WO2014033934A1

WO2014033934A1 - Tubular graphene laminate, and method for producing tubular graphene laminate

Info

Publication number: WO2014033934A1
Application number: PCT/JP2012/072260
Authority: WO
Inventors: 正治長谷川
Original assignee: グラフェンプラットフォーム株式会社
Priority date: 2012-08-31
Filing date: 2012-08-31
Publication date: 2014-03-06

Abstract

Provided are: a tubular graphene laminate which contains a graphene layer and is easy to handle; and a method for producing the tubular graphene laminate. The tubular graphene laminate (1'A to F) comprises: a graphene film (2) to which a carbon atom is bound via a covalent bond; an adhesive layer (3D or 3E) having physical adhesion force; and a tubular support layer (4A or 4B) having predetermined strength. The graphene film (2) is arranged along the inside surface side of the tubular support layer (4A) and the outer surface side of the tubular support layer (4B). In this manner, the graphene film (2) can be formed into a tubular shape.

Description

Tubular graphene laminate and method for producing tubular graphene laminate

The present invention relates to a tubular graphene laminate in which a graphene film is formed in a tubular shape, and a method for producing a tubular graphene laminate.

In recent years, research on graphene has been actively conducted, and the technology for manufacturing large-area graphene has been dramatically developed in recent years. Graphene is composed of carbon atoms in layers or sheets, has electrical, mechanical and chemical stability, and has excellent electrical conductivity. It is attracting attention as a basic element. Graphene has been found to be easily adsorbed by molecules such as gas due to the structure of carbon atoms forming a hexagonal plane. This is due to the van der Waals force acting between the carbon atom of graphene and other molecules, and the force is about a few tenths of a chemical bond. It is expected that this adsorption function will be used because the pressure of carbon atoms is a considerable pressure when integrated. Further, graphene has a function as a gas barrier because it has impermeable properties.

As a conventional method for manufacturing such graphene, a hydrophilic oxide layer is formed on a silicon wafer on which a hydrophobic metal catalyst layer is formed, and the graphene layer is formed into a metal by using chemical vapor deposition. Some of them are formed in a film shape on the upper surface of the catalyst layer (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2011-063506 (paragraphs 0032 to 0040, FIG. 1)

As shown in Patent Document 1, a sheet-like configuration is known as the shape of graphene, but it is also desired to use a shape other than the sheet shape. However, if the sheet-like graphene is deformed to another shape, the graphene is peeled off or damaged during the deformation, so that it is difficult to deform the sheet-like shape.

The present invention has been made paying attention to such problems, and aims to provide a tubular graphene laminate formed into a tubular shape and a method for producing the tubular graphene laminate in order to facilitate the handling of the graphene film. To do.

In order to solve the above problems, the tubular graphene laminate of the present invention is
A graphene film in which carbon atoms are covalently bonded;
A tubular support layer having a predetermined strength;
With
A tubular graphene laminate, wherein the graphene film is formed in a tubular shape by disposing the graphene film along an inner surface side or an outer surface side of the tubular support layer.
According to this feature, since the graphene film in which carbon atoms are covalently bonded is disposed along the inner surface side or outer surface side of the tubular support layer having a predetermined strength, the graphene film can be formed into a tubular shape, and By providing the support layer with a predetermined strength, the tubular graphene laminate can be easily handled. Here, the term “tubular” refers to a hollow, elongated structure that can be formed into a cylindrical or hollow prismatic shape with a pipe-like configuration. By constituting the tubular graphene laminate, it can be used for, for example, a pipe, a flexible tube (hose), a soaking bar, an artificial blood vessel for a living body, an artificial heart, and the like. In this case, a product made of a tubular graphene laminate having barrier properties and corrosion resistance, chemical resistance, and antifouling properties can be formed due to the impermeable nature of the graphene film.

In the tubular graphene laminate of the present invention,
The graphene film and the support layer are each formed with a porosity,
Through holes are formed in the graphene film and the support layer by overlapping the porosity of the graphene film and the porosity of the support layer.
According to this feature, a graphene film having a porosity and a support layer are provided, and a through hole is formed in the graphene film and the support layer by overlapping the porosity of the graphene film and the porosity of the support layer. Thus, the tubular graphene laminate can be used as a filter. For example, it can be used for applications such as putting seawater into the tubular graphene laminate and making it fresh water by a reverse osmosis membrane method. It can also be used for biological membranes (built-in, blood vessels, etc.) and membrane filters.

In the tubular graphene laminate of the present invention,
The graphene film and the support layer are each formed with a porosity,
The porous diameter of the support layer is set to be larger than the porous diameter of the graphene film, whereby through holes are formed in the graphene film and the support layer.
According to this feature, the graphene film and the support layer are provided with a pore, and the pore diameter of the support layer is set larger than the pore diameter of the graphene film, so that the graphene film and the support A through-hole can be formed in the layer, so that the tubular graphene laminate can be used as a filter.

In the tubular graphene laminate of the present invention,
Between the graphene film and the tubular support layer, provided with a physical adhesive force, comprising an adhesive layer in which a pore is formed,
Through holes are formed in the graphene film, the support layer, and the adhesive layer by overlapping the porosity of the graphene film, the porosity of the support layer, and the porosity of the adhesive layer.
According to this feature, when the adhesion / adhesion between the support layer and the graphene film is poor, by providing the adhesive layer, the support layer and the graphene film can be stably bonded to each other via the adhesive layer. For example, when the surface of the support layer is rough, it may be difficult to adsorb only by van der Waals force of the graphene film, but by providing an adhesive layer, the support layer and the graphene film are attached to the adhesive layer. And can be pasted together stably. In addition, as the pressure-sensitive adhesive layer in which the pores are formed, the graphene film, the support layer, and the pressure-sensitive adhesive layer overlap so that a through-hole is formed in the graphene film, the support layer, and the pressure-sensitive adhesive layer. This tubular graphene laminate can be used as a filter.

