JP2021179005A - Apparatus and method for continuously manufacturing nano carbon material - Google Patents

Abstract

To provide an apparatus and method for continuously manufacturing a nano carbon material, continuously manufacturing a nano carbon material having one or more layers at a constant speed at a low cost.SOLUTION: An apparatus 1 for continuously manufacturing a nano carbon material comprises: a continuous conveying device 110 for continuously conveying a continuous conveyance substrate 15; a carrying-in port 65 for carrying in the continuous conveyance substrate 15; a carrying-out port 67 for carrying out the continuous conveyance substrate 15; a reaction vessel 60 for storing the continuous conveyance substrate 15 during the conveyance; a gas carbon source supply part 30 for supplying a gas carbon source 35 in the reaction vessel 60; and a heating part 50 for depositing a nano carbon material layer 90 on the surface of the continuous conveyance substrate by heating the continuous conveyance substrate in the reaction vessel. The heating part 50 includes an optical heater 51 for heating the continuous conveyance substrate in the reaction vessel by emitting light into the reaction vessel.SELECTED DRAWING: Figure 2

Description

The present invention relates to a device for continuously producing a nanocarbon material and a method for continuously producing a nanocarbon material.

In recent years, it has been studied to use nanocarbon materials for electrical contacts of electrical connection parts such as connectors. Here, the nanocarbon material means a carbon material containing one or more of graphene, a graphene carbon material composed of a laminate of two or more layers of graphene, and amorphous carbon.

It is preferable that the nanocarbon material can be continuously manufactured at a constant speed because the manufacturing cost is reduced and mass production is facilitated.

Patent Document 1 discloses a graphene film forming method using plasma CVD, in which a plasma containing radicals is generated from a raw material gas by applying microwaves at a predetermined position and the radicals are forcibly diffused on the surface of a substrate. Has been done. According to the method of Patent Document 1, a large-area graphene film can be continuously produced.

JP-A-2017-66506

However, the graphene film forming method of Patent Document 1 generates plasma, so that the manufacturing cost is high.

The present invention has been made in view of the problems of the prior art. An object of the present invention is to provide a continuous production apparatus for nanocarbon materials and a continuous production method for nanocarbon materials, which continuously produce nanocarbon materials having a single layer or more at a constant rate at low cost.

The continuous manufacturing apparatus for a nanocarbon material according to an aspect of the present invention includes a continuous transport device for continuously transporting a continuous transport substrate, an inlet for carrying in the continuous transport substrate, and a carry-out outlet for carrying out the continuous transport substrate. By heating the reaction vessel that has and accommodates the continuous transport substrate being transported, the gas carbon source supply unit that supplies the gaseous carbon source into the reaction vessel, and the continuous transport substrate in the reaction vessel. A heating unit for forming a nanocarbon material layer on the surface of the continuous transfer substrate is provided, and the heating unit heats the continuous transfer substrate in the reaction vessel by irradiating the inside of the reaction vessel with light. Equipped with a heating device.

In the continuous production apparatus for nanocarbon materials, it is preferable that the optical heating apparatus irradiates light having a wavelength of 0.70 μm to 5.00 μm and an intensity of 1 kW to 8 kW.

In the continuous production apparatus for nanocarbon materials, the optical heating apparatus is preferably one or more of a laser heating apparatus and a flash lamp heating apparatus.

In the continuous production apparatus for nanocarbon materials, the continuous transfer apparatus may include a winding unit for winding the continuous transfer substrate in a roll shape and a winding unit for winding the continuous transfer substrate in a roll shape. preferable.

It is preferable that the continuous production apparatus for the nanocarbon material further includes a pre-winding cooling unit that cools the continuous transport substrate carried out from the reaction vessel before being wound by the winding unit.

In the continuous production apparatus for nanocarbon materials, it is preferable that the reaction vessel is further provided with a direction changing roller that changes the transport direction of the continuous transport substrate in the reaction vessel.

In the continuous manufacturing apparatus for nanocarbon materials, the pre-winding cooling unit is preferably a cooling roller that comes into contact with the continuous transport substrate before being wound by the winding unit.

In the method for continuously producing a nanocarbon material according to an aspect of the present invention, a continuous transfer substrate is heated in a reaction vessel in the presence of a gaseous carbon source, whereby a nanocarbon material layer is formed on the surface of the continuous transfer substrate. The film forming step comprises a film forming step of heating the continuous transfer substrate in the reaction vessel by irradiating the inside of the reaction vessel with light.

In the method for continuously producing a nanocarbon material, it is preferable that the optical heating device irradiates light having a wavelength of 0.70 μm to 5.00 μm and an intensity of 1 kW to 8 kW.

In the method for continuously producing a nanocarbon material, the optical heating device is preferably one or more of a laser heating device and a flash lamp heating device.

In the method for continuously producing a nanocarbon material, the continuous transfer substrate is continuously conveyed using a continuous transfer device, and the continuous transfer device includes a winding portion for unwinding the roll-shaped continuous transfer substrate and the continuous transfer substrate. It is preferable to provide a winding unit for winding the material into a roll.

In the method for continuously producing a nanocarbon material, it is preferable to further include a pre-winding cooling step of cooling the continuous transport substrate carried out from the reaction vessel before being wound up by the winding unit.

In the method for continuously producing a nanocarbon material, it is preferable that in the film forming step, the transport direction of the continuous transfer substrate is changed in the reaction vessel, and the film formation process is performed on the changed direction continuous transfer substrate.

In the method for continuously producing a nanocarbon material, it is preferable that the pre-winding cooling step is performed by using a cooling roller that comes into contact with the continuous transport substrate before being wound by the winding unit.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a continuous production apparatus for nanocarbon materials and a continuous production method for nanocarbon materials, which continuously produce nanocarbon materials having a single layer or more at a constant rate at low cost.

It is sectional drawing which shows typically the nanocarbon material composite manufactured by the continuous manufacturing apparatus of nanocarbon material which concerns on 1st Embodiment. It is a figure which shows typically the continuous manufacturing apparatus of the nano carbon material which concerns on 1st Embodiment. It is a figure which shows the state change of the surface of the continuous transfer substrate 15 when the nanocarbon material composite 95 is manufactured from the continuous transfer substrate 15 by using the continuous production apparatus of the nano carbon material shown in FIG. 2. 3 (A), 3 (B) and 3 (C) are examples of heat treatment times of 0 minutes, 17 minutes and 25 minutes, respectively. It is a graph which shows the Raman analysis result of the nanocarbon material layer 90 shown in FIG. 3C. FIG. 4A is an optical micrograph of the surface of the nanocarbon material layer 90 shown in FIG. 3C. FIG. 4B is a graph showing the average value of Raman analysis results at the measurement site 1, the measurement site 11 of FIG. 4A, and nine measurement sites (not shown) existing between them. It is a figure which shows the relationship between the film formation time of the nanocarbon material layer 90, and the coverage | coverage in the nanocarbon material composite 95 shown in FIG. FIG. 5A is a graph showing the relationship between the film formation time and the coverage of the nanocarbon material layer 90. FIG. 5B is a diagram showing the relationship between the film formation time and the coverage of the nanocarbon material layer 90 in a table. It is a figure which shows typically the continuous manufacturing apparatus of the nano carbon material which concerns on 2nd Embodiment. It is a figure which shows typically the continuous manufacturing apparatus of the nano carbon material which concerns on 3rd Embodiment. It is a figure which shows typically the continuous manufacturing apparatus of the nano carbon material which concerns on 4th Embodiment.

