WO2016080526A1 - カーボンナノチューブシートの製造方法及びカーボンナノチューブシート - Google Patents
カーボンナノチューブシートの製造方法及びカーボンナノチューブシート Download PDFInfo
- Publication number
- WO2016080526A1 WO2016080526A1 PCT/JP2015/082723 JP2015082723W WO2016080526A1 WO 2016080526 A1 WO2016080526 A1 WO 2016080526A1 JP 2015082723 W JP2015082723 W JP 2015082723W WO 2016080526 A1 WO2016080526 A1 WO 2016080526A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon nanotube
- nanotube sheet
- carbon nanotubes
- carbon
- sheet
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/08—Aligned nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
Definitions
- the present invention relates to a carbon nanotube sheet manufacturing method and a carbon nanotube sheet.
- Patent Document 1 a method for producing a carbon nanotube sheet using a carbon nanotube forest has been proposed (see, for example, Patent Document 1).
- a carbon nanotube grown by chemical vapor deposition (CVD) on the surface of a growth substrate is pulled out by a jig, and then pulled out.
- the carbon nanotubes are arranged on a substrate to form a carbon nanotube sheet.
- the carbon nanotube sheet is infiltrated with acetone or the like together with the base material and subjected to a densification treatment, whereby the carbon nanotube sheet is modified and the strength and light transmittance are improved.
- the carbon nanotube sheet drawn out from the carbon nanotube forest is arranged on the base material and densified. Therefore, the interaction between the base material and the carbon nanotubes may hinder the assembly of the carbon nanotubes, and the strength and light transmittance may not necessarily be sufficiently improved.
- the modified carbon nanotube sheet may be in close contact with the substrate, and it may be difficult to separate the modified carbon nanotube sheet from the substrate.
- the present invention has been made in view of such circumstances, and an object thereof is to provide a carbon nanotube sheet manufacturing method and a carbon nanotube sheet excellent in light transmittance and conductivity.
- the method of manufacturing a carbon nanotube sheet according to the present invention includes contacting a free-standing unmodified carbon nanotube sheet in which a plurality of carbon nanotubes are aligned in a predetermined direction with either or both of a liquid substance vapor and a liquid particle.
- the densified portion is modified to contain a plurality of carbon nanotubes preferentially aligned in a predetermined direction, and the densified portion in which the plurality of carbon nanotubes are aggregated is more relative to the densified portion.
- the method includes a first reforming step of obtaining a carbon nanotube sheet having a low density portion having a low density of carbon nanotubes.
- a lamination step of laminating at least two modified carbon nanotube sheets to form a carbon nanotube sheet laminate, and the laminate in a free-standing state It is preferable to include a second reforming step for reforming by a densification treatment in which either or both of the vapor of the liquid substance and the liquid particles are brought into contact.
- the unmodified carbon nanotube sheet is brought into contact with a liquid substance in a free standing state and subjected to a densification treatment, it becomes possible to efficiently aggregate the carbon nanotubes, For example, it is possible to obtain a modified carbon nanotube sheet having a light transmittance of 70% or more and a resistance of 500 ⁇ / ⁇ or less and excellent conductivity.
- the size of the liquid particles is 200 ⁇ m or less.
- the liquid particles are formed by either or both of aerosol of the liquid substance and discharge of the liquid substance by inkjet.
- the liquid substance is preferably an organic solvent.
- the organic solvent is preferably an alcohol compound.
- the alcohol compound is preferably at least one selected from the group consisting of methanol, ethanol and isopropyl alcohol.
- the carbon nanotube sheet of the present invention is manufactured by the above-described method for manufacturing a carbon nanotube sheet.
- the non-modified carbon nanotube sheet of the present invention is produced in a free-standing state by being brought into contact with a liquid substance and densified, so that the carbon nanotubes can be efficiently assembled.
- a modified carbon nanotube sheet having a light transmittance of 70% or more and a resistance of 500 ⁇ / ⁇ or less and excellent conductivity.
- the light transmittance is preferably 70% or more.
- the resistance is preferably 500 ⁇ / ⁇ or less.
- the carbon nanotube sheet of the present invention preferably has a light transmittance of 70% or more and a resistance of 500 ⁇ / ⁇ or less.
- the carbon nanotube sheet of the present invention contains a plurality of carbon nanotubes in a state of being preferentially aligned in a predetermined direction, and a densified portion in which a plurality of carbon nanotubes are aggregated in a fiber shape, and a relative position from the densified portion.