In the tubular graphene laminate of the present invention,
Between the graphene film and the tubular support layer, provided with a physical adhesive force, comprising an adhesive layer in which a pore is formed,
The pore diameter of the support layer and the pore diameter of the adhesive layer are set larger than the pore diameter of the graphene film, so that through holes are formed in the graphene film, the support layer, and the adhesive layer. It is characterized by being.
According to this feature, when the adhesion / adhesion between the support layer and the graphene film is poor, by providing the adhesive layer, the support layer and the graphene film can be stably bonded to each other via the adhesive layer. Further, as the pressure-sensitive adhesive layer in which the pores are formed, the pore diameter of the support layer and the pore diameter of the pressure-sensitive adhesive layer are set larger than the pore diameter of the graphene film, whereby the graphene film and the support layer And a through-hole can be formed in the said adhesion layer, and this tubular graphene laminated body can be utilized as a filter.

In the tubular graphene laminate of the present invention,
A tubular second support layer having a predetermined strength;
The graphene film is disposed so as to be sandwiched between the second support layer and the tubular support layer.
According to this feature, since the graphene film is sandwiched between the second support layer and the tubular support layer, the support layer and the second support layer are disposed on both sides of the graphene film, so that it is more stable, An easy-to-handle tubular graphene laminate can be constructed.

In addition, the method for producing the tubular graphene laminate of the present invention includes:
A method for producing a tubular graphene laminate in which a graphene film in which carbon atoms are covalently bonded is formed in a tubular shape along an inner surface side or an outer surface side of a tubular support layer having a predetermined strength,
A film forming step of forming the graphene film into a tubular shape by holding the tubular metal substrate and forming a graphene film along the inner surface side or the outer surface side of the tubular metal substrate;
A support layer forming step of coating a support layer having a predetermined strength along the graphene film side formed in the film forming step;
A metal melting step for holding the support layer formed by the support layer forming step and melting the tubular metal substrate;
It is characterized by providing.
According to this feature, the graphene film is formed into a tubular shape by holding the tubular metal substrate and forming the graphene film along the inner surface or the outer surface of the tubular metal substrate in the film forming step. Then, in the support layer forming step, a support layer having a predetermined strength is coated along the graphene film side formed in the film forming step, and the support layer formed by the support layer forming step in the metal melting step Graphene laminate in which a graphene film in which carbon atoms are covalently bonded is arranged along the inner surface side or outer surface side of a tubular support layer having a predetermined strength by holding the tubular metal substrate Can be manufactured. Further, when forming the graphene film of the tubular graphene laminate, by holding, for example, the end of the tubular metal substrate, the entire inner surface or outer surface side of the tubular metal substrate. A graphene film can be deposited along the film. Further, in the metal melting step, in order to melt the tubular metal substrate, the support layer formed in the support layer forming step is retained, so that the metal is not damaged without damaging the graphene film of the tubular graphene laminate. The substrate can be melted.

In the method for producing a tubular graphene laminate of the present invention,
A plug step is provided in which an end of the tubular metal substrate is plugged so that the film forming step is not performed on the inner surface side of the tubular metal substrate.
According to this feature, in the plugging process, the end of the tubular metal substrate is plugged so that the film forming process on the inner surface side of the tubular metal substrate is not performed. By the process, the graphene film can be formed only on the outer surface side of the tubular metal substrate.

In the method for producing a tubular graphene laminate of the present invention,
During the film forming step, the graphene is formed to be porous,
In the support layer forming step, the support layer is formed to be porous, and the pores of the graphene film and the support layer overlap to form through holes in the graphene film and the support layer. Features.
According to this feature, the graphene film and the support layer can be formed as a porous layer, and the through hole is formed in the graphene film and the support layer by overlapping the porosity of the graphene film and the support layer. Tubular graphene laminate can be used as a filter.

In the method for producing a tubular graphene laminate of the present invention,
Before the support layer forming step, forming a pressure-sensitive adhesive layer on the graphene film side formed in the film-forming step, the pores of the graphene film and the pores of the pressure-sensitive adhesive layer overlap, An adhesive layer forming step of forming through holes in the graphene film and the adhesive layer is provided.
According to this feature, when the adhesion / adhesion between the support layer and the graphene film is poor, by providing the adhesive layer, the support layer and the graphene film can be stably bonded to each other via the adhesive layer. For example, when the surface of the support layer is rough, it may be difficult to adsorb only by van der Waals force of the graphene film, but by providing an adhesive layer, the support layer and the graphene film are attached to the adhesive layer. And can be pasted together stably. Moreover, the tubular graphene laminated body can be utilized as a filter by setting it as the adhesion layer in which the porosity was formed.

In the method for producing a tubular graphene laminate of the present invention,
After the metal melting step, a second support layer forming step of coating a second support layer having a predetermined strength along the graphene film on the side where the tubular metal substrate is melted is provided.
According to this feature, since the graphene film is sandwiched between the second support layer and the tubular support layer, the support layer and the second support layer are disposed on both sides of the graphene film. An easy tubular graphene laminate can be constructed.

