Here, the diameter of the single minute hole is 10 micrometers or less. Since the carbon nanotubes in the carbon nanotube structure are arranged so as to be entangled with each other, the carbon nanotube structure is excellent in flexibility and can be formed to be bent into an arbitrary shape. Depending on the application, the length and width of the carbon nanotube structure can be adjusted. The carbon nanotube structure has a thickness of 1.0 micrometer to 1.0 millimeter, preferably 100 micrometers.

  The method for producing the carbon nanotube film includes the following steps.

  In the first step, carbon nanotubes that serve as a basis for the carbon nanotube film are provided.

  The carbon nanotubes are peeled off from the substrate with a tool such as a knife to form a carbon nanotube raw material. The carbon nanotubes are intertwined with each other to some extent. In the raw material of the carbon nanotube, the carbon nanotube has a length of 10 micrometers or more, preferably 200 micrometers to 900 micrometers.

  In the second step, the carbon nanotube raw material is immersed in a solvent, and the carbon nanotube raw material is treated to form a fluffy carbon nanotube structure.

  After the carbon nanotube raw material is immersed in the solvent, the carbon nanotube is formed into a fluff structure by a method such as ultrasonic dispersion, high intensity stirring or vibration. The solvent is water or a volatile organic solvent. Treatment is performed for 10 to 30 minutes with respect to the solvent containing carbon nanotubes by an ultrasonic dispersion method. Since the carbon nanotube has a large specific surface area and a large intermolecular force is generated between the carbon nanotubes, the carbon nanotubes are entangled and formed into a fluff structure.

  In the third step, the solution containing the fluff structure carbon nanotube structure is filtered to take out the final fluff structure carbon nanotube structure.

  First, provide a funnel with filter paper. When the solvent containing the fluffy carbon nanotube structure is applied to the funnel on which the filter paper is placed and then left standing for a while to dry, the fluffy carbon nanotube structure is separated. Referring to FIG. 10, the carbon nanotubes in the carbon nanotube structure having the fluff structure are entangled with each other to form an irregular fluff structure.

  The separated fluff structure carbon nanotube structure is placed in a container, the fluff structure carbon nanotube structure is expanded into a predetermined shape, and a predetermined pressure is applied to the expanded fluff structure carbon nanotube structure, When the solvent remaining in the fluffy carbon nanotube structure is roasted or the solvent naturally evaporates, the fluffy carbon nanotube film shown in FIGS. 8 and 9 is formed.

  The thickness and surface density of the fluffy carbon nanotube film can be controlled by the area where the fluffy carbon nanotube structure is developed. That is, the fluff-structured carbon nanotube structure having a certain volume has a smaller thickness and areal density of the fluff-structured carbon nanotube film as the developed area increases.

  In addition, a carbon nanotube film having a fluff structure is formed using a microporous film and an air pump funnel. Specifically, a microporous membrane and an air pump funnel are provided, and the solvent containing the fluff-structured carbon nanotube structure is passed through the microporous membrane to the air pump funnel, and then extracted to the air pump funnel and dried. As a result, a carbon nanotube film having a fluff structure is formed. The microporous film has a smooth surface. In the microporous membrane, the diameter of a single micropore is 0.22 micrometers. Since the microporous membrane has a smooth surface, the carbon nanotube film can be easily peeled off from the microporous membrane. Furthermore, since air pressure is applied to the fluffy carbon nanotube film by using the air pump, a uniform fluffy carbon nanotube film can be formed.

(4) Ultra-long structure carbon nanotube film The carbon nanotube structure includes at least one ultra-long structure carbon nanotube film. Referring to FIG. 11, the carbon nanotube film includes a plurality of carbon nanotubes having substantially the same length. In the single carbon nanotube film, the plurality of carbon nanotubes are arranged in parallel along the same direction. The thickness of the single carbon nanotube film is 10 nanometers to 100 micrometers. The plurality of carbon nanotubes are arranged in parallel to the surfaces of the plurality of carbon nanotube films, and are arranged in parallel to each other. Adjacent carbon nanotubes are separated and installed at a predetermined distance. The distance is from 0 to 5 micrometers. When the distance is 0 micrometer, the adjacent carbon nanotubes are connected by intermolecular force. The length of each carbon nanotube in the carbon nanotube film is basically the same as the length of the carbon nanotube film. The length of the single said carbon nanotube is 1 centimeter or more, and it is preferable that they are 1 centimeter-30 centimeters. Further, each carbon nanotube has no nodules. In the present embodiment, the carbon nanotube film has a thickness of 10 micrometers. The length of the single carbon nanotube is 10 centimeters.

The carbon nanotube structure may include at least one carbon nanotube linear structure. The carbon nanotube linear structure includes at least one carbon nanotube wire. The heat capacity of one carbon nanotube wire is 2 × 10 ⁻⁴ J / cm ² · K or less, preferably 0 (not including 0) to 5 × 10 ⁻⁵ J / cm ² · K. . The diameter of one carbon nanotube wire is 4.5 nm to 1 cm, preferably 1.0 μm to 100 μm.

  Referring to FIG. 12, the carbon nanotube wire (non-twisted carbon nanotube wire) includes a plurality of carbon nanotube segments (not shown) connected end to end. The carbon nanotube segments have the same length and width. Further, a plurality of carbon nanotubes having the same length are arranged in parallel in each of the carbon nanotube segments. The plurality of carbon nanotubes are arranged parallel to the central axis of the carbon nanotube wire. In this case, the diameter of one carbon nanotube wire is 1 μm to 1 cm.