- the carbon nanotube has a low density portion having a low density of carbon nanotubes, has a light transmittance of 70% or more, and a resistance of 500 ⁇ / ⁇ or less.
- the carbon nanotube sheet of the present invention includes a densified portion containing a plurality of carbon nanotubes preferentially aligned in a predetermined direction, and a reduced density portion having a density lower than that of the densified portion. Therefore, it becomes possible to efficiently aggregate the carbon nanotubes.
- a modified carbon nanotube sheet having a light transmittance of 70% or more and a resistance of 500 ⁇ / ⁇ or less and excellent conductivity is obtained. It becomes possible.
- the densified portion is formed by arranging linear bodies including carbon nanotubes in parallel, and the reduced density portion is provided between the densified portions. Is preferred.
- FIG. 1A is a schematic plan view showing an example of a carbon nanotube sheet according to the first embodiment of the present invention.
- FIG. 1B is a schematic plan view showing an example of a carbon nanotube sheet according to the second embodiment of the present invention.
- FIG. 2 is a flowchart of the carbon nanotube sheet manufacturing method according to the first embodiment of the present invention.
- FIG. 3 is an explanatory diagram of the method of manufacturing the carbon nanotube sheet according to the embodiment of the present invention.
- FIG. 4A is an explanatory diagram of the method of manufacturing the carbon nanotube sheet according to the embodiment of the present invention.
- FIG. 4B is an explanatory diagram of a conventional method for producing a carbon nanotube sheet.
- FIG. 5 is a conceptual diagram of a carbon nanotube sheet manufacturing method according to an embodiment of the present invention.
- FIG. 6 is a conceptual diagram of a carbon nanotube sheet manufacturing method according to an embodiment of the present invention.
- FIG. 7 is a diagram showing an example of the first reforming step according to the embodiment of the present invention.
- FIG. 8 is a diagram showing an example of the second reforming step according to the embodiment of the present invention.
- FIG. 9 is a flow diagram of a method of manufacturing a carbon nanotube sheet according to the second embodiment of the present invention.
- FIG. 10A is an explanatory diagram of a twisting process in the method of manufacturing a carbon nanotube sheet according to the present embodiment.
- FIG. 10B is an explanatory diagram of an arrangement step in the method of manufacturing a carbon nanotube sheet according to the present embodiment.
- FIG. 1A is a schematic plan view showing an example of a carbon nanotube sheet 1A according to the first embodiment of the present invention
- FIG. 1B shows an example of the carbon nanotube sheet 1B according to the second embodiment of the present invention. It is a plane schematic diagram which shows.
- the carbon nanotube sheet 1A contains a plurality of carbon nanotubes 12 preferentially aligned in a predetermined direction.
- the carbon nanotube sheet 1A includes a densified portion P1 in which central portions of a plurality of adjacent carbon nanotubes 12 arranged in parallel are densely packed, and the density of the carbon nanotubes 12 is relatively higher than the densified portion P1.
- the density of the carbon nanotube 12 is between the high density portion P1 and the low density portion P2.
- the state in which the carbon nanotubes 12 are preferentially aligned in a predetermined direction means that the number of carbon nanotubes 12 arranged along the predetermined direction is arranged along another direction different from the predetermined direction. More than the number of carbon nanotubes 12.
- the densified portion P1 has an unmodified carbon nanotube sheet 14A (not shown in FIG. 1A) drawn from the carbon nanotube forest 13 (not shown in FIG. 1A, see FIG. 3).
- the carbon nanotubes 12 included in the reference are gathered and provided by a predetermined densification process.
- the densification part P2 is provided as a space S in which the carbon nanotubes 12 are not moved and the carbon nanotubes 12 do not exist due to the densification process between the densification parts P1.
- the carbon nanotube sheet 1A has improved conductivity due to the densified portion A1 of the carbon nanotubes 12 and a reduced density portion A2 as compared with the case where the carbon nanotubes 12 are uniformly present in the plane. As a result, the light transmittance can be improved.
- the carbon nanotube sheet 1B includes a densified portion A1 in which a plurality of carbon nanotubes 12 are twisted and gathered into a fibrous shape, and the high density And a density-reducing portion A2 in which the density of the carbon nanotubes 12 is relatively lower than that of the reducing portion A1.
- the carbon nanotube sheet 1B contains a plurality of carbon nanotubes 12 in a state of being preferentially aligned in a predetermined direction.
- the densified portion P1 is provided from a linear body in which the carbon nanotubes 12 are in the form of threads or ribbons.