1 is a cross-sectional view (a) to (f) of a tubular graphene laminate in an example. FIG. It is explanatory drawing (a)-(e) which shows the manufacturing process of the tubular graphene laminated body in an Example. It is explanatory drawing (a)-(e) which shows the other manufacturing process of the tubular graphene laminated body in an Example. It is explanatory drawing which shows the usage example of the tubular graphene laminated body in an Example. It is a schematic diagram at the time of superposing | stacking the surface of the support layer of the tubular graphene laminated body in an Example, the surface of a graphene film | membrane, and them. It is a schematic diagram at the time of laminating | stacking the surface of the adhesion layer of the tubular graphene laminated body in an Example, the surface of a support layer, the surface of a graphene film | membrane.

DETAILED DESCRIPTION OF EMBODIMENTS Embodiments of a tubular graphene laminate and a method for producing a tubular graphene laminate according to the present invention will be described below based on examples.

First, the configuration of the tubular graphene laminate used in the examples will be described with reference to FIG.

FIG. 1 shows a tubular circular sectional view and a longitudinal sectional view of a tubular graphene laminate in an example, and FIG. 1A shows a graphene film 2 disposed along the inner surface side of a support layer 4A. A cross-sectional view of the tubular graphene laminate 1′A is shown, and FIG. 1B is a graphene film 2 disposed along the inner surface side of the support layer 4A, and an adhesive layer 3D is provided between the support layer 4A and the graphene film 2. FIG. 1C shows a cross-sectional view of the tubular graphene laminate 1′C in which the graphene film 2 is arranged along the outer surface side of the support layer 4B. 1D shows a cross section of a tubular graphene laminate 1′D in which the graphene film 2 is disposed along the outer surface side of the support layer 4B, and the adhesive layer 3E is disposed between the support layer 4B and the graphene film 2. FIG. 1 (e) shows the inner side of the support layer 4A. The graphene film 2 is disposed, and the graphene film 2 is disposed along the outer surface side of the support layer 4B so that the graphene film 2 is sandwiched between the support layer 4A and the support layer 4B. FIG. 1F shows a cross-sectional view of the body 1′E, in which the graphene film 2 is arranged along the inner surface side of the support layer 4A and the graphene film 2 is arranged along the outer surface side of the support layer 4B. The graphene film 2 is sandwiched between the support layer 4A and the support layer 4B, the adhesive layer 3D is disposed between the support layer 4A and the graphene film 2, and the adhesive layer 3E is disposed between the support layer 4B and the graphene film 2. Sectional drawing of tubular graphene laminated body 1'F made to show was shown.

1A to 1F, the tubular graphene laminates 1′A to F include at least one graphene film 2 in which carbon atoms are covalently bonded, and a

tubular support layer

4A or 4B having a predetermined strength. The graphene film 2 is formed in a tubular shape by disposing the graphene film 2 along the inner surface or the outer surface of the

support layer

4A or 4B. Further, the

support layer

4A or 4B has a predetermined strength, so that the tubular graphene laminate can be easily handled. Here, the term “tubular” refers to a hollow elongated structure, which can be a cylindrical shape or a hollow prismatic shape, and the diameter and the length in the longitudinal direction of the tubular circular portion are used in a manufacturing method described later. It can be set by arbitrarily setting the diameter of the metal substrate and the length in the longitudinal direction. For example, the diameter of the tubular circular portion is from several μm to several tens of cm, the length in the longitudinal direction is from several μm to several m, It can be set arbitrarily. Note that the tubular graphene laminates 1′A to F in this example are different from carbon nanotubes, which are hollow cylindrical materials obtained by rolling a graphene sheet in which carbon atoms are regularly arranged. While the outer diameter is on the order of nm and the length is usually a minute substance of 0.5 to several tens of μm, the tubular graphene laminates 1′A to F in this example are stable by including a support layer. It is easy to handle, its size can be set larger than that of carbon nanotubes, and it has the characteristics of graphene.

In the present embodiment, as the

support layer

4A or 4B, for example, a material having a predetermined strength such as a resin composition, glass, metal, or ceramic can be used. The resin composition contains nylon, polyurethane, polyacetal, polycarbonate, vinylidene fluoride, polyethylene, ABS resin, vinyl chloride, polytetrafluoroethylene, synthetic rubber, PDMS, etc., and is composed of one or more types Is done. Moreover, the tubular graphene laminated body 1 ′ can be deformed by using a deformable material having flexibility or elasticity as the support layer 4 A or 4 B. Further, the

support layer

4A or 4B may be provided with at least one of thermosetting, thermoplasticity, heat shrinkability, biodegradability, and water solubility.

In FIG. 1A, the tubular graphene laminate 1′A has a graphene film 2 disposed along the inner surface side of the support layer 4A, and is composed of two layers of the support layer 4A and the graphene film 2. . The tubular graphene laminate 1'A has a support layer 4A on the outer peripheral side, so that the tubular graphene laminate 1'A can be easily held.

Moreover, in FIG.1 (c), tubular graphene laminated body 1'C has arrange | positioned the graphene film | membrane 2 along the outer surface side of the support layer 4B, and is comprised by the two layers of the support layer 4B and the graphene film | membrane 2. ing. Since the tubular graphene laminate 1 ′ C has the support layer 4 B on the inner peripheral side, the tubular graphene laminate 1 ′ C can be grasped by grasping the cavity 160.

Moreover, in FIG.1 (e), tubular graphene laminated body 1'E is the inner surface side of support layer 4A, Comprising: Support layer 4A is arrange | positioned by arrange | positioning the graphene film 2 along the outer surface side of support layer 4B. The graphene film 2 is disposed so as to be sandwiched between the support layer 4B, and the support layer 4B includes three layers of the support layer 4A, the graphene film 2, and the support layer 4B. The tubular graphene laminate 1'E has a support layer 4A on the outer peripheral side and a support layer 4B on the inner peripheral side, so that the graphene film 2 is less likely to be scratched and easier to grip.