  Referring to FIG. 13, the carbon nanotube wire can be twisted to form a twisted carbon nanotube wire. Here, the plurality of carbon nanotubes are arranged in a spiral shape around the central axis of the carbon nanotube wire. In this case, the diameter of one carbon nanotube wire is 1 μm to 1 cm. The carbon nanotube linear structure is made of any one of the non-twisted carbon nanotube wire, the twisted carbon nanotube wire, or a combination thereof.

  The method of forming the carbon nanotube wire uses a carbon nanotube film drawn from a carbon nanotube array. There are the following three methods for forming the carbon nanotube wire. The first type cuts the carbon nanotube film with a predetermined width along the longitudinal direction of the carbon nanotube in the carbon nanotube film to form a carbon nanotube wire. In the second type, the carbon nanotube film can be formed by immersing the carbon nanotube film in an organic solvent and shrinking the carbon nanotube film. In the third type, the carbon nanotube film is machined (for example, a spinning process) to form a twisted carbon nanotube wire. More specifically, first, the carbon nanotube film is fixed to a spinning device. Next, the spinning device is operated to rotate the carbon nanotube film to form a twisted carbon nanotube wire.

  When the carbon nanotube linear structure includes two or more carbon nanotube wires, the carbon nanotube wires are arranged in parallel to form a non-twisted carbon nanotube linear structure. Alternatively, the carbon nanotube wires are arranged in a spiral shape to form a twisted carbon nanotube linear structure. That is, the carbon nanotube wires in the non-twisted carbon nanotube linear structure are arranged along the longitudinal direction of the carbon nanotube linear structure. The carbon nanotube wires in the twisted carbon nanotube linear structure are spirally arranged along the axial direction of the linear structure.

  The carbon nanotube wire in the non-twisted carbon nanotube linear structure is a non-twisted carbon nanotube wire or a twisted carbon nanotube wire. The carbon nanotube wire in the twisted carbon nanotube linear structure is a non-twisted carbon nanotube wire or a twisted carbon nanotube wire.

  The carbon nanotube linear structure has a diameter of 0.5 nanometers to 2 millimeters. The diameter of the carbon nanotube linear structure increases as the diameter of the single carbon nanotube wire increases and the number of the carbon nanotube wires increases. Conversely, the smaller the diameter of the single carbon nanotube wire and the smaller the number of carbon nanotube wires, the smaller the diameter of the carbon nanotube linear structure.

  Since the carbon nanotubes in the carbon nanotube wire are oriented and arranged, the carbon nanotubes in the carbon nanotube linear structure made of the carbon nanotube wire are oriented and arranged.

  Further, the twisted carbon nanotube wire may be treated with a volatile organic solvent. Adjacent carbon nanotubes in the twisted carbon nanotube wire are tightly connected by intermolecular force due to the action of the surface force of the volatile organic solvent, so that the twisted carbon nanotube wire has a small diameter and specific surface area. It has a large density, excellent mechanical strength and excellent toughness.

  When the carbon nanotube structure includes one carbon nanotube linear structure, both ends of the carbon nanotube in the carbon nanotube linear structure are electrically connected to the electrodes, respectively. When the carbon nanotube structure includes a plurality of carbon nanotube linear structures, the plurality of carbon nanotube linear structures are arranged in parallel or crossed. The crossing angle of the cross-arranged carbon nanotube linear structures is not limited. A method of installing each of the carbon nanotube linear structures is not limited, and it may be ensured that a uniform heating element can be formed.

  The carbon nanotube linear structure is formed by treating the drone structure carbon nanotube film with a volatile organic solvent or mechanical external force, and the drone structure carbon nanotube film has a self-supporting structure. The carbon nanotube linear structure also has a free-standing structure. Since there is a gap between the carbon nanotubes in the carbon nanotube linear structure, the carbon nanotube linear structure has a plurality of micropores, and the diameter of the micropores is 10 micrometers or less.

  The base material may be one or several types such as a polymer material and an inorganic non-metallic material. In the process of manufacturing the heating element of the hollow heat source, the base material or the preform formed on the base material penetrates into the micropores of the carbon nanotube structure, and the carbon nanotube structure and It can be tightly joined. The substrate material must be liquid or gas at a predetermined temperature so that after solidification, a composite structure is formed. Further, in order to prevent the hollow heat source from being destroyed or deformed by the heat generated by the operation of the hollow heat source, the substrate needs to be made of a heat resistant material.

  Specifically, the polymer material is one or several of a thermoplastic polymer and a thermosetting polymer. For example, it is one or several kinds of epoxy resin, phenol resin, polyamide resin, fiber, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and the like. The inorganic nonmetallic material is one or several kinds of glass, ceramics, and semiconductor materials. The base material may be a flexible polymer material. For example, it is one or several kinds of silicone rubber, polyurethane, and polymethyl methacrylate resin.

  The base material may be added only into the micropores of the carbon nanotube structure, or the carbon nanotube structure may be completely covered. When the heating element includes a plurality of carbon nanotube structures, the carbon nanotube structures are disposed in the base material at intervals or in contact with each other. When the carbon nanotube structure is a two-dimensional structure, the two-dimensional structure is placed in the substrate at a distance or in contact. When the carbon nanotube structure is a linear structure, the linear structure is placed in the substrate at a distance or in contact therewith. Also, the carbon nanotube structure can be placed at a predetermined position in the substrate material in order to heat different regions of the heating element to different temperatures.