Hereinafter, the continuous manufacturing apparatus for the nanocarbon material and the continuous manufacturing method for the nanocarbon material according to the embodiment will be described in detail with reference to the drawings.

First, the nanocarbon material composite manufactured by the continuous manufacturing apparatus for nanocarbon materials according to the first embodiment will be described.

<Nanocarbon material composite>
FIG. 1 is a cross-sectional view schematically showing a nanocarbon material composite manufactured by the nanocarbon material continuous manufacturing apparatus according to the first embodiment. The nanocarbon material composite 95 shown in FIG. 1 includes a continuous transfer substrate 15 and a nanocarbon material layer 90 formed on the surface of the continuous transfer substrate 15. The arrow C in FIG. 1 indicates the transport direction of the continuous transfer substrate 15 in the continuous production apparatus for nanocarbon materials according to the first embodiment shown in FIG.

[Continuous transfer board]
The continuous transfer substrate 15 can react in a physically continuous state by having the substrate itself has a continuous shape in the transfer direction or by physically connecting adjacent substrates separated from each other by a connecting member. It means a substrate 15 having a shape.

As the form of the continuous transfer substrate 15, for example, a plate shape, a strip shape, a foil shape, a thin film shape, a tubular shape, a rod shape, a linear shape, a long shape, or the like is used. In the case of a rod shape or a linear shape, the continuous transfer substrate 15 may be a single wire, a multi-wire, a stranded wire or the like.

The length of the continuous transfer substrate 15 is, for example, 30 cm to 30 m. In the case of a rod shape or a linear shape, the width of the continuous transfer substrate 15 is, for example, 5 mm to 50 mm.

As the material of the continuous transfer substrate 15, for example, pure copper, copper alloy, pure nickel, nickel alloy, gold, platinum and the like are used. Of these, pure copper or a copper alloy is preferable because it is relatively inexpensive and the formation of the nanocarbon material on the continuous transfer substrate 15 is good.

The surface state of the continuous transfer substrate 15 is not particularly limited. The surface of the continuous conveying substrate 15, for example, the surface roughness _{R Z} may be the mirror-polished of about 0.2 to 0.6 [mu] m.

[Nanocarbon material layer]
The nanocarbon material layer 90 is a layer made of a nanocarbon material and formed on the surface of the continuous transfer substrate 15. Here, the nanocarbon material means a carbon material containing one or more of graphene, a graphene multilayer body composed of a laminated body of two or more layers of graphene; and amorphous carbon.

In the nanocarbon material composite 95, the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15.

The thickness of the nanocarbon material layer 90 is, for example, 0.34 to 3.4 nm, preferably 0.34 to 1.7 nm. When the thickness of the nanocarbon material layer 90 is within the above range, any carbon material of a carbon material containing one or more of graphene, a graphene multilayer composed of a laminate of two or more layers of graphene, and amorphous carbon; Is also preferable because it can be produced.

Next, the continuous manufacturing apparatus for the nanocarbon material and the continuous manufacturing method for the nanocarbon material according to the embodiment will be described in detail.

[First Embodiment]
(Continuous manufacturing equipment for nano-carbon materials)
FIG. 2 is a diagram schematically showing a continuous manufacturing apparatus for nanocarbon materials according to the first embodiment. As shown in FIG. 2, the continuous production apparatus 1A (1) for nanocarbon materials includes a continuous transfer apparatus 110, a reaction vessel 60A (60), a gas carbon source supply unit 30, a heating unit 50A (50), and a heating unit 50A (50). To prepare for.

<Continuous transfer device>
The continuous transfer device 110 is a unit that continuously conveys the continuous transfer board 15. The continuous transfer device 110 is usually adapted to continuously transfer the continuous transfer board 15 at a constant speed.

As the continuous transfer device 110, a device including a winding unit 112 for unwinding the roll-shaped continuous transfer substrate 15 and a winding unit 114 for winding the continuous transfer substrate 15 in a roll shape is usually used.

When the continuous transfer substrate 15 unwound by the continuous transfer substrate 1A of the nanocarbon material is subjected to the film formation treatment, the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15, and the nanocarbon material composite 95 is formed. Will be. Since the nanocarbon material composite 95 includes the continuous transfer substrate 15, the winding unit 114 for winding the nanocarbon material composite 95 in a roll shape is also a device for winding the continuous transfer substrate 15 in a roll shape.

In the continuous transfer device 110, at least the winding unit 114 is usually driven. The unwinding unit 112 may be driven.

The unwinding portion 112 and the continuous transport substrate 15 to be unwound are arranged in the continuous transport device chamber 115A1 (115) in order to accommodate the film-forming base material and prevent exposure to the atmosphere.

The winding unit 114 and the continuous transfer substrate 15 or the nanocarbon material composite 95 wound up are inside the continuous transfer device chamber 115A2 in order to store the base material after film formation and prevent exposure to the atmosphere. Is placed in.

<Reaction vessel>
The reaction container 60A has a carry-in inlet 65 into which the continuous transfer board 15 is carried in and a carry-out port 67 in which the continuous transfer board 15 is carried out, and is a container for accommodating the continuous transfer board 15 being carried. Here, the reaction vessel 60A is a vessel that hinders the flow of an object or substance inside and outside the reaction vessel 60A through the wall surface of the reaction vessel 60A, and allows heat to flow through the wall surface of the reaction vessel 60A.

The reaction vessel 60A includes a hollow reaction vessel body 61. A translucent wall portion 62 that transmits light emitted from the light heating device 51 of the heating portion 50 is formed on at least a part of the inner wall of the reaction vessel main body 61B (61). The entire reaction vessel body 61B may have translucency.

The shapes of the reaction vessel 60A and the reaction vessel main body 61B constituting the reaction vessel 60A are not particularly limited, but in the nanocarbon material continuous production apparatus 1A shown in FIG. 2, the reaction vessel 60A and the reaction vessel main body 61 are tubular bodies. When the reaction vessel 60A is a tubular body, the length of the reaction vessel 60A is, for example, 100 to 2000 mm, preferably 400 to 600 mm. When the reaction vessel 60A is a tubular body, the inner diameter of the reaction vessel 60A is, for example, 5 to 50 mm.

The carry-in inlet 65 is a portion for carrying the continuous transfer substrate 15 into the reaction vessel inner space 63, which is the space inside the reaction vessel 60A. The carry-out port 67 is a portion where the continuous transport substrate 15 is carried out from the reaction vessel inner space 63 in the reaction vessel 60A. The carry-in inlet 65 and the carry-out port 67 each have a gate-like structure so that the inside of the reaction vessel 60A can be substantially kept in a predetermined atmosphere when the continuous transport substrate 15 is carried in and out. It is preferable that the carry-in inlet 65 and the carry-out port 67 have a small gap between the carry-in inlet 65 and the carry-out port 67 and the continuous transfer board 15. Further, if necessary, a flexible plate-like body or the like that can keep the inside of the reaction vessel 60A in a predetermined atmosphere may be provided around the carry-in inlet 65 and the carry-out port 67.