Furthermore, an

adhesive layer

3D or 3E may be disposed between the

tubular support layer

4A or 4B having a predetermined strength and the graphene film 2. The configuration in this case is shown in FIGS. 1B, 1D, and 1F, respectively. In this configuration, the tubular graphene laminate 1 ′ has an

adhesive layer

3D or 3E formed on the inner surface side or outer surface side of the

support layer

4A or 4B, and further a graphene film 2 on the inner surface side or outer surface side of the

adhesive layer

3D or 3E. Is formed, it is laminated in three or five layers. The

adhesive layer

3D or 3E has a physical adhesive force larger than the van der Waals force acting between the carbon atom of the graphene film 2 and other molecules. That is, the graphene film 2 and the

support layer

4A or 4B are physically adhered by providing the physical adhesive force larger than the adsorption force that the graphene film 2 adsorbs to the

support layer

4A or 4B. By disposing the

adhesive layer

3D or 3E, the support layer and the graphene film can be stably bonded to each other via the adhesive layer. For example, when the surface of the support layer is rough, it may be difficult to adsorb only by van der Waals force of the graphene film, but by providing an adhesive layer, the support layer and the graphene film are attached to the adhesive layer. And can be pasted together stably.

In this embodiment, the pressure-

sensitive adhesive layer

3D or 3E contains at least one of pressure-sensitive adhesives such as urea resin, melamine resin, phenol resin, epoxy resin, cyanoacrylate, polyurethane, and acrylic resin. And the resin composition comprised from 1 type or multiple can be utilized.

In FIG. 1B, the tubular graphene laminate 1′B has a graphene film 2 disposed along the inner surface side of the support layer 4A, and an adhesive layer 3D disposed between the support layer 4A and the graphene film 2. The support layer 4 A, the adhesive layer 3 D, and the graphene film 2 are composed of three layers. The tubular graphene laminate 1′B has a support layer 4A on the outer peripheral side, so that the tubular graphene laminate 1′B can be easily held, and the support layer and the graphene film are stably bonded to each other via the adhesive layer 3D. Can.

In FIG. 1D, the tubular graphene laminate 1′D has a graphene film 2 disposed along the outer surface side of the support layer 4B, and an adhesive layer 3E disposed between the support layer 4B and the graphene film 2. The support layer 4 B, the adhesive layer 3 E, and the graphene film 2 are composed of three layers. Since the tubular graphene laminate 1′D has the support layer 4B on the inner peripheral side, the tubular graphene laminate 1′D can be grasped by holding the portion of the cavity 160, and the support layer 4B and the graphene film 2 are adhered to each other. It can be bonded stably through the layer 3E.

In FIG.1 (f), tubular graphene laminated body 1'F arrange | positions the graphene film 2 along the inner surface side of the support layer 4A, and arrange | positions the graphene film 2 along the outer surface side of the support layer 4B. The graphene film 2 is sandwiched between the support layer 4A and the support layer 4B, the adhesive layer 3D is disposed between the support layer 4A and the graphene film 2, and the adhesive layer 3E is disposed between the support layer 4B and the graphene film 2. The support layer 4A, the adhesive layer 3D, the graphene film 2, the adhesive layer 3E, and the support layer 4B are configured by five layers. The tubular graphene laminate 1′F has a support layer 4A on the outer peripheral side and a support layer 4B on the inner peripheral side, so that the graphene film 2 is less likely to be scratched and easier to grip, and the support layer 4A and the support layer 4B And the graphene film 2 can be stably bonded to each other through the

adhesive layers

3D and 3E.

These tubular graphene laminates 1'A to F can be used for, for example, pipes, flexible tubes (hoses), soaking bars, artificial blood vessels for living bodies, artificial hearts, and the like. In this case, a product made of a tubular graphene laminate having barrier properties and corrosion resistance, chemical resistance, and antifouling properties can be formed due to the impermeable nature of the graphene film.

Furthermore, in this embodiment, the graphene film 2 of the tubular graphene laminates 1'A to F can be made porous by forming a porous graphene film. Note that the hole formed in the graphene film is a physically formed hole unlike the space formed by the hexagonal lattice structure formed by bonding carbon atoms, specifically, the graphene film The size is larger than the hexagonal lattice structure having a carbon-carbon bond distance of about 0.142 nm. As a method for forming a porous graphene film, it can be formed into a porous shape by doping an inorganic gas at the time of film formation. In this case, the pore diameter can be set to about 0.3 nm to several tens of μm depending on the particle size of the inorganic gas. In addition to doping the inorganic gas at the time of film formation, the hole is formed by adding a metal atom such as palladium after the graphene film 2 is formed, so that the graphene film 2 in the portion to which the metal atom is attached When holes are formed in the holes and metal atoms are removed from the end portions of the holes, the expansion of the holes stops and a through hole can be formed. Thereby, for example, the pore diameter of the graphene film 2 can be set to several nm to several hundred μm. Further, the sizes of the holes may be the same or different sizes.