  Since the base material is immersed in the micropores of the carbon nanotube structure, the carbon nanotubes in the carbon nanotube structure can be fixed. Therefore, in the process of using the hollow heat source, the carbon nanotubes in the carbon nanotube structure cannot be detached by an external force. When the carbon nanotube structure is coated with the base material, the carbon nanotube structure can be further protected, and when the base is an insulating organic polymer material or an inorganic non-metallic material, the heating element Insulate from the outside. Moreover, heat can be uniformly transmitted by the base. When the temperature of the carbon nanotube structure rapidly increases, the heating element can be gradually heated by the base. Further, a flexible polymer material can be adopted as the material of the base, and the flexibility and toughness of the hollow heat source can be increased.

  In the heating element manufactured by directly combining the base material and the carbon nanotube structure having the self-supporting structure, the carbon nanotubes are uniformly distributed and the content thereof reaches 99%. The heat radiation temperature of the heat source using the heating element can be increased. The carbon nanotubes in the heating element can be uniformly distributed to form a conductive path, and compared with the carbon nanotubes in the prior art limited to the concentration dispersed in the solution, the carbon nanotubes The content in the heating element can reach 99%.

  The first electrode and the second electrode must be electrically connected to the heating element. The first electrode and the second electrode are made of a conductive material, and are installed on the same surface of the heating element or on both surfaces of the heating element facing each other. The first electrode and the second electrode can be installed on the surface of the heating element using the adhesive property of the carbon nanotube structure or the conductive adhesive. When the conductive adhesive is used, the first electrode and the second electrode are electrically connected to the carbon nanotube structure, and at the same time, the first electrode and the second electrode are attached to the surface of the carbon nanotube structure. Can be fixed well. A voltage can be applied to the heating element by the first electrode and the second electrode. When the heating element is activated, the first element is connected to the first electrode and the second electrode to prevent a short circuit and to connect a predetermined resistance between the first electrode and the second electrode. The first electrode and the second electrode must be installed at a predetermined distance.

  When the base of the heating element is added only to the micropores of the carbon nanotube structure, some of the carbon nanotubes in the carbon nanotube structure are exposed on the surface of the heating element. The second electrode may be installed on the same surface or a different surface of the heating element and electrically connected to the carbon nanotube structure. When the carbon nanotube structure is coated on the substrate of the heating element, the first electrode and the second electrode are electrically connected to the first electrode, the second electrode, and the carbon nanotube structure. An electrode is placed in the carbon nanotube composite structure and directly connected to the carbon nanotube structure. In order to electrically connect the first electrode and the second electrode to an external power source, a part of the first electrode and the second electrode is exposed to the outside of the heating element, or two lead wires Thus, the first electrode and the second electrode are pulled out of the carbon nanotube composite structure, respectively.

  When the arrangement direction of the carbon nanotubes in the carbon nanotube structure is the same, the carbon nanotubes are arranged so as to extend from the first electrode to the second electrode. For example, when the carbon nanotube structure includes a drone-structured carbon nanotube film, the first electrode and the second electrode are respectively disposed perpendicular to the long axis direction of the carbon nanotube in the carbon nanotube film. When the carbon nanotube structure includes a plurality of carbon nanotube linear structures arranged in parallel, the carbon nanotube linear structures are electrically connected to the first electrode and the second electrode, respectively, at both ends of the carbon nanotube linear structure Let

  The first electrode and the second electrode are a conductive film, a metal sheet, or a metal lead wire. The material of the conductive film is a metal, an alloy, an indium tin oxide (ITO) film, an antimony tin oxide (ATO), a silver paste, a conductive polymer, or a carbon nanotube structure. The metal is aluminum, copper, tungsten, molybdenum, gold, titanium, neodymium, palladium, cesium, or the like. The alloy is an alloy of the metal. When the first electrode and the second electrode are made of a carbon nanotube structure, the carbon nanotube structure is the carbon nanotube film shown in FIG. 3 or FIG. 11 or the carbon nanotube film shown in FIG. 12 or FIG. Carbon nanotube wires. The carbon nanotube film or the carbon nanotube wire needs to contain carbon nanotubes having metallic properties. In this case, the carbon nanotube structure is fixed to the surface of the heating element or the carbon nanotube structure by its own adhesiveness or conductive adhesive. The material of the metal sheet or the metal lead wire is copper or aluminum. When the first electrode and the second electrode are metal sheets, the metal sheet can be fixed to the surface of the heating element or the carbon nanotube structure with a conductive adhesive. The conductive adhesive electrically connects the first electrode and the second electrode to the carbon nanotube structure, and at the same time, is well fixed to the surface of the carbon nanotube structure to the first electrode and the second electrode. Let

  The hollow heat source may include a plurality of first electrodes and a plurality of second electrodes. The plurality of first electrodes and the plurality of second electrodes are disposed at intervals, and are each electrically connected to the heating element. By applying a voltage to the different electrodes, the heating element installed between the two electrodes can be operated, so that a portion of the heating element can dissipate heat.

  The hollow heat source further includes a reflective layer. The reflective layer reflects the heat released from the heating element, and releases the heat to the hollow structure of the hollow three-dimensional support to increase the heating efficiency. When the heating element is installed on the back surface of the hollow three-dimensional support, the reflective layer may be installed between the hollow three-dimensional support and the heating element. You may install in the outer surface of a support body. When the heating element is installed on the outer surface of the hollow three-dimensional support, the reflective layer is installed on the surface of the heating element opposite to the surface facing the hollow three-dimensional support. . That is, the heating element is installed between the hollow three-dimensional support and the reflective layer. The reflective layer is made of an insulating material such as metal oxide, metal salt, and ceramics.