The reaction vessel 60A is capable of heating the reaction vessel inner space 63 inside the reaction vessel 60A by a heating unit 50 provided outside the reaction vessel 60A.

In the reaction vessel 60A, it is preferable that the degree of vacuum in the reaction vessel inner space 63 can be preferably an ultra-high vacuum to 2 atm. Here, the ultra-high vacuum means a vacuum degree of ^10-8 to ^{10-5 Pa.}

As the material of the reaction vessel 60A, for example, quartz, ceramic or the like is used. Of these, quartz is preferable because it is transparent and allows infrared rays to pass therethrough, so that the contents in the space 63 inside the reaction vessel can be easily heated.

As the reaction vessel 60A, for example, a quartz tube is used.

<Gas carbon source supply unit>
The gaseous carbon source supply unit 30 is a unit that supplies the gaseous carbon source 35 into the reaction vessel 60A. The gaseous carbon source supply unit 30 is a unit that supplies at least the gaseous carbon source 35. If necessary, the gas carbon source supply unit 30 may be capable of introducing a gas such as a carrier gas or a hydrogen gas (not shown) into the reaction vessel 60A.

The gaseous carbon source 35 is a gas that is a raw material for a nanocarbon material. As the gaseous carbon source 35, for example, a carbon-containing gas such as methane gas, ethylene gas, acetylene gas, butane gas, ethanol gas, methanol gas, and propane gas is used. Of these, methane gas is preferable because it is easy to form the nanocarbon material layer 90.

As the carrier gas, for example, an inert gas such as argon gas or nitrogen gas is used. Of these, argon gas is preferable because it can be used as a diluting gas for a gaseous carbon source and has an excellent gas purging power.

The flow rate of a gas such as a gas carbon source 35, a carrier gas (not shown), and a hydrogen gas is controlled by using a mass flow controller or the like.

In the nanocarbon material continuous production apparatus 1A shown in FIG. 2, the gas carbon source supply unit 30 is provided on the wall surface of the reaction vessel 60A. However, as a modification of the continuous production apparatus 1A for the nanocarbon material, for example, the gas carbon source supply unit 30 may be formed so as to be connected to the carry-in inlet 65 instead of the wall surface of the reaction vessel 60A.

<Heating part>
The heating unit 50 is a unit that forms a nanocarbon material layer 90 on the surface of the continuous transfer substrate 15 by heating the continuous transfer substrate 15 in the reaction vessel 60A.

The heating unit 50 is provided in each of the vertical directions outside the reaction vessel 60A so that the continuous transfer substrate 15 arranged in the reaction vessel inner space 63 can be heated from the vertical direction.

The heating unit 50 is a heating means capable of heating the continuous transfer substrate 15 to 900 ° C. or higher. Further, the heating unit 50 includes a light heating device 51 that heats the continuous transfer substrate 15 in the reaction vessel 60A by irradiating the inside of the reaction vessel 60A with light.

The heating unit 50 heats the continuous transfer substrate 15 to usually 900 to 1250 ° C, preferably 1000 to 1800 ° C.

The light heating device 51 preferably irradiates light having a wavelength of 0.70 μm to 5.00 μm and an intensity of 1 kW to 36 kW. Further, it is more preferable that the light heating device 51 irradiates light having a wavelength of 1.10 μm to 2.00 μm and an intensity of 1 kW to 8 kW. When the wavelength and intensity of the light emitted by the optical heating device 51 are within the above ranges, the continuous transfer substrate can be efficiently heated, which is preferable.

As the light heating device 51, for example, one or more of a laser heating device and a flash lamp heating device are used. Of these, the laser heating device is preferable because it is easy to control the range of the heating region.

The operation of the nanocarbon material continuous production apparatus 1A according to the first embodiment will be described in the nanocarbon material continuous production method according to the first embodiment below.

(Continuous manufacturing method of nano carbon material)
The method for continuously producing a nanocarbon material according to the first embodiment is a continuous production method using the nanocarbon material continuous production apparatus 1A according to the first embodiment.

The method for continuously producing a nanocarbon material according to the first embodiment includes a film forming step.

<Film formation process>
The film forming step is a step of forming a nanocarbon material layer 90 on the surface of the continuous transfer substrate 15 by heating the continuously transferred substrate 15 in the reaction vessel 60A in the presence of the gas carbon source 35. be. In the film forming step, an optical heating device 51 that heats the continuous transfer substrate 15 in the reaction vessel 60A by irradiating the inside of the reaction vessel 60A with light is used.

In the film forming step, the continuous transfer substrate 15 is heated by using the optical heating device 51 in the presence of the gas carbon source 35. As a result, in this step, the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15, and as a result, the nanocarbon material composite including the continuous transfer substrate 15 and the nanocarbon material layer 90 formed on the surface thereof is formed. Body 95 is obtained.

In a general batch-type method for producing a nanocarbon material, the base material is usually annealed before the film forming step so that the nanocarbon material is suitably formed on the surface of the base material. Here, the annealing treatment of the base material is, for example, a treatment of heating the metal base material to smooth the surface of the base material.

On the other hand, in the method for continuously producing a nanocarbon material according to the embodiment, since heating in the film forming step also has an annealing treatment action, it is not necessary to separately provide an annealing treatment step in addition to the film forming step. In the method for continuously producing a nanocarbon material according to the embodiment, if necessary, an annealing treatment may be performed on the continuous transfer substrate 15 before the film forming step.

The transfer speed of the continuous transfer substrate 15 is preferably 10 to 200 mm / min.

The film formation in the film formation step is performed by heating using the heating unit 50. Specifically, the film forming step is performed by, for example, a CVD film forming method using an optical heating device 51, resistance heating, hot air heating, infrared heating, induction heating, a laser heating method, or the like.

In this step, the ratio of the concentration of the gaseous carbon source 35 to the concentration of the carrier gas in the reaction vessel 60A is usually 1-1000000 ppm, preferably 10 to 50,000 ppm.

For example, when the carrier gas is argon gas and the gas carbon source 35 is methane gas, the ratio of the concentration of methane gas to the concentration of argon gas is usually 1 to 59000 ppm, preferably 10 to 40,000 ppm. When the ratio of the concentration of methane gas is within the above range, the nanocarbon material layer 90 can be formed in a state where the methane gas as the gas carbon source 35 is less than the explosion limit, which is preferable.

In this step, hydrogen gas may be introduced into the reaction vessel 60A in addition to the carrier gas and the gaseous carbon source 35. The ratio of the concentration of hydrogen gas to the concentration of carrier gas in the reaction vessel 60A in this step is usually 1-1000000 ppm, preferably 1-40000 ppm.

For example, when the carrier gas is argon gas, the ratio of the concentration of hydrogen gas to the concentration of argon gas is usually 1 to 48,000 ppm, preferably 10 to 40,000 ppm.