Further, by making the

support layer

4A or 4B and the

adhesive layer

3D or 3E porous, through-holes are formed in the graphene film 2, the

support layer

4A or 4B, and the

adhesive layer

3D or 3E, and the tubular graphene laminate 1′A to F can be used as filters. In this case, the ratio of the total area of pores to the surface area of the

support layer

4A or 4B (hereinafter referred to as support layer) from the ratio of the total area of pores to the surface area of the graphene film (hereinafter referred to as the aperture ratio of the graphene film 2). By increasing the aperture ratio of 4A or 4B), a portion where the hole portion of the graphene film 2 overlaps and penetrates the hole portion of the

support layer

4A or 4B can be formed. Similarly, the ratio of the total area of pores due to the porosity to the surface area of the

adhesive layer

3D or 3E (hereinafter referred to as the opening ratio of the

adhesive layer

3D or 3E) is also made larger than the opening ratio of the graphene film, thereby making the graphene film A portion in which the two hole portions overlap and penetrate through the hole portions of the

support layer

4A or 4B can be formed. For example, when the surface area of the graphene film 2 is 30 mm ² , the hole diameter of the graphene film 2 is 1 nm, and the total total area of the hole portions is 0.3 mm ² , the aperture ratio of the graphene film = 0.3 / 30 = 1/100, the surface area of the

support layer

4A or 4B is 30 mm ² , the diameter of the holes of the

support layer

4A or 4B is 20 nm, and the total area of the holes is 0.6 mm ^2. Opening ratio = 0.6 / 30 = 1/50. Moreover, what is necessary is just to make it the opening ratio of the

adhesion layer

3D or 3E become these intermediate values. For example, the

adhesive layer

3D or 3E has a surface area of 30 mm ² , the pore diameter of the

adhesive layer

3D or 3E is 10 nm, and the total total area of the holes is 0.45 mm ^2. = 0.45 / 30 = 3/200. In addition, the relationship between the hole diameters is set so that the hole diameter of the graphene film 2 ≦ the hole diameter of the

support layer

3D or 3E≈the hole diameter of the

adhesive layer

3D or 3E. By setting the diameter of the hole of the

support layer

3D or 3E to about 1,000,000 times at most with respect to the diameter of the hole of the graphene film 2, the

support layer

3D or 3E does not break the graphene film 2 Can be supported. Thereby, the hole part of the graphene film 2 can form the part which overlaps and penetrates the hole part of the

support layer

4A or 4B and the hole part of the

adhesion layer

3D or 3E. For example, FIG. 5 shows a schematic diagram of the surface of the

support layer

4A or 4B, the surface of the graphene film 2, and the case where they are superimposed. In this case, the

support layer

4A or 4B is made of a porous material such as PP (polypropylene) or PE (polyethylene), the diameter of the hole 4K is about 10 μm, the opening ratio is about 50%, and the thickness of the support layer is 1 μm to 10 μm. It is said. Further, the diameter of the hole 2K of the graphene film 2 is about 1 nm, the aperture ratio is about 30%, and the film thickness is about 0.3 nm. As shown in FIG. 5, the tubular graphene laminates 1 ′ A and 1 ′ C have holes penetrating by overlapping the hole 2 K portion of the graphene film 2 and the hole 4 K portion of the support layer 4 A or 4 B. Can be formed. Moreover, since the diameter of the hole 4K of the

support layer

4A or 4B is set larger than the diameter of the hole 2K of the graphene film 2, a through-hole can be formed in the graphene film 2 and the

support layer

4A or 4B. In the case of three layers, for example, the surface of the pressure-

sensitive adhesive layer

3D or 3E, the surface of the

support layer

4A or 4B, the surface of the graphene film 2, and a schematic diagram when they are superimposed are shown in FIG. . In this case, the

support layer

4A or 4B and the graphene film 2 have the same configuration as that described above shown in FIG. The pressure-

sensitive adhesive layer

3D or 3E uses a pressure-sensitive adhesive made porous by bubbling or bubbling when the epoxy resin is in a liquid state. The diameter of the hole 3K is about 10 μm, the opening ratio is about 50%, and the thickness is 1 μm to 10 μm. As shown in FIG. 6, the tubular graphene laminates 1′B and 1′D include a hole 2K portion of the graphene film 2, a hole 4K portion of the

support layer

4A or 4B, and a hole 3E of the

adhesive layer

3D or 3E. When this part overlaps, a through-hole can be formed. Further, since the diameter of the hole 4K of the

support layer

4A or 4B and the diameter of the hole of the

adhesive layer

3D or 3E are set larger than the diameter of the hole 2K of the graphene film 2, the graphene film 2, the

adhesive layer

3D or 3E And a through-hole can be formed in

support layer

4A or 4B. Further, if the thickness of the support layer becomes more than 1 times the diameter of the hole of the support layer, a high pressure is required until the fluid passes through when using as a filter. If the aperture is too large, the graphene film may not be supported. Therefore, by setting the thickness to 1 times or less of the aperture, it can be used as a filter without applying high pressure. Similarly, by setting the ratio of the thickness to the diameter of each of the graphene film 2 and the

adhesive layer

3D or 3E to be 1 or less, it can be used as a filter without applying high pressure. Furthermore, the diameter of the hole of the

support layer

4A or 4B may be larger than the diameter of the hole of the

adhesive layer

3D or 3E.

When forming the pores, the

support layer

4A or 4B can use a porous material, for example, porous ceramic, metal, silicon, cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, Fiber materials such as polyethylene, polyacrylonitrile, polypropylene, polycarbonate, polytetrafluoroethylene, PDMS, and other resin compositions composed of polymer resins, nonwoven fabrics, and glass fibers can be used. The

adhesive layer

3D or 3E contains at least one of a pressure-sensitive adhesive such as urea resin, melamine resin, phenol resin, epoxy resin, cyanoacrylate, polyurethane, and acrylic. A porous adhesive can be used by using a resin composition composed of one kind or plural kinds. By forming each of the graphene film 2, the

support layer

4A or 4B, and the

adhesive layer

3D or 3E of the tubular graphene laminates 1′A to F shown in FIGS. 1A to 1F in a porous shape, a filter or a membrane It can be used as a purification membrane (reverse osmosis membrane) or a biological membrane (artificial skin, digestive organ, etc.).