  The hollow heat source may further include a protective layer. The protective layer is formed on the surface of the heating element opposite to the surface facing the reflective layer using a coating or sputtering link method. The material of the protective layer is, for example, an insulating material such as plastic, rubber and resin. The thickness of the protective layer is not limited and can be selected according to actual application, and the thickness of the protective layer is preferably 0.5 millimeters to 2 millimeters. The protective layer is used to protect the heating element by allowing the hollow heat source to be used in an insulated state, preventing dust from adhering to the heating element.

  Referring to FIG. 14, the present invention provides a method of manufacturing a hollow heat source. Specifically, the following steps are included.

  In the first step, a carbon nanotube structure is provided, and the carbon nanotube structure has a plurality of micropores.

  The structure of the carbon nanotube structure and the manufacturing method thereof are the above-described structure of the carbon nanotube structure and the manufacturing method thereof.

  In the second step, a hollow three-dimensional support is provided, and the carbon nanotube structure is placed on the surface of the hollow three-dimensional support.

  The hollow three-dimensional support is used for supporting the heating element and forming the heating element into a hollow three-dimensional structure. The material of the hollow three-dimensional support may be a hard material such as ceramics, glass, resin, or quartz, or may be a flexible material such as plastic or soft fiber.

  The carbon nanotube structure can be coated on or wound around the outer surface of the hollow three-dimensional support. Alternatively, the carbon nanotube structure can be fixed to the back surface or outer surface of the hollow three-dimensional support using an adhesive or a mechanical system.

  In the third step, the first electrode and the second electrode are placed at an interval, and the first electrode and the second electrode are electrically connected to the carbon nanotube structure.

  The installation method of the first electrode and the second electrode is related to the structure of the carbon nanotube structure. The direction extending from the first electrode to the second electrode needs to be the same as the major axis direction of the carbon nanotubes in the carbon nanotube structure.

  The first electrode and the second electrode are made of a conductive material, and are installed on the same surface of the carbon nanotube structure, both opposing surfaces of the carbon nanotube structure, or wound around the surface of the carbon nanotube structure. It is burned. The first electrode and the second electrode may be installed on the surface of the heating element using an adhesive property of the carbon nanotube structure or a conductive adhesive. The conductive adhesive fixes the first electrode and the second electrode to the surface of the carbon nanotube structure at the same time that the first electrode and the second electrode are electrically connected to the carbon nanotube structure. Can do. A voltage can be applied to the heating element by the first electrode and the second electrode. When the heating element is heated, the first electrode and the second electrode have to be installed at a predetermined distance in order to connect a predetermined resistance so as to prevent a short circuit.

  The first electrode and the second electrode are a conductive film, a metal sheet, or a metal lead wire. The material of the conductive film is a metal, an alloy, an indium tin oxide (ITO) film, an antimony tin oxide (ATO), a silver paste, a conductive polymer, or a carbon nanotube structure. The conductive film is formed on the surface of the carbon nanotube structure by physical vapor deposition, chemical vapor deposition, or other methods. The material of the metal sheet or the metal lead wire is copper or aluminum. The metal sheet or metal lead wire can be fixed to the surface of the carbon nanotube structure with a conductive adhesive.

  The first electrode and the second electrode may be a metallic carbon nanotube structure. The carbon nanotube structure has the structure shown in FIG. 3, FIG. 11, FIG. 12, or FIG. It is preferable to coat the surface of the carbon nanotubes in the carbon nanotube structure with a metal layer to increase the conductivity of the carbon nanotube structure.

  In the fourth step, a preform of the substrate is provided, and the preform of the substrate and the carbon nanotube structure are combined to form a heating element.

  The preform of the substrate is a substrate material, a solution comprising the substrate material, and a preformed reaction product for producing the substrate material. The preform of the substrate is liquid or gas at a predetermined temperature. The method in which the preform of the substrate and the carbon nanotube structure are combined is one kind of application, deposition, printing, immersion, and the like.

  The base material may be one or several types such as a polymer material and a non-metallic material. Specifically, since the polymer material is one or several of a thermoplastic polymer and a thermosetting polymer, the material of the preform of the base is a single polymer formed on the thermoplastic polymer and the thermosetting polymer. Solution. Alternatively, it is a mixed solution formed by dissolving the thermoplastic polymer or thermosetting polymer in a volatile organic solvent. After the carbon nanotube structure is immersed in the liquid substrate preform, the liquid substrate preform is solidified to combine the substrate and the carbon nanotube structure.

  Since the non-metallic material is glass, ceramics, semiconductor material, or the like, the preform of the base is a paste made of non-metallic material particles, a reaction gas for producing the non-metallic material, or a non-metallic material in a gaseous state. It is. Specifically, a preform of a gaseous substrate is formed by a method such as vacuum vapor deposition, sputtering, chemical vapor deposition, or physical vapor deposition, and the preform of the substrate is carbon in the carbon nanotube structure. Deposit on the surface of the nanotubes. Further, a plurality of non-metallic material particles are dispersed in a solvent, a paste is formed, and the carbon nanotube structure is immersed in the paste as a preform of the substrate, and then the solvent is evaporated, The carbon nanotube structure is combined.