The heating temperature is, for example, 900 to 1250 ° C, preferably 950 to 1050 ° C. The heating time is, for example, 0.5 to 60 minutes, preferably 1 to 60 minutes.

The light heating device 51 preferably irradiates light having a wavelength of 0.70 μm to 5.00 μm and an intensity of 1 kW to 36 kW. Further, it is more preferable that the light heating device 51 irradiates light having a wavelength of 1.10 μm to 2.00 μm and an intensity of 1 kW to 8 kW. When the wavelength and intensity of the light emitted by the optical heating device 51 are within the above ranges, the continuous transfer substrate can be efficiently heated, which is preferable.

As the light heating device 51, for example, one or more of a laser heating device and a flash lamp heating device are used. Of these, the laser heating device is preferable because it is easy to control the range of the heating region.

When the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15 by heating the continuous transfer substrate 15 using the optical heating device 51 by the heating unit 50, the continuous transfer substrate 15 and the nanocarbon formed on the surface thereof are formed. A nanocarbon material composite 95 containing the material layer 90 is obtained.

FIG. 3 is a diagram showing an example of a state change of the surface of the continuous transfer substrate 15 when the nanocarbon material composite 95 is manufactured from the continuous transfer substrate 15 using the continuous production apparatus for the nanocarbon material shown in FIG. 2. be. 3 (A), 3 (B) and 3 (C) are examples of heat treatment times of 0 minutes, 17 minutes and 25 minutes, respectively.

The processing conditions in FIG. 3 are as follows. That is, a continuous production apparatus 1A for a nanocarbon material equipped with a reaction vessel 60A having a length of 360 mm was used. Further, the continuous transfer substrate 15 having a width of 10 mm and a thickness of 0.5 mm whose surface was polished with pure copper was conveyed at a transfer speed of 14.4 mm / min. Further, methane gas having a concentration of 10 ppm was used as the gas carbon source 35, and the heating temperature was set to 1000 ° C. The temperature was measured accurately using a K thermocouple and an R thermocouple.

The coverage in FIG. 3 is determined after the sample of the nanocarbon material composite 95 is oxidized to emphasize the contrast of brightness between the pure copper of the continuous transfer substrate 15 and the nanocarbon material layer 90 made of graphene. Calculated. Here, the coverage is a ratio of the surface area of the nanocarbon material layer 90 to the surface area of the continuous transfer substrate 15.

As shown in FIG. 3A, when the heat treatment time was 0 minutes, only pure copper of the continuous transfer substrate 15 was observed on the surface, and the coverage was 0%.

Further, as shown in FIG. 3B, when the heat treatment time is 17 minutes, the surface of the nanocarbon material layer 90 made of a large number of graphene aggregates having a crystal size of 5 μm and the continuous transfer substrate 15 are formed. Pure copper was observed, and the coverage was 50%.

Further, as shown in FIG. 3C, when the heat treatment time was 25 minutes, only the nanocarbon material layer 90 made of graphene was observed as a surface state, and the coverage was 100%.

FIG. 4 is a graph showing the Raman analysis results of the nanocarbon material layer 90 shown in FIG. 3 (C). FIG. 4A is an optical micrograph of the surface of the nanocarbon material layer 90 shown in FIG. 3C.

Note that FIG. 4B is a graph showing the average value of the Raman analysis results at the measurement site 1 and the measurement site 11 of FIG. 4A, and nine measurement sites (not shown) existing between them. ^{The peak of the G band (1590 cm -1} ) and the 2D band (1590 cm -1) indicating the presence of graphene at the measurement site 1, the measurement site 11, and all nine measurement sites (11 measurement points) (not shown) existing between them. A peak of 2700 cm ^-1 ) was observed. Therefore, FIG. 4B shows the average value of 11 measurement points.

The peak height of the 2D band from background (2700 cm ^-1), 2D / G which is calculated by dividing the peak height of the G band from background (1590 cm ^-1) was 1.38 ( Peak G <Peak 2D). Therefore, it can be seen that the graphene constituting the nanocarbon material layer 90 in FIG. 4A is a single layer.

In the Raman spectrum, when the height of the peak 2D from the background is smaller than the height of the peak G from the background (peak G> peak 2D), it represents a multilayer graphene composed of three or more layers of graphene. It is said that. Further, in the Raman spectrum, when the height of the peak G from the background and the height of the peak 2D from the background are the same (peak G = peak 2D), it is said to represent a multi-layer graphene composed of two layers of graphene. ing. Further, in the Raman spectrum, when the height of the peak 2D from the background is larger than the height of the peak G from the background (peak G <peak 2D), it represents a single-layer graphene composed of one layer of graphene. It is said that.

FIG. 5 is a diagram showing the relationship between the film formation time and the coverage of the nanocarbon material layer 90 in the nanocarbon material composite 95 shown in FIG. FIG. 5A is a graph showing the relationship between the film formation time and the coverage of the nanocarbon material layer 90. FIG. 5B is a diagram showing the relationship between the film formation time and the coverage of the nanocarbon material layer 90 in a table.

As shown in FIG. 5A, it was found that the graph showing the relationship between the film formation time and the coverage shows a so-called logistic curve. Therefore, if a logistic curve is created in advance, it is possible to control the coverage of the nanocarbon material layer 90 in the nanocarbon material composite 95 based on this logistic curve.

(Effect of continuous manufacturing apparatus for nanocarbon material according to the first embodiment)
According to the nanocarbon material continuous production apparatus according to the first embodiment, it is possible to provide a nanocarbon material continuous production apparatus for continuously producing a single layer or more nanocarbon material at a constant speed at a low cost. ..

The reason why this continuous manufacturing apparatus can manufacture nanocarbon materials at low cost is that since annealing treatment or reduction treatment for the continuous transfer substrate 15 is not essential, equipment related to these treatments can be omitted. ..

(Effect of continuous production method of nanocarbon material according to the first embodiment)
According to the method for continuously producing a nanocarbon material according to the first embodiment, it is possible to provide a method for continuously producing a nanocarbon material having a single layer or more at a low cost and continuously at a constant speed. ..

The reason why this continuous manufacturing method can manufacture nanocarbon materials at low cost is that annealing treatment or reduction treatment for the continuous transfer substrate 15 is not essential.

[Second Embodiment]
(Continuous manufacturing equipment for nano-carbon materials)
FIG. 6 is a diagram schematically showing a continuous manufacturing apparatus for nanocarbon materials according to the second embodiment. As shown in FIG. 6, the continuous production apparatus 1B (1) for the nanocarbon material includes a continuous transfer apparatus 110, a reaction vessel 60B (60), a gas carbon source supply unit 30, a heating unit 50B (50), and the heating unit 50B (50). It is provided with a pre-winding cooling unit 120B (120).

The nanocarbon material continuous manufacturing apparatus 1B according to the second embodiment differs from the nanocarbon material continuous manufacturing apparatus 1A according to the first embodiment only in that it further includes a prewind cooling unit 120B. , Other configurations are the same.