- a linear body includes, for example, a plurality of unmodified carbon nanotube sheets 14A (not shown in FIG. 1B, see FIG. 3) drawn from the carbon nanotube forest 13 (not shown in FIG. 1B, see FIG. 3).
- the carbon nanotubes 12 can be obtained as linear carbon nanotubes 12 gathered in a fibrous form.
- the linear carbon nanotubes 12 aggregated in a fibrous form may be a filamentous linear body as a twisted yarn in which a plurality of carbon nanotubes 12 are twisted, and the plurality of carbon nanotubes 12 are twisted. It may be a ribbon-like linear body assembled by friction or the like without putting. That is, the densified portion P1 formed by the plurality of carbon nanotubes 12 can be obtained as a filamentous linear body if the plurality of carbon nanotubes 12 are twisted yarns that are twisted, and the plurality of carbon nanotubes 12 are twisted yarns that are not twisted. If it is, it will be obtained as a ribbon-like linear body.
- the ribbon-like linear body of the carbon nanotube 12 does not have a structure in which the carbon nanotube 12 is twisted.
- the densified portion P1 may be obtained as a linear body in which the carbon nanotubes 12 are formed into yarns by spinning from the dispersion of the carbon nanotubes 12.
- the linear body of the carbon nanotubes 12 is preferably a linear body in which the carbon nanotubes 12 are threaded from the viewpoint of increasing the thickness uniformity of the linear body, and the purity of the carbon nanotubes 12 in the linear body can be increased. From the viewpoint, those obtained by twisting the carbon nanotube sheet 12 are preferable.
- the densified portion P1 is provided with a plurality of linear carbon nanotubes 12 arranged in a substantially parallel manner at a predetermined interval in a predetermined direction.
- the low density part P2 is provided as a space S in which the carbon nanotubes 12 between the linear carbon nanotubes 12 between the high density parts P1 do not exist.
- the carbon nanotube sheet 1B is improved in conductivity by the densified portion A1 of the carbon nanotubes 12 and has the reduced density portion A2.
- the light transmittance can be improved.
- the manufacturing method of the carbon nanotube which concerns on the said 1st Embodiment and the said 2nd Embodiment is demonstrated in detail.
- FIG. 2 is a flowchart of the carbon nanotube sheet manufacturing method according to the first embodiment of the present invention. As shown in FIG. 2, the method of manufacturing a carbon nanotube sheet according to the present embodiment uses a free-standing unmodified carbon nanotube sheet in which a plurality of carbon nanotubes are aligned in a predetermined direction.
- Densification part P1 in which a plurality of carbon nanotubes 12 are assembled by modification by densification treatment in contact with either one or both of the liquid particles, and the density of carbon nanotubes 12 relative to the densification part P1
- a single layer of unmodified carbon nanotube sheet is laminated to make carbon nanotubes
- the lamination step ST12 and the second modification step ST13 are not necessarily performed, and are appropriately performed according to the properties of the carbon nanotube sheet to be manufactured.
- the carbon nanotube sheet manufacturing method according to the present embodiment will be described in detail.
- FIG. 3 is an explanatory diagram of the method of manufacturing the carbon nanotube sheet according to the present embodiment.
- first modification step ST11 first, an unmodified carbon nanotube sheet 14A in which a plurality of carbon nanotubes 12 are aligned in a predetermined direction (hereinafter, also simply referred to as “unmodified carbon nanotube sheet 14A”) is prepared. To do.
- An example of a method for producing the unmodified carbon nanotube sheet 14A is shown in FIG. 3.
- a pair of support rods A plurality of carbon nanotubes 12 forming a ribbon-like aggregate are obtained by pulling out with the support 15.
- the axial direction of the cylindrical shape is aligned so as to preferentially approach the pulling direction.
- the unmodified carbon nanotube sheet 14A is obtained by cutting the drawn carbon nanotubes 12 to a desired size. In this case, the carbon nanotubes 12 are preferentially aligned in one direction within the plane of the carbon nanotube sheet 14A.
- the support rod 15 is not particularly limited as long as the carbon nanotube 12 can be pulled out, and examples thereof include those using various resin materials.
- the conditions for pulling out the carbon nanotubes 12 are not limited, but the temperature is ⁇ 20 ° C. or higher and 500 ° C. or lower, and it is preferable to pull out the unmodified carbon nanotube sheet 14A under normal pressure conditions.
- the obtained unmodified carbon nanotube sheet 14A is transferred from the pair of support rods 15 to the jig 16 having the pair of rod-shaped support portions 16a and held. Thereafter, either or both of the vapor of the liquid substance L and the liquid particles are dispersed in the atmosphere by the sprayer 17, and are brought into contact with the unmodified carbon nanotube sheet 14 ⁇ / b> A in a free standing state held by the jig 16.
- the sheet 14A is densified.
- the carbon nanotubes 12 constituting the unmodified carbon nanotube sheet 14A are agglomerated with each other to form a modified carbon nanotube sheet 14B (hereinafter also simply referred to as “modified carbon nanotube sheet 14B”).
- the spraying of the liquid substance L from the sprayer 17 can be performed at normal temperature and normal pressure, for example, but is not limited thereto.
- the sprayer 17 is not particularly limited as long as it can generate vapor of the liquid substance L or spray the liquid substance L in the form of liquid particles.
- the free standing state refers to a state in which the carbon nanotubes 12 are held between the pair of support portions 16a of the jig 16 without being disposed on the base material.
- the free-standing state is the state of all the unmodified carbon nanotube sheets 14A. It is not necessary to be held in the area, and a part of the area may be held by the holding body.
- FIG. 4A is an explanatory diagram of a carbon nanotube sheet manufacturing method according to the present embodiment
- FIG. 4B is an explanatory diagram of a conventional carbon nanotube sheet manufacturing method.
- the unmodified carbon nanotube sheet 14A is held by the jig 16 (not shown in FIG. 4A, see FIG. 3) and is in a free standing state. Densify processing.
- the unmodified carbon nanotube sheet 14A is infiltrated with a liquid substance such as acetone. Densification processing is necessary.
- the densification process since the densification process is performed in a free-standing state, it is not affected by the interaction between the base material 21 and the carbon nanotubes 12 constituting the unmodified carbon nanotube sheet 14A.
- the unmodified carbon nanotube sheet 14A can be efficiently densified.
- FIGS. 5 and 6 are conceptual diagrams of the method of manufacturing the carbon nanotube sheet according to the present embodiment.
- FIG. 6 schematically shows a cross section taken along line VV in FIG.
- the unmodified carbon nanotube sheet 14A in which a plurality of carbon nanotubes 12 are aligned substantially in parallel is not held on a substrate or the like, and is in a free standing state.
- the densification process is performed at As a result, the carbon nanotubes 12 gather together without the carbon nanotubes 12 being entangled with each other, so that the carbon nanotubes 12 can be bound and densely gathered (hereinafter, this phenomenon is referred to as “bundling”). is there.).
- the carbon nanotubes 12 are closely packed while maintaining the preferential alignment of the carbon nanotube sheet 14A in a predetermined direction, and the contacts between the carbon nanotubes 12 are increased, so that the strength and conductivity of the modified carbon nanotube sheet 14B are increased. While improving, since the space S is formed between the bundles of the dense carbon nanotubes 12, the light transmittance of the modified carbon nanotube sheet 14B is improved. Therefore, the modified carbon nanotube sheet 14B having excellent conductivity and light transmittance can be realized.
- the non-modified carbon nanotube sheet 14A when the non-modified carbon nanotube sheet 14A is infiltrated into the liquid substance L and densified, the carbon nanotubes 12 in a free standing state are collapsed, and thus it is necessary to fix the carbon nanotubes 12 on the substrate. There is. For this reason, even when the carbon nanotubes 12 are infiltrated into the liquid substance L, the interaction between the carbon nanotubes 12 and the base material 21 inhibits the assembly of the carbon nanotubes 12, so that the conductivity and light transmission are reduced.
- the modified carbon nanotube sheet 14B having an excellent rate cannot be obtained.
- the liquid substance L in the first reforming step ST11 is not particularly limited as long as it is a substance that becomes liquid at room temperature (for example, 25 ° C.), and water and various organic solvents are used within a range where the effects of the present invention can be achieved. it can.
- an organic solvent is preferable from the viewpoint that the affinity with the carbon nanotubes 12 is high, the aggregation of the carbon nanotubes 12 proceeds efficiently, and the volatilization quickly after the aggregation of the carbon nanotubes 12.
- organic solvent alcohol compounds having 1 to 6 carbon atoms such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, pentyl alcohol and hexyl alcohol are preferable.
- the organic solvent it is preferable to use at least one selected from the group consisting of methanol, ethanol and isopropyl alcohol from the viewpoint of reducing environmental burden and easy handling.
- the size (particle diameter) of the liquid particles of the liquid substance L in