  When the preform of the substrate is liquid, the carbon nanotube structure is immersed in the preform of the liquid substrate, and then the preform of the liquid substrate is solidified, thereby The material penetrates into the micropores of the carbon nanotube structure to form a heating element. When the preform of the substrate is a gas, the substrate preform is deposited on the surface of the carbon nanotube in the carbon nanotube structure, so that the material of the substrate is contained in the micropores of the carbon nanotube structure. Is added to form a heating element.

  In the third step, the step of forming the first electrode and the second electrode may be performed after forming the carbon nanotube composite structure in the fourth step. When the base material is added only in the micropores of the carbon nanotube structure, that is, when some of the carbon nanotubes are exposed on the surface of the carbon nanotube composite structure, the same method as in the second step The first electrode and the second electrode are directly formed on the surface of the heating element, and the first electrode and the second electrode are electrically connected to the carbon nanotube structure in the heating element. When the base material covers the surface of the carbon nanotube structure, the carbon nanotube composite structure is cut by a method of cutting so that the carbon nanotube is exposed on the surface of the carbon nanotube composite structure. Thereafter, the exposed carbon nanotube structure can be electrically connected to the first electrode and the second electrode in the same manner as in the second step.

Example 1
15 and 16, the hollow heat source 100 according to the first embodiment of the present invention includes a hollow three-dimensional support 102, a heating element 104, a first electrode 110, a second electrode 112, a reflective layer 108, a protective layer ( (Not shown). The hollow three-dimensional support 102 is a hollow ceramic tube having a circular cross section. The heating element 104 is installed on the outer surface of the hollow three-dimensional support 102 and includes a base and a carbon nanotube structure, and the carbon nanotube structure is composited in the base. The heating element 104 is electrically connected to the first electrode 110 and the second electrode 112.

  The base material is an epoxy resin. The carbon nanotube structure includes one hundred drone structure carbon nanotube films stacked. In the carbon nanotube structure, the aligned directions of the carbon nanotubes in adjacent carbon nanotube films are parallel to each other. The carbon nanotubes are arranged along a direction extending from the first electrode 110 to the second electrode 112. Since the base material is immersed in the micropores of the carbon nanotube structure, the carbon nanotubes in the carbon nanotube structure can be fixed. In addition, since the base material covers the carbon nanotube structure, the carbon nanotube structure can be further protected. The first electrode 110 and the second electrode 112 are made of palladium and have a thickness of 5 nanometers. The first electrode 110 and the second electrode 112 are installed on the heating element 104 with silver paste, and are electrically connected to the carbon nanotube structure. Since the palladium and the carbon nanotube have excellent metal wettability, the first electrode 110 and the second electrode 112 and the heating element 104 have an excellent electrical connection, and the hollow heat source 100 can increase the proportion of utilization of electrical energy.

  Since the heating element 104 is installed on the outer surface of the hollow three-dimensional support 102, the reflective layer 108 is a surface opposite to the surface of the heating element 104 facing the hollow three-dimensional support 102. Installed. That is, the heating element 104 is installed between the hollow three-dimensional support 102 and the reflective layer 108. The reflective layer 108 is an aluminum oxide film and has a thickness of 100 micrometers to 0.5 millimeters. Of course, the reflective layer 108 may not be provided. Accordingly, the heating direction of the hollow heat source 100 is not limited, and heat can be released from the back surface or the outer surface of the hollow heat source 100. When the heating element is formed of a carbon nanotube structure having a self-supporting structure, the heating element can be formed into a hollow three-dimensional structure without using the hollow three-dimensional support.

FIG. 17 is a photograph of a cross section formed by cutting the carbon nanotube composite structure along a direction perpendicular to the major axis direction of the carbon nanotube in Example 1 of the present invention. Referring to FIG. 17, it can be seen that after the carbon nanotubes and the epoxy resin are combined, the carbon nanotubes can keep a state of being aligned along the same direction in the epoxy resin. They are arranged along the same direction.

  The present embodiment provides a method for heating a heating target using the hollow heat source 100.

  First, an object to be heated is provided.

  Next, the heating target is placed inside the hollow structure of the hollow heat source 100.

  When the first electrode 110 and the second electrode 112 of the hollow heat source 100 are electrically connected to a power source (not shown) having a voltage of 10 to 20 volts, the hollow heat source 100 emits an electromagnetic wave having a long wavelength. be able to. When measured with a temperature surveying instrument, it can be seen that the surface temperature of the heating element 104 in the hollow heat source 100 is raised to 50 ° C. to 500 ° C. to heat the heating target. Accordingly, it can be seen that the carbon nanotube structure has high efficiency in converting electric energy into heat energy. Since the heat of the surface of the heating element 104 is transmitted to the object to be heated by heat radiation, the object to be heated can be uniformly heated. For carbon nanotubes that are black bodies, when the temperature is 200 ° C. to 450 ° C., infrared rays that are invisible to human eyes can be emitted. The heat radiation at this time is stable, the efficiency of heat release is high, and the amount of heat released is excellent.

  The heating object may be installed in direct contact with the hollow heat source 100 or at a predetermined distance from the hollow heat source 100. The heating target is heated using electromagnetic waves emitted from the carbon nanotube structure. The hollow heat source 100 using the carbon nanotube structure can be applied to factory pipes, laboratories, electric heaters, electric heaters, and the like.

  By controlling the dimensions of the heating element 104 and the voltage applied to the heating element 104, the heat released from the heating element 104 can be controlled. When the voltage is constant, the wavelength of the electromagnetic wave emitted from the heating element 104 can be adjusted by changing the thickness of the heating element 104. That is, the thicker the heating element 104, the shorter the wavelength of the electromagnetic wave emitted from the heating element 104. When the thickness of the heating element 104 is constant, the wavelength of the electromagnetic wave emitted from the heating element 104 becomes shorter as the voltage applied to the heating element 104 increases. Therefore, the hollow heat source 100 can be easily controlled.