Therefore, the same components of the nanocarbon material continuous manufacturing apparatus 1B and the nanocarbon material continuous manufacturing apparatus 1A are designated by the same reference numerals, and the description of the configuration and operation is omitted or simplified. For example, the reaction vessel 60B, the heating unit 50B1, the continuous transfer device chamber 115B1 and the like of the nanocarbon material continuous production apparatus 1B are the reaction vessel 60A, the heating unit 50A1, the continuous transfer device chamber 115A1 and the like of the nanocarbon material continuous production apparatus 1A. Is the same as. Hereinafter, the pre-winding cooling unit 120 will be described.

<Cooling section before winding>
The pre-winding cooling unit 120B is a unit that cools the continuous transfer substrate 15 carried out from the reaction vessel 60B before being wound up by the winding unit 114. The pre-winding cooling unit 120B is provided between the carry-out port 67 of the reaction vessel 60B and the winding unit 114.

When the continuous transfer substrate 15 unwound by the continuous production apparatus 1B for the nanocarbon material is subjected to the film formation treatment, the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15, and the nanocarbon material composite 95 is formed. Will be. Since the nanocarbon material composite 95 includes the continuous transfer substrate 15, the pre-winding cooling unit 120B that cools the nanocarbon material composite 95 before winding it by the winding unit 114 winds the continuous transfer substrate 15 into the winding unit 114. It is also a unit that cools before winding up with.

The pre-winding cooling unit 120B is a unit that cools the continuous transfer substrate 15. When the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15 to obtain the nanocarbon material composite 95, the pre-winding cooling unit 120B can also be a unit for cooling the nanocarbon material composite 95. be.

The cooling of the nanocarbon material composite 95 obtained in the film forming treatment has an effect of stopping the catalytic reaction in the film forming process of the nanocarbon material layer 90. Therefore, by controlling the cooling conditions in the pre-winding cooling unit 120B, the chemical properties, physical properties, and the like of the obtained nanocarbon material layer 90 can be changed.

As the pre-winding cooling unit 120B, for example, a device in which a cooling device such as a fan or a blower, a cooling device using the Pelche effect, a cooling device using natural cooling, or the like is installed in the housing is used.

The cooling rate in the pre-winding cooling unit 120B is not particularly limited. As the cooling in the pre-winding cooling unit 120B, natural cooling (releasing cooling) slow cooling, forced quenching, or the like can be used.

The operation of the nanocarbon material continuous production apparatus 1B according to the second embodiment will be described in the nanocarbon material continuous production method according to the second embodiment below.

(Continuous manufacturing method of nano carbon material)
The method for continuously producing a nanocarbon material according to a second embodiment is a continuous manufacturing method using the continuous manufacturing apparatus 1B for a nanocarbon material according to the second embodiment.

The method for continuously producing a nanocarbon material according to a second embodiment includes a pre-winding cooling step in addition to the various steps of the method for continuously producing a nanocarbon material according to the first embodiment. Since the operation of the continuous production method of the nanocarbon material according to the second embodiment is the same as the operation of the continuous production method of the nanocarbon material according to the first embodiment except for the pre-winding cooling step, the winding is performed. The description of the process other than the pre-cooling process will be omitted.

<Cooling process before winding>
The pre-winding cooling step is a step of cooling the continuous transfer substrate 15 carried out from the reaction vessel 60B before being wound up by the winding unit 114.

The pre-winding cooling step is a step of cooling the continuous transfer substrate 15 by using the pre-winding cooling unit 120B. When the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15 to obtain the nanocarbon material composite 95, the pre-winding cooling step is also a step of cooling the nanocarbon material composite 95. ..

Cooling of the nanocarbon material composite 95 obtained in the film forming step has an effect of stopping the catalytic reaction in the film forming process of the nanocarbon material layer 90. Therefore, by controlling the cooling conditions in the pre-winding cooling step, the chemical properties, physical properties, and the like of the obtained nanocarbon material layer 90 can be changed.

The cooling rate in the pre-winding cooling unit 120B is not particularly limited. As the cooling in the pre-winding cooling unit 120B, natural cooling (releasing cooling) slow cooling, forced quenching, or the like can be used.

(Effect of continuous manufacturing apparatus for nanocarbon material according to the second embodiment)
According to the nano-carbon material continuous production apparatus 1B according to the second embodiment, the same effect as that of the nano-carbon material continuous production apparatus 1A according to the first embodiment is obtained.

Further, according to the nanocarbon material continuous production apparatus 1B according to the second embodiment, the chemical properties and physics of the nanocarbon material layer 90 obtained by controlling the cooling conditions in the pre-winding cooling unit 120B. It is possible to change the physical characteristics.

(Effect of continuous production method of nanocarbon material according to the second embodiment)
According to the method for continuously producing a nanocarbon material according to the second embodiment, the same effect as the method for continuously producing a nanocarbon material according to the first embodiment is obtained.

Further, according to the method for continuously producing a nanocarbon material according to the second embodiment, the chemical and physical properties of the nanocarbon material layer 90 obtained by controlling the cooling conditions in the pre-winding cooling step. Etc. can be changed.

[Third Embodiment]
(Continuous manufacturing equipment for nano-carbon materials)
FIG. 7 is a diagram schematically showing a continuous manufacturing apparatus for nanocarbon materials according to a third embodiment. As shown in FIG. 7, the continuous production apparatus 1C (1) for the nanocarbon material includes a continuous transfer apparatus 110, a reaction vessel 60C (60), a gas carbon source supply unit 30, a heating unit 50C (50), and the heating unit 50C (50). It includes a direction changing roller 127 and a planetary roller 123C (123).

The nanocarbon material continuous manufacturing apparatus 1C according to the third embodiment is further provided with a direction changing roller 127 and a planetary roller 123 as compared with the nanocarbon material continuous manufacturing apparatus 1A according to the first embodiment. different. Further, the continuous manufacturing apparatus 1C for the nanocarbon material has a different arrangement of the unwinding portion 112 and the winding portion 114 of the continuous transport device 110 as compared with the continuous manufacturing apparatus 1A for the nanocarbon material, and reacts with the reaction vessel 60C. It differs in that it has a different structure from the container 60A. The nanocarbon material continuous production apparatus 1C and the nanocarbon material continuous production apparatus 1A are substantially the same except for the above configuration.

Therefore, the same components of the nanocarbon material continuous manufacturing apparatus 1C and the nanocarbon material continuous manufacturing apparatus 1A are designated by the same reference numerals, and the description of the configuration and operation is omitted or simplified. For example, the heating unit 50C1 is the same as the heating unit 50A1. Hereinafter, the arrangement of the turning roller 127, the planetary roller 123C, the unwinding portion 112 and the winding portion 114 of the continuous transfer device 110, and the reaction vessel 60C will be described.

<Turn-turn roller>
The direction changing roller 127 is a member further provided in the reaction vessel 60C as a member for changing the direction of the continuous conveying substrate 15 in the reaction vessel 60C.

The direction changing roller 127 improves the efficiency of the film forming process of the nanocarbon material layer 90 by increasing the transport distance of the continuous transport substrate 15 in the reaction vessel 60C with respect to the length of the reaction vessel 60C.