Next, an example of the manufacturing process of the tubular graphene laminate in the present embodiment will be described with reference to FIGS. FIG. 2 shows the production of a tubular graphene laminate 1′A, a tubular graphene laminate 1′B, a tubular graphene laminate 1′E, and a tubular graphene laminate 1′F when the support layer 4A is provided outside the graphene film 2. FIG. 3 shows a process, and FIG. 3 shows a manufacturing process of the tubular graphene laminated body 1′C and the tubular graphene laminated body 1′D when the support layer 4B is provided inside the graphene film 2.

First, the manufacturing process of the tubular graphene laminate will be described with reference to FIG. As shown in FIG. 2A, a metal substrate 7 as a catalyst (for example, copper Cu, nickel Ni, aluminum AL, iron Fe, cobalt Co, etc.) formed in a cylindrical shape is prepared, and the holding device 162 is held. The end portion of the tubular metal substrate 7 is held by the

portions

163A and 163B. When the graphene film 2 is formed on the outer surface of the cylindrical metal substrate 7, the holding by the holding

portions

163A and 163B holds the cylindrical end of the metal substrate 7 so as not to interfere with the film formation. Keep it.

Next, as shown in FIG. 2B, plugs 161 are provided at both ends of the cylindrical shape of the metal substrate 7 so as not to form a graphene film inside the cylinder of the metal substrate 7. At this time, the stopper 161 may be plugged by the holding device 162.

Next, as shown in FIG. 2C, a single-layer or multi-layer graphene film 2 is formed on the outside of the cylinder of the metal substrate 7 by a chemical vapor deposition (CVD) apparatus. Further, when the graphene film 2 is made porous, it can be made porous by doping with an inorganic gas at the time of film formation. In this case, helium ion bombardment, chemical etching, a self-organizing system, or the like can be used as a method for controlling the hole diameter. In this case, even when it is made porous, a monolayer monomolecular graphene film 2 or a multilayer graphene film may be formed.

Next, as shown in FIG. 2 (d), a support layer 4 A is coated on the outer surface of the graphene film 2. When the graphene film 2 is made porous, the support layer 4A is also coated using a porous material. Alternatively, the support layer 4A may be made of a porous material even when the graphene film 2 is not porous. After the support layer 4A is formed, the end portions of the support layer 4A are held by the holding

portions

164A and 164B, and the holding of the metal substrate 7 by the holding

portions

163A and 163B is released. Further, the plugs 161 at the cylindrical ends of the metal substrate 7 are removed.

Next, as shown in FIG. 2 (e), an etching solution is put into the cylinder of the metal substrate 7 to melt the metal base material 7, so that only the graphene film 2 and the support layer 4 A are obtained. In this case, it may be immersed in a water tank filled with an etching solution. Thereby, as shown to Fig.1 (a), tubular graphene laminated body 1'A comprised by 2 layers of support layer 4A and the graphene film | membrane 2 can be manufactured. In this case, the tubular graphene laminated body 1′A can be formed with either the support layer 4A and the graphene film 2 in which no hole is formed, or the support layer 4A and the graphene film 2 in which a hole is formed. .

When the adhesive layer 3D is provided, the adhesive layer 3D is applied to the outer surface of the graphene film 2 after the formation of the graphene film 2 shown in FIG. As shown, the support layer 4A is coated. Moreover, what is necessary is just to utilize the porous thing for the adhesive to apply | coat, when forming porosity in adhesion layer 3D. Thereby, as shown in FIG.1 (b), tubular graphene laminated body 1'B comprised by three layers of support layer 4A, adhesion layer 3D, and the graphene film | membrane 2 can be manufactured. In this case, the tubular graphene laminate 1′B is porous in the support layer 4A, the pressure-sensitive adhesive layer 3D, and the graphene film 2, and in the support layer 4A, the pressure-sensitive adhesive layer 3D, and the graphene film 2. Both can be formed.

Further, after the etching of the metal substrate 7 shown in FIG. 2E, the support layer 4B is coated on the inner surface of the graphene film 2, so that the graphene film 2 is sandwiched between the support layer 4A and the support layer 4B. be able to. When the graphene film 2 is made porous, the support layer 4B is also coated using a porous material. Thereby, as shown in FIG. 1E, a tubular graphene laminate 1'E composed of three layers of the support layer 4A, the graphene film 2, and the support layer 4B can be manufactured.

When the adhesive layer 3E is provided, after the metal substrate 7 shown in FIG. 2 (e) is etched, the adhesive layer 3E is applied to the inner surface of the graphene film 2 and then the support layer 4B is coated. . Moreover, what is necessary is just to utilize the porous thing for the adhesive to apply | coat, when forming porosity in the adhesion layer 3E. Thereby, as shown in FIG. 1 (f), a tubular graphene laminate 1′F composed of five layers of the support layer 4A, the adhesive layer 3D, the graphene film 2, the adhesive layer 3E, and the support layer 4B is manufactured. be able to.