  When the area of the heating element 104 is constant, the amount of voltage applied to the heating element 104 and the thickness of the carbon nanotube structure are controlled to control the heat released from the heating element 104. be able to. When the voltage is constant, the wavelength of the electromagnetic wave emitted from the heating element 104 can be adjusted by changing the thickness of the heating element 104. That is, the thicker the heating element 104, the shorter the wavelength of the electromagnetic wave emitted from the heating element 104. As the heating element 104 becomes thinner, the wavelength of the electromagnetic wave emitted from the heating element 104 becomes longer. When the thickness of the heating element 104 is constant, the wavelength of the electromagnetic wave emitted from the heating element 104 becomes shorter as the voltage applied to the heating element 104 increases. As the voltage applied to the heating element 104 decreases, the wavelength of the electromagnetic wave emitted from the heating element 104 increases. Therefore, the hollow heat source 100 can be easily controlled.

  When the carbon nanotube structure in the hollow heat source 100 has a small thickness and is transparent, and the material of the substrate is a transparent organic material or a transparent inorganic material, the hollow heat source 100 is a transparent hollow heat source. . When the base of the heating element 104 in the hollow heat source 100 is made of a flexible polymer, the hollow heat source 100 is a flexible hollow heat source.

  Referring to FIG. 18, when the heating element 104 is a single linear carbon nanotube composite structure, the linear carbon nanotube composite structure is formed on the surface of the hollow three-dimensional support 102. Wound around. Referring to FIG. 19, when the heating element 104 is a plurality of linear carbon nanotube composite structures, the plurality of linear carbon nanotube composite structures are installed so as to cross each other and have a film-like structure. The hollow three-dimensional support 102 is knitted and can be wrapped and wound.

  With reference to FIGS. 15 and 16, the method for manufacturing the hollow heat source 100 of the first embodiment will be described in detail as an example.

  In the first step, a carbon nanotube structure is provided, and the carbon nanotube structure has a plurality of micropores.

  The carbon nanotube structure includes one hundred drone structure carbon nanotube films stacked. In the carbon nanotube structure, the aligned directions of the carbon nanotubes in adjacent carbon nanotube films are parallel to each other.

  In the second step, a hollow three-dimensional support 102 is provided, and the carbon nanotube structure is placed on the surface of the hollow three-dimensional support 102.

  The hollow three-dimensional support 102 is a hollow ceramic tube. The carbon nanotube structure includes hundreds of drone-structured carbon nanotube films stacked, and the arrangement direction of the carbon nanotubes in adjacent drone-structure carbon nanotube films is parallel, and the thickness of the carbon nanotube structure is 300 Micrometer. The surface of the hollow three-dimensional support 102 is coated with the carbon nanotube structure by utilizing the adhesiveness of the carbon nanotube structure itself.

  In the third step, the first electrode 110 and the second electrode 112 are placed at an interval, and the first electrode 110 and the second electrode 112 are electrically connected to the carbon nanotube structure.

  After depositing two palladium films as the first electrode 110 and the second electrode 112 on the surface of the carbon nanotube structure by a sputtering method, the two palladium films are electrically connected to the metal lead wires, respectively. .

  In the fourth step, a preform of the substrate is provided, and the preform of the substrate and the carbon nanotube structure are combined to form the heating element 104.

  In this embodiment, the heating element 104 is formed by combining the polymer material and the carbon nanotube structure by a method of injecting glue. The method includes the following steps.

  In the first sub-step, a liquid thermosetting polymeric material is provided.

  The viscosity of the liquid thermosetting polymer material is 5 Pascal · second or less, and the viscosity can be maintained for 30 minutes or more at room temperature. The thermosetting polymer material includes a polymer material and additives such as a solidifying agent, a modifier, a filler, or a diluent.

  The mass percentage content of the polymer material in the thermosetting polymer material is 70% to 95%. The content by mass of the additive in the thermosetting polymer material is 5% to 30%. Examples of the polymer material include phenol resin, epoxy resin, bismaleimide resin, polybenzoxazine resin, cyanate ester resin, dei lyi, and polyimide resin. resin), polyurethane (Polyurethane), polymethyl methacrylate resin (PMMA) and the like.

  The solidifying agent is used for accelerating solidification of the thermosetting polymer material, and includes an aliphatic amine, an alicyclic amine, an aromatic amine, a polyamide ( It is one or several kinds such as Polyamide, acid anhydride, tertiary amine, and resin.

  The modifying agent can enhance the flexibility, shear resistance, bending resistance, insulation, and the like of the thermosetting polymer material. The modifier is one or several types such as polysulfide rubber and polyamide resin.

  The additive is used to improve heat dissipation conditions when the thermosetting polymer material is solidified, and can reduce the dose of the thermosetting polymer material and reduce the cost. . The additive is one or several kinds of asbestos fiber, glass fiber, quartz powder, aluminum oxide, silica gel powder and the like.

  The diluent is one or several kinds such as diglycidyl ether, polyglycidyl ether, and allylphenol.

  In this embodiment, a liquid thermosetting polymer material is produced with an epoxy resin. Specifically, the following steps are included.

  First, a mixture of glycidyl ether type epoxy resin and glycidic acid ester type epoxy resin is placed in a container, the mixture is heated to 30 ° C. to 60 ° C., and the mixture is mixed for 10 minutes so that the mixture is uniformly mixed. Stir.