For example, when the direction changing roller 127 is arranged as shown in the nano carbon material continuous manufacturing apparatus 1C, the transport distance of the continuous transport substrate 15 in the reaction vessel 60C is twice that of the nano carbon material continuous manufacturing apparatus 1A. Can be. In this way, if the transport distance of the continuous transfer substrate 15 in the reaction vessel 60C is doubled by using the turning roller 127, the speed of the film forming process is doubled even if the transfer speed of the continuous transfer substrate 15 is the same. be able to.

Further, when the direction changing roller 127 is arranged as in the nanocarbon material continuous manufacturing apparatus 1C shown in FIG. 7, even if the length of the reaction vessel 60C is halved of the reaction vessel 60A, the transport distance of the continuous transfer substrate 15 can be increased. It can be the same as the continuous manufacturing apparatus 1A for nanocarbon materials. As described above, when the direction change roller 127 is used and the length of the reaction vessel 60C is reduced to 1/2 of the reaction vessel 60A, the compact nanocarbon material continuous production apparatus 1C is used to make the nanocarbon material continuous production apparatus 1A. The same film forming process as above can be performed.

As the material of the turning roller 127, for example, quartz glass, ceramic, or the like is used. Of these, quartz glass is preferable because it is heat resistant and can withstand sudden temperature changes.

<Planet roller>
The planetary roller 123C is a member that eliminates the bending of the continuously conveyed substrate 15 and applies tension to the continuously conveyed substrate 15. The planetary roller 123C is provided between the unwinding portion 112 and the carry-in inlet 65 of the reaction vessel 60C, eliminates the bending of the continuous transport substrate 15 transported to the reaction vessel 60C, and applies tension to the continuous transport substrate 15. ..

When tension is applied to the continuous transfer substrate 15 by the planetary roller 123C, the bending of the continuous transfer substrate 15 to be conveyed is suppressed, and the accuracy of the film forming process is improved. The planetary roller 123C may be configured not to move in the vertical direction or the like in the figure, but may be configured to be movable in the vertical direction or the like in the figure in order to apply appropriate tension to the continuous transfer substrate 15.

The unwinding unit 112, the planetary roller 123C, and the winding unit 114 are all arranged in the continuous transfer device chamber 115C1. When the unwinding unit 112, the planetary roller 123C, and the winding unit 114 are arranged in the same continuous transport device chamber 115C1, a constant tension for preventing slack to the continuous transport substrate 15 can be applied. .. Therefore, when the unwinding portion 112, the planetary roller 123C, and the winding portion 114 are arranged in the same continuous transport device chamber 115C1, the nanocarbon material layer 90 formed on the surface of the continuous transport substrate 15 cracks or the like. It is preferable because it does not easily cause damage.

The planetary roller 123C is not an essential configuration for the continuous manufacturing apparatus 1C for nanocarbon materials according to the third embodiment. For example, if the bending of the continuous transfer substrate 15 to be conveyed is eliminated by optimizing the sizes and arrangements of the direction change roller 127, the unwinding portion 112, and the take-up portion 114, the planetary roller 123C is not provided. You can also do it.

<Continuous transfer device>
In the continuous manufacturing apparatus 1C for nanocarbon materials shown in FIG. 7, the unwinding unit 112 and the winding unit 114 constituting the continuous transfer device 110 are arranged on the right side in the drawing, and both are in the continuous transfer device chamber 115C1 (115). Is placed in.

When both the unwinding unit 112 and the winding unit 114 are arranged in the continuous transfer device chamber 115C1 (115), {the continuous transfer substrate 15 and the nanocarbon material layer 90} are prevented from being exposed to the atmosphere and the carrier gas is prevented. It is preferable because it can prevent leakage of the gaseous carbon source to the outside.

As shown in FIG. 7, the unwinding portion 112 is arranged on the lower side in the drawing, and the winding portion 114 is arranged on the upper side in the drawing. When the unwinding portion 112 is arranged on the lower side and the winding portion 114 is arranged on the upper side, a constant tension for preventing slack to the continuous transport substrate 15 can be applied. Therefore, when the unwinding portion 112, the planetary roller 123C, and the winding portion 114 are arranged in the same continuous transport device chamber 115C1, the nanocarbon material layer 90 formed on the surface of the continuous transport substrate 15 cracks or the like. It is preferable because it does not easily cause damage.

<Reaction vessel>
The reaction vessel 60C is a reaction vessel 60A of the continuous production apparatus 1A for nanocarbon materials according to the first embodiment, in which the positions of the carry-in inlet 65 and the carry-out outlet 67 are changed. Specifically, in the reaction vessel 60A, the carry-in inlet 65 and the carry-out port 67 are formed at one end and the other end in the longitudinal direction of the reaction vessel 60A, but in the reaction vessel 60C, the carry-in inlet 65 and the carry-out port 67 react. The container 60A is formed so as to be located in the vertical direction on one end side in the longitudinal direction.

The arrangement of the carry-in inlet 65 and the carry-out port 67 in the reaction vessel 60C corresponds to the arrangement of the direction change roller 127 and the continuous transfer substrate 15 being conveyed in each of the vertical directions in the reaction vessel 60C. ..

The operation of the nanocarbon material continuous production apparatus 1C according to the third embodiment will be described in the nanocarbon material continuous production method according to the third embodiment below.

(Continuous manufacturing method of nano carbon material)
The method for continuously producing a nanocarbon material according to a third embodiment is a continuous manufacturing method using the continuous manufacturing apparatus 1C for a nanocarbon material according to the third embodiment.

In the method for continuously producing a nanocarbon material according to a third embodiment, in the film forming step of the method for continuously producing a nanocarbon material according to the first embodiment, a film forming process is performed on the continuous transfer substrate 15 whose direction has been changed. The method. In the film forming step of the method for continuously producing a nanocarbon material according to a third embodiment, the nanocarbon material according to the first embodiment is continuously produced except that the film forming process is performed on the continuous transfer substrate 15 whose direction has been changed. It is the same as the film forming process of the method. Therefore, hereinafter, only the points different from the film forming step of the continuous production method of the nanocarbon material according to the first embodiment will be described.

<Film formation process>
In the film formation step in the method for continuously producing a nanocarbon material according to the third embodiment, the transfer direction of the continuous transfer substrate 15 is changed in the reaction vessel 60C, and the film formation process is performed on the changed direction continuous transfer substrate 15. Is the process of performing.

Specifically, in the film forming step, the continuous manufacturing apparatus 1C for the nanocarbon material according to the third embodiment is used, and the direction of the continuous transfer substrate 15 is changed in the reaction vessel 60C by the direction change roller 127. This is a process of forming a film while forming a film.

According to this film forming step, the film forming treatment of the nanocarbon material layer 90 is performed by using the direction changing roller 127 and increasing the conveying distance of the continuous conveying substrate 15 in the reaction vessel 60C with respect to the length of the reaction vessel 60C. Efficiency can be improved.

For example, when the direction changing roller 127 is arranged as in the nanocarbon material continuous production apparatus 1C shown in FIG. 7, in the present film forming step, the transfer distance of the continuous transfer substrate 15 in the reaction vessel 60C is set to the continuous nanocarbon material. It can be doubled as the manufacturing apparatus 1A. In this way, when the transport distance of the continuous transfer substrate 15 in the reaction vessel 60C is doubled by using the turning roller 127, in the main film formation step, even if the transfer speed of the continuous transfer substrate 15 is the same, the film formation process is performed. The speed can be doubled.