Next, a manufacturing process of the tubular graphene laminate 1 ′ C and the tubular graphene laminate 1 ′ D when the support layer 4 B is provided inside the graphene film 2 will be described with reference to FIG. 3. As shown in FIG. 3A, a metal substrate 7 as a catalyst (for example, copper Cu, nickel Ni, aluminum AL, iron Fe, cobalt Co, etc.) formed in a cylindrical shape is prepared, and the holding device 162 is held. The end portion of the tubular metal substrate 7 is held by the

portions

163A and 163B. When the graphene film 2 is formed on the inner surface of the cylindrical metal substrate 7, the holding by the holding

portions

Next, as shown in FIG. 3B, a single-layer or single-layer or multi-layer graphene film 2 is formed on both the outside and inside of the cylinder of the metal substrate 7 by a chemical vapor deposition (CVD) apparatus. . Further, when the graphene film 2 is made porous, it can be made porous by doping with an inorganic gas at the time of film formation. In this case, helium ion bombardment, chemical etching, a self-organizing system, or the like can be used as a method for controlling the hole diameter. In this case, even when it is made porous, a monolayer monomolecular graphene film 2 or a multilayer graphene film may be formed.

Next, as shown in FIG. 3C, plugs 161 are provided at both ends of the cylindrical shape of the metal substrate 7 so as not to damage the graphene inside the cylindrical shape of the metal substrate 7. At this time, the stopper 161 may be plugged by the holding device 162. After plugging 161, the graphene outside the cylinder of the metal substrate 7 is removed by mechanical or plasma etching.

Next, as shown in FIG. 3 (d), a support layer 4 B is coated on the inner surface of the graphene film 2. When the graphene film 2 is made porous, the support layer 4B is also coated using a porous material. Alternatively, even when the graphene film 2 is not porous, the support layer 4B may be made of a porous material. After the support layer 4B is formed, the end portions of the support layer 4B are held by the holding

portions

164A and 164B, and the holding of the metal substrate 7 by the holding

portions

Next, as shown in FIG. 3 (e), an etching solution is flowed outside the cylinder of the metal substrate 7 to melt the metal substrate 7, so that only the graphene film 2 and the support layer 4 B are obtained. In this case, it may be immersed in a water tank filled with an etching solution. Thereby, as shown in FIG.1 (c), tubular graphene laminated body 1'C comprised by two layers of the support layer 4B and the graphene film | membrane 2 can be manufactured. In this case, the tubular graphene laminated body 1′C can be formed either with the support layer 4B and the graphene film 2 having no holes or with the support layer 4B and the graphene film 2 having pores. .

When the adhesive layer 3E is provided, after removing the graphene film 2 outside the cylinder shown in FIG. 3 (c), the adhesive layer 3E is applied to the inner surface of the graphene film 2, and then FIG. As shown in d), the support layer 4B is coated. Moreover, what is necessary is just to utilize the porous thing for the adhesive to apply | coat, when forming porosity in the adhesion layer 3E. Thereby, as shown in FIG.1 (d), tubular graphene laminated body 1'D comprised by the three layers of the support layer 4B, the adhesion layer 3E, and the graphene film | membrane 2 can be manufactured. In this case, the tubular graphene laminate 1′D is porous in the support layer 4B, the adhesion layer 3E, and the graphene film 2, and in the support layer 4B, the adhesion layer 3E, and the graphene film 2. Both can be formed.

As described above with reference to FIG. 2 and FIG. 3, the tubular graphene laminates 1'A to F can be manufactured. In this case, the graphene film 2 can be formed in a tubular shape by forming the metal substrate in a cylindrical shape, and the graphene film can be maintained in a tubular shape by coating a support layer on the inside or the outside thereof. it can. In the above manufacturing, the case where the etching process of the metal substrate 7 is performed by only one is taken as an example. However, a plurality of etching processes may be performed simultaneously by bundling a plurality of metal substrates. Further, in FIG. 2B, the plugs 161 are provided on both ends of the cylindrical shape of the metal substrate 7, so that the graphene film 2 is not formed at unnecessary positions. In addition, since the holding device 162 holds the cylindrical end portion of the metal substrate 7 or the end portion of the support layer 4A and does not hold the tubular portion, the graphene film 2 can be uniformly formed into a tubular shape. it can.

The tubular graphene laminates 1′A to F of the embodiment described above can be used for various applications, and in particular, by utilizing the gas barrier function of the graphene film 2, the corrosion resistance, chemical resistance, and antifouling properties are improved. By using the provided tubular graphene laminate, it can be used for, for example, pipes, flexible tubes (hoses), soaking rods, living artificial blood vessels, artificial hearts, and the like. Further, by forming each of the graphene film 2, the

support layer

4A or 4B, and the

adhesion layer

3D or 3E of the tubular graphene laminate 1′A to F in a porous shape, a filter, a membrane, a purification membrane (reverse osmosis membrane), It can be used as a biological membrane (artificial skin, digestive organ, etc.). In the case of use for a living body, the

support layer

4A or 4B is made of a material that does not cause a problem even when placed in a living body such as ceramics or PDMS. When used as a pipe or flexible tube (hose), the graphene film 2 provides corrosion resistance, chemical resistance, and antifouling properties, so that chemicals, solvents, oils, foods, powders, water, pure water, etc. are tubular. Can flow inside.

FIG. 4 shows an example of use when the graphene film 2, the

support layer

4A or 4B, and the

adhesive layer

3D or 3E of the tubular graphene laminates 1'A to F are formed in a porous shape. FIG. 4 shows an example of use when seawater is desalinated by the reverse osmosis membrane method by placing seawater inside the tubular graphene laminates 1'A to F.