  Next, an aliphatic amine and diglycidyl ether are added to the mixture and a chemical reaction is performed to form a reaction product.

  Finally, the reaction product is heated to 30 ° C. to 60 ° C. to form a liquid thermosetting polymer material containing an epoxy resin.

  In the second sub-step, the carbon nanotube structure is immersed in the liquid thermosetting polymer material.

  The method of immersing the carbon nanotube structure with the liquid thermosetting polymer material includes the following steps.

  First, the hollow three-dimensional support 102 on which the carbon nanotube structure is installed is placed in a mold.

  Next, in order to immerse the carbon nanotube structure, the liquid thermosetting polymer material is injected into the mold. In order for the liquid thermosetting polymer material to sufficiently immerse the carbon nanotube structure, the time for immersing the carbon nanotube structure is 10 minutes or more.

  In this example, first, the laminated hundreds of drone-structured carbon nanotube films were coated on the surface of the hollow ceramic tube, and then the hollow ceramic tube on which the carbon nanotube structure was installed was formed into a mold. Put in. Next, in order to immerse the carbon nanotube structure, a liquid thermosetting polymer material containing the epoxy resin is injected into the mold and immersed for 20 minutes.

  It should be understood that the method of immersing the carbon nanotube structure in the liquid thermosetting polymer material is not limited to the method of injection, and the liquid thermosetting polymer material is Due to capillary action, the carbon nanotube structure is sucked into the carbon nanotube structure, or the carbon nanotube structure is immersed, or the carbon nanotube structure is immersed in the liquid thermosetting polymer material. is there.

  In the third sub-step, the carbon nanotube structure immersed in the liquid thermosetting polymer material is solidified to form a carbon nanotube composite structure.

  In this embodiment, a method for solidifying a thermosetting polymer material containing an epoxy resin includes the following steps.

  First, the mold is heated to 50 ° C. to 70 ° C. by a heating device, and at this temperature, the thermosetting polymer material containing the epoxy resin is liquid. The temperature is maintained for 1 to 3 hours to increase the degree of solidification of the thermosetting polymer material, and the thermosetting polymer material continues to absorb heat.

  Next, the mold is continuously heated to 80 ° C. to 100 ° C. so as to increase the degree to which the thermosetting polymer material is solidified, and held at the temperature for 1 hour to 3 hours.

  Thereafter, the mold is continuously heated to 110 ° C. to 150 ° C. and held at the temperature for 2 hours to 20 hours so as to increase the degree of solidification of the thermosetting polymer material.

  Finally, heating is stopped, and after the mold has cooled to room temperature, the mold is released to form a carbon nanotube composite structure.

  In the heating method, the thermosetting polymer material can be solidified by directly heating the mold to 110 to 150 ° C.

  In the fourth sub-step, a reflective layer 108 is formed on the outer surface of the carbon nanotube structure.

  An aluminum oxide film serving as the reflective layer 108 is formed on the outer surface of the carbon nanotube structure by a sputtering method. The reflective layer 108 has a thickness of 100 micrometers.

  When the heating element 104 in the first embodiment is a flexible carbon nanotube composite structure, the hollow heat source 100 can be manufactured by the following method.

  In the first step, a carbon nanotube structure is provided.

  In the second step, a preform of a flexible substrate material is provided, and the preform of the flexible substrate material and the carbon nanotube structure are combined to form a flexible carbon nanotube composite structure.

  In the third step, a hollow three-dimensional support 102 is provided, and the flexible carbon nanotube composite structure is installed on the surface of the hollow three-dimensional support 102.

  In the fourth step, the first electrode 110 and the second electrode 112 are provided at intervals, and the first electrode 110 and the second electrode 112 are electrically connected to the carbon nanotube structure in the flexible carbon nanotube composite structure, respectively. Connect.

  Of course, after the first electrode 110 and the second electrode 112 are formed at an interval so as to be electrically connected to the carbon nanotube structure, the carbon nanotube structure and the flexible base material are pre-made. The carbon nanotube composite structure may be formed by combining the bodies.

(Example 2)
Referring to FIGS. 20, 21, and 22, the present embodiment provides a hollow heat source 200. The hollow heat source 200 according to this embodiment includes a heating element 204, a reflective layer 208, two first electrodes 210, and two second electrodes 212. The heating element 204 is a carbon nanotube structure formed in a hollow rectangular parallelepiped, and the carbon nanotube structure is one of the carbon nanotube structures described above. The two first electrodes 210 and the two second electrodes 212 are respectively installed at positions where the side surfaces of the hollow rectangular parallelepiped hollow structure are joined, and are electrically connected to the heating element 204. . The first electrode 210 and the second electrode 212 serve to support the heating element 204. The reflective layer 208 is disposed on the surface of the heating element 204 opposite to the surface facing the first electrode 210 and the second electrode 212.

  In the hollow heat source 200, the number of the first electrode 210 and the second electrode 212 is not limited, the first electrode 210 and the second electrode 212 are arranged in a predetermined shape, and the above-mentioned carbon nanotube structure is formed as described above. It is only necessary to wrap around the first electrode 210 and the second electrode 212 arranged in a predetermined shape to form a hollow heating element 204. The first electrode 210 and the second electrode 212 are used to pass a current through the carbon nanotube structure and simultaneously support the carbon nanotube structure.