Further, when the direction changing roller 127 is arranged as shown in FIG. 7, in the present film forming step, even if the length of the reaction vessel 60C is halved of the reaction vessel 60A, the transfer distance of the continuous transfer substrate 15 is set to the nanocarbon material. It can be the same as the continuous manufacturing apparatus 1A of. As described above, when the direction change roller 127 is used and the length of the reaction vessel 60C is reduced to 1/2 of that of the reaction vessel 60A, nanocarbon is used in the present film forming step by using the compact continuous production apparatus 1C for nanocarbon material. A film forming process similar to that of the material continuous manufacturing apparatus 1A can be performed.

(Effect of continuous manufacturing apparatus for nanocarbon material according to the third embodiment)
According to the nano-carbon material continuous production apparatus 1C according to the third embodiment, the same effect as that of the nano-carbon material continuous production apparatus 1A according to the first embodiment is obtained.

Further, according to the nanocarbon material continuous production apparatus 1C according to the third embodiment, the nanocarbon material is obtained by increasing the transport distance of the continuous transfer substrate 15 in the reaction vessel 60C with respect to the length of the reaction vessel 60C. The efficiency of the film forming process of the layer 90 can be improved.

(Effect of continuous production method of nanocarbon material according to the third embodiment)
According to the method for continuously producing a nanocarbon material according to a third embodiment, the same effect as that for the method for continuously producing a nanocarbon material according to the first embodiment is obtained.

Further, according to the method for continuously producing a nanocarbon material according to the third embodiment, the nanocarbon material layer is formed by increasing the transport distance of the continuous transport substrate 15 in the reaction vessel 60C with respect to the length of the reaction vessel 60C. The efficiency of the film forming process of 90 can be improved.

[Fourth Embodiment]
(Continuous manufacturing equipment for nano-carbon materials)
FIG. 8 is a diagram schematically showing a continuous manufacturing apparatus for nanocarbon materials according to a fourth embodiment. As shown in FIG. 8, the continuous production apparatus 1D (1) for the nanocarbon material includes a continuous transfer apparatus 110, a reaction vessel 60D (60), a gas carbon source supply unit 30, a heating unit 50D (50), and the heating unit 50D (50). It is provided with a pre-winding cooling unit 120D (120).

The nanocarbon material continuous manufacturing apparatus 1D according to the fourth embodiment is further provided with a prewinding cooling unit 120D as compared with the nanocarbon material continuous manufacturing apparatus 1C according to the third embodiment, and is a continuous transfer device. The chamber 115 differs in that the form is different, and the other configurations are substantially the same.

Therefore, the same components of the continuous manufacturing device 1D for nanocarbon materials and the continuous manufacturing device 1C for nanocarbon materials are designated by the same reference numerals, and the description of the structure and operation is omitted or simplified. For example, the reaction vessel 60D, the heating unit 50D1, the direction changing roller 127D, etc. of the continuous manufacturing apparatus 1D for nanocarbon materials are the same as the reaction vessel 60C, the heating unit 50C1, the direction changing roller 127C, etc. of the continuous manufacturing apparatus 1C for nanocarbon materials. Is. Hereinafter, the cooling roller 125 as the pre-winding cooling unit 120D will be described.

<Cooling section before winding>
The pre-winding cooling unit 120D is the same as the pre-winding cooling unit 120B of the continuous manufacturing apparatus 1B for nanocarbon materials according to the second embodiment, and the continuous transport substrate 15 carried out from the reaction vessel 60D is taken up by the winding unit 114. It is a unit that cools before winding up with. The pre-winding cooling unit 120D is provided between the carry-out port 67 of the reaction vessel 60D and the winding unit 114.

As shown in FIG. 8, the pre-winding cooling unit 120D is a cooling roller 125D1 and 125D2 (125) that come into contact with the continuous transfer substrate 15 before being wound by the winding unit 114.

As for the cooling roller 125, the cooling roller 125D1 is arranged on the reaction vessel 60D side, and the cooling roller 125D2 is arranged on the winding portion 114 side.

The cooling roller 125 (125D1, 125D2) is an aspect of the pre-winding cooling unit 120, and is a unit for cooling the continuous transfer substrate 15 like the pre-winding cooling unit 120B of the continuous manufacturing apparatus 1B for nanocarbon materials. .. When the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15 to obtain the nanocarbon material composite 95, the cooling rollers 125 (125D1, 125D2) cool the nanocarbon material composite 95. It is also a unit.

Since the cooling roller 125 (125D1, 125D2) has the form of a roller in the pre-winding cooling unit 120, it is easy to inline the nanocarbon material into the continuous manufacturing apparatus 1D.

The cooling of the nanocarbon material composite 95 obtained in the film forming treatment has an effect of stopping the catalytic reaction in the film forming process of the nanocarbon material layer 90. Therefore, by controlling the cooling conditions of the cooling rollers 125 (125D1, 125D2), the chemical properties, physical properties, and the like of the obtained nanocarbon material layer 90 can be changed.

The cooling roller 125 (125D1, 125D2) is not particularly limited, and for example, a cooling roller using the Perche effect, a cooling roller in which a cryogen flows inside, and the like are used.

As the cryogen used for the cooling roller through which the cryogen flows, for example, water, ethylene glycol, liquid nitrogen or the like is used. Of these, ethylene glycol is preferable because it is a liquid and can be easily dissolved in water or the like and diluted before use. Further, ethylene glycol is preferable because it has a lower melting point than water. Further, ethylene glycol is preferable because it is easy to use in a commercially available cooling device.

Similar to the planetary roller 123C of the continuous manufacturing apparatus 1C for nanocarbon materials according to the third embodiment, the cooling rollers 125D1 and 125D2 eliminate the bending of the continuously conveyed substrate 15 and apply tension to the continuously conveyed substrate 15. It also functions as a member to be applied.

The cooling rollers 125D1 and 125D2 are arranged in the continuous transfer device chamber 115D2 (115) together with the winding unit 114. When the cooling rollers 125D1 and 125D2 and the winding unit 114 are arranged in the same continuous transfer device chamber 115D2, a constant tension for preventing slack to the continuous transfer substrate 15 can be applied and cooling is performed. It is efficient. Therefore, when the unwinding portion 112, the planetary roller 123C, and the winding portion 114 are arranged in the same continuous transport device chamber 115C1, the nanocarbon material layer 90 formed on the surface of the continuous transport substrate 15 cracks or the like. Is preferable because it is less likely to occur and a high cooling function can be imparted.

A planetary roller 123D (123) is provided on the unwinding portion 112 side of the continuous manufacturing apparatus 1D for nanocarbon materials. Since the action of the planet roller 123D is the same as the action of the planet roller 123C of the continuous manufacturing apparatus 1C for nanocarbon materials according to the third embodiment, the description of the planet roller 123D will be omitted.