In FIG. 4, the purification filter 154 includes one or more of the tubular graphene laminates 1′A to F arranged as a tubular graphene laminate group 150 in the inside thereof. One end is used as a seawater inlet, and the other end is used as a seawater outlet. Seawater 152 is introduced from the tank 157 containing the seawater or directly from the sea through the seawater inlet of the purification filter 154 by the pump 153, and the seawater is injected into the tubular shape of the tubular graphene laminate group 150, thereby desalinating the seawater. Thus, the fresh water 155 can be stored in the tank 156. In this case, seawater enriched with salt is discharged to the outside 151 by pumping up seawater with the pump 153 from the seawater outlet at the other end of the purification filter 154. In this case, the pore diameter of the tubular graphene laminate group 150 is set to about 1 nm so that chlorine ions and sodium ions do not pass through the graphene film, so that only water molecules permeate the graphene film, and chlorine Ions and sodium ions can be prevented from permeating. Desalination by the reverse osmosis membrane method has a problem that if the film thickness is large, high water pressure must be applied to allow water to pass through. However, the tubular graphene laminates 1′A to F in this embodiment are used. In this case, since the film thickness can be made extremely thin, water can be permeated at a low water pressure, so that energy consumption is small and the processing speed can be increased.

Although the embodiments of the present invention have been described with reference to the drawings, the specific configuration is not limited to these embodiments, and modifications and additions within the scope of the present invention are included in the present invention. It is.

The combination of materials and functions of the

support layer

4A or 4B and the

adhesive layer

3D or 3E in the above-described embodiment can be freely set. Further, by providing the

support layer

4A or 4B and the

adhesive layer

3D or 3E with a biodegradable function, the

support layer

4A or 4B and the

adhesive layer

3D or 3E can be decomposed by microorganisms after use, thereby reducing the burden on the natural environment. it can.

The end faces of the tubular graphene laminates 1'A to F in the above-described embodiments are formed in a bottomed cylindrical shape, but may have a face (cover face / bottom face) that covers the end.

In the above-described embodiments, when the graphene film is formed, the film is formed by the CVD method, but a film forming method by thermal CVD or a film forming method by plasma CVD may be used.

1′A to F Tubular graphene laminate 2

Graphene films

3D, 3E Adhesive layers 2K, 3K, 4K Holes 4A, 4B Support layer 150 Tubular graphene laminate group 151 External 152 Seawater 153 Pump 154 Purification filter 155 Fresh water 156, 157 Tank 160 Cavity 162

Holding Device

163A, 163B, 164A, 164B Holding Unit

Claims

A graphene film in which carbon atoms are covalently bonded;
A tubular support layer having a predetermined strength;
With
A tubular graphene laminate, wherein the graphene film is formed in a tubular shape by disposing the graphene film along an inner surface side or an outer surface side of the tubular support layer.
The graphene film and the support layer are each formed with a porosity,
2. The tubular graphene laminate according to claim 1, wherein through holes are formed in the graphene film and the support layer by overlapping the porosity of the graphene film and the porosity of the support layer.
The graphene film and the support layer are each formed with a porosity,
The porous diameter of the support layer is set to be larger than the porous diameter of the graphene film so that through holes are formed in the graphene film and the support layer. The tubular graphene laminate according to the description.
Between the graphene film and the tubular support layer, provided with a physical adhesive force, comprising an adhesive layer in which a pore is formed,
The through hole is formed in the graphene film, the support layer, and the adhesive layer by overlapping the porosity of the graphene film, the porosity of the support layer, and the porosity of the adhesive layer. Or the tubular graphene laminate according to 3.
Between the graphene film and the tubular support layer, provided with a physical adhesive force, comprising an adhesive layer in which a pore is formed,
The pore diameter of the support layer and the pore diameter of the adhesive layer are set larger than the pore diameter of the graphene film, so that through holes are formed in the graphene film, the support layer, and the adhesive layer. The tubular graphene laminate according to any one of claims 2 to 4, wherein the tubular graphene laminate is provided.
A tubular second support layer having a predetermined strength;
6. The tubular graphene laminate according to claim 1, wherein the graphene film is disposed so as to be sandwiched between the second support layer and the tubular support layer.
A method for producing a tubular graphene laminate in which a graphene film in which carbon atoms are covalently bonded is formed in a tubular shape along an inner surface side or an outer surface side of a tubular support layer having a predetermined strength,
A film forming step of forming the graphene film into a tubular shape by holding the tubular metal substrate and forming a graphene film along the inner surface side or the outer surface side of the tubular metal substrate;
A support layer forming step of coating a support layer having a predetermined strength along the graphene film side formed in the film forming step;
A metal melting step for holding the support layer formed by the support layer forming step and melting the tubular metal substrate;
A method for producing a tubular graphene laminate, comprising:
The end of the tubular metal base is plugged so as to prevent the film forming process from being performed on the inner surface side of the tubular metal base. Manufacturing method for tubular graphene laminates.
During the film forming step, the graphene is formed to be porous,
In the support layer forming step, the support layer is formed to be porous, and the pores of the graphene film and the support layer overlap to form through holes in the graphene film and the support layer. The method for producing a tubular graphene laminate according to claim 7 or 8, characterized in that:
Before the support layer forming step, an adhesive layer having a pore formed on the graphene film side formed in the film forming step is formed, and the porosity of the graphene film, the porosity of the support layer, and the porosity of the adhesive layer The manufacturing method of the tubular graphene laminated body of Claim 9 provided with the adhesion layer formation process which forms a through-hole in the said graphene film | membrane, the said support layer, and the said adhesion layer by overlapping.
A second support layer forming step of coating a second support layer having a predetermined strength along the graphene film on the side where the tubular metal base material is melted after the metal melting step. Item 11. A method for producing a tubular graphene laminate according to any one of Items 7 to 10.