(Example 3)
Referring to FIGS. 23 and 24, the present embodiment provides a hollow heat source 300. The hollow heat source 300 of this embodiment includes a hollow three-dimensional support 302, a heating element 304, a first electrode 310, a second electrode 312, a reflective layer 308, and a protective layer 309. The reflective layer 308 is installed on the back surface of the hollow three-dimensional support 302. The heating element 304 is installed on the surface of the reflective layer 308 opposite to the surface facing the hollow three-dimensional support 302. The protective layer 309 is disposed on the surface of the heating element 304 opposite to the surface facing the reflective layer 308. The first electrode 310 and the second electrode 312 are respectively disposed between the heating element 304 and the reflective layer 308, and are electrically connected to the heating element 304. The heating element 304 is electrically connected to a power source. Connect.

  In this embodiment, the hollow three-dimensional support 302 is a hollow semi-elliptical sphere, and the hollow semi-elliptical sphere has a hollow structure. The reflective layer 308 is placed on the surface of the hollow semi-elliptical sphere facing the hollow structure. The heating element 304 is one of the carbon nanotube structures described above, and covers the surface of the reflective layer 308 opposite to the surface facing the hollow semi-elliptical sphere. The first electrode 310 is installed on the surface of the bottom of the heating element 304 that contacts the reflective layer 308 and is electrically connected to the heating element 304. The second electrode 312 has a ring shape, is disposed on the surface of the opening of the heating element 304 that contacts the reflective layer 308, and is electrically connected to the heating element 304. The protective layer 309 is formed on the surface of the heating element 304 opposite to the surface facing the reflective layer 308 by coating or sputtering. The material of the protective layer is, for example, an insulating material such as plastic, rubber and resin. The thickness of the protective layer is not limited and can be selected according to actual application, and the thickness of the protective layer is preferably 0.5 millimeters to 2 millimeters. The protective layer is used to protect the heating element 304 by using the hollow heat source 300 in an insulated state, preventing dust from adhering to the heating element 304. The hollow three-dimensional support 302 has a space for accommodating a heating target, and may have any shape as long as the heating target can be heated.

  The hollow heat source and the method for producing the hollow heat source have the following excellent points.

  By directly combining the base material and the carbon nanotube structure having the self-supporting structure to form a heating element, the carbon nanotube retains the form of the carbon nanotube structure in the heating element. The carbon nanotubes in the heating element can be uniformly distributed to form a conductive path, and compared with the carbon nanotubes in the prior art limited to the concentration dispersed in the solution, the carbon nanotubes The content in the heating element can reach 99%. Therefore, the hollow heat source is highly efficient in converting electrical energy into heat energy, and can increase the heat radiation temperature of the hollow heat source.

  In the hollow heat source, the heating element includes a carbon nanotube structure, the carbon nanotubes in the carbon nanotube structure are uniformly arranged, and the heating element has a uniform thickness and resistance. Heat can be released. Since the carbon nanotube has a high efficiency of converting electric energy into heat energy, the hollow heat source has a high temperature rising rate, a high thermal response speed, and a high heat exchange rate.

  Since the carbon nanotube in the heating element has excellent mechanical performance, excellent toughness and excellent mechanical strength, the heating element has excellent mechanical performance, excellent toughness and mechanical strength, and has a long service life. Further, when the carbon nanotube structure and the flexible substrate are combined to form the heating element, a flexible hollow heat source can be manufactured using the heating element.

  Since the diameter of the carbon nanotube in the heating element is small, the heating element has a small thickness. Therefore, an extremely small hollow heat source can be manufactured, and a small element to be heated can be heated using the small hollow heat source.

  The material of the substrate is not limited to a polymer, and since the temperature range is wide, the hollow heat source can be more widely applied.

  When the carbon nanotube structure is made of a drone structure carbon nanotube film, the plurality of carbon nanotubes in the carbon nanotube film are connected to each other along the same direction, so that the carbon nanotube structure has excellent conductivity. Therefore, the hollow heat source has excellent heating performance. Further, since the carbon nanotube film has a predetermined transparency, a transparent hollow heat source can be manufactured.

  A method of directly combining the base material and the carbon nanotube structure having the self-supporting structure to form a heating element is simple. In addition, the content of the carbon nanotubes in the heating element can be easily controlled. After the carbon nanotube structure having the self-standing structure and the base material are directly combined, the carbon nanotube structure can maintain the conventional state. Therefore, the heating element can release almost the same heat as the heating element made of a pure carbon nanotube structure.

100, 200, 300 Hollow heat source 110, 210, 310 First electrode 112, 212, 312 Second electrode 104, 204, 304 Heating element 108, 208, 308 Reflective layer 102, 302 Hollow three-dimensional support 143a Carbon nanotube film 143b carbon nanotube segment 145 carbon nanotube 309 protective layer

Claims (1)

A heating element and at least two electrodes electrically connected to the heating element;
The heating element has a hollow structure including a carbon nanotube composite structure, and the carbon nanotube composite structure includes at least one linear carbon nanotube composite structure,
The linear carbon nanotube composite structure comprises at least one carbon nanotube wire-like structure and the substrate material, the carbon nanotube wire-like structure and the substrate material are compounded,
The carbon nanotube linear structure is composed of only a plurality of carbon nanotubes,
In the carbon nanotube linear structure, a plurality of micropores are formed, the base material is penetrated only into the plurality of micropores, and a part of the carbon nanotubes in the carbon nanotube linear structure is heated. Exposed on the surface of the element,
The hollow heat source, wherein the at least two electrodes are disposed on the same surface or different surfaces of the heating element and are electrically connected to the carbon nanotube linear structure .