In the nanocarbon material continuous production apparatus 1D, the unwinding portion 112 and the planetary roller 123D are both arranged in the continuous transfer apparatus chamber 115D1 (115). When the unwinding portion 112 and the planetary roller 123D are arranged in the same continuous transfer device chamber 115D1, a constant tension for preventing slack to the continuous transfer substrate 15 can be applied. Therefore, when the unwinding portion 112, the planetary roller 123C, and the winding portion 114 are arranged in the same continuous transport device chamber 115C1, the nanocarbon material layer 90 formed on the surface of the continuous transport substrate 15 cracks or the like. It is preferable because it does not easily cause damage.

The operation of the nanocarbon material continuous production apparatus 1D according to the fourth embodiment will be described in the nanocarbon material continuous production method according to the fourth embodiment below.

(Continuous manufacturing method of nano carbon material)
The method for continuously producing a nanocarbon material according to a fourth embodiment is a continuous manufacturing method using the continuous manufacturing apparatus 1D for a nanocarbon material according to the fourth embodiment.

The method for continuously producing a nanocarbon material according to a fourth embodiment includes a pre-winding cooling step in addition to the various steps of the method for continuously producing a nanocarbon material according to the third embodiment. Since the operation of the continuous production method of the nanocarbon material according to the fourth embodiment is the same as the operation of the continuous production method of the nanocarbon material according to the third embodiment except for the pre-winding cooling step, the winding is performed. The description of the process other than the pre-cooling process will be omitted.

<Cooling process before winding>
The pre-winding cooling step is a step of cooling the continuous transfer substrate 15 carried out from the reaction vessel 60D before being wound up by the winding unit 114.

The pre-winding cooling step is a step of cooling the continuous transfer substrate 15 by using the pre-winding cooling unit 120D (120). When the nanocarbon material layer 90 is formed on the surface of the continuous transfer substrate 15 to obtain the nanocarbon material composite 95, the pre-winding cooling step is also a step of cooling the nanocarbon material composite 95. ..

Specifically, the pre-winding cooling step in the method for continuously producing a nanocarbon material according to a fourth embodiment includes cooling rollers 125D1 and 125D2 (125) that come into contact with the continuous transfer substrate 15 before being wound by the winding unit 114. ) Is the process to be performed.

Cooling of the nanocarbon material composite 95 obtained in the film forming step has an effect of stopping the catalytic reaction in the film forming process of the nanocarbon material layer 90. Therefore, by controlling the cooling conditions in the pre-winding cooling step, the chemical properties, physical properties, and the like of the obtained nanocarbon material layer 90 can be changed.

(Effect of the continuous manufacturing apparatus for nanocarbon materials according to the fourth embodiment)
According to the nano-carbon material continuous production apparatus 1D according to the fourth embodiment, the same effect as that of the nano-carbon material continuous production apparatus 1C according to the third embodiment is obtained.

Further, according to the nano-carbon material continuous production apparatus 1D according to the fourth embodiment, the nano-carbon material layer obtained by controlling the cooling conditions of the cooling rollers 125D1 and 125D2 as the pre-winding cooling unit 120D. The chemical properties, physical properties, etc. of 90 can be changed.

(Effect of continuous production method of nanocarbon material according to the fourth embodiment)
According to the method for continuously producing a nanocarbon material according to a fourth embodiment, the same effect as that for the method for continuously producing a nanocarbon material according to a third embodiment is obtained.

Further, according to the method for continuously producing a nanocarbon material according to the fourth embodiment, the chemical and physical properties of the nanocarbon material layer 90 obtained by controlling the cooling conditions in the pre-winding cooling step. Etc. can be changed.

Although the present embodiment has been described above, the present embodiment is not limited to these, and various modifications can be made within the scope of the gist of the present embodiment.

1, 1A, 1B, 1C, 1D Nano carbon material continuous production equipment 15 Continuous transfer substrate 30 Gas carbon source supply unit 35 Gas carbon source 50 Heating unit 51 Optical heating equipment 60, 60A, 60B, 60C, 60D Reaction vessel 61 Reaction Container body 62 Translucent wall 63 Reaction vessel space 65 Carry-in port 67 Carry-out port 90 Nano-carbon material layer 95 Nano-carbon material composite 110 Continuous transport device 112 Unwinding part 114 Winding part 115, 115A1, 115A2, 115B1, 115B2, 115C, 115D1, 115D2 Continuous transfer device Chamber 120, 120B, 120D Pre-winding cooling unit 123 Planetary roller 125 Cooling roller 127 Direction change roller

Claims (14)

Continuous transport A continuous transport device that continuously transports boards and
A reaction vessel having a carry-in inlet for carrying in the continuous transfer board and a carry-out port for carrying out the continuous transfer board, and accommodating the continuous transfer board being carried.
A gaseous carbon source supply unit that supplies a gaseous carbon source into the reaction vessel,
A heating unit for forming a nanocarbon material layer on the surface of the continuous transfer substrate by heating the continuous transfer substrate in the reaction vessel is provided.
The heating unit is a continuous production apparatus for nanocarbon materials including an optical heating apparatus for heating the continuous transfer substrate in the reaction vessel by irradiating the inside of the reaction vessel with light. The device for continuously producing a nanocarbon material according to claim 1, wherein the optical heating device irradiates light having a wavelength of 0.70 μm to 5.00 μm and an intensity of 1 kW to 8 kW. The device for continuously producing a nanocarbon material according to claim 1 or 2, wherein the light heating device is one or more of a laser heating device and a flash lamp heating device. 6. Continuous manufacturing equipment for nano-carbon materials. The continuous manufacturing apparatus for a nanocarbon material according to claim 4, further comprising a pre-winding cooling unit that cools the continuous transport substrate carried out from the reaction vessel before being wound up by the winding unit. The continuous manufacturing apparatus for a nanocarbon material according to any one of claims 1 to 5, further comprising a direction changing roller for changing the direction of the continuous transport substrate in the reaction vessel. The continuous manufacturing apparatus for nanocarbon materials according to claim 5, wherein the pre-winding cooling unit is a cooling roller that comes into contact with the continuous transport substrate before being wound by the winding unit. A film forming step of forming a nanocarbon material layer on the surface of the continuously conveyed substrate by heating the continuously conveyed substrate in the presence of a gaseous carbon source in a reaction vessel is provided.
The film forming step is a method for continuously producing a nanocarbon material using an optical heating device that heats the continuous transfer substrate in the reaction vessel by irradiating the inside of the reaction vessel with light. The method for continuously producing a nanocarbon material according to claim 8, wherein the optical heating device irradiates light having a wavelength of 0.70 μm to 5.00 μm and an intensity of 1 kW to 8 kW. The method for continuously producing a nanocarbon material according to claim 8 or 9, wherein the optical heating device is one or more of a laser heating device and a flash lamp heating device. The continuous transfer board is continuously conveyed using a continuous transfer device.
6. A method for continuously manufacturing nanocarbon materials. The method for continuously producing a nanocarbon material according to claim 11, further comprising a pre-winding cooling step of cooling the continuous transport substrate carried out from the reaction vessel before winding it by the winding unit. The nano. A method for continuously manufacturing carbon materials. The method for continuously producing a nanocarbon material according to claim 12, wherein the pre-winding cooling step is performed by using a cooling roller that comes into contact with the continuous transport substrate before being wound by the winding unit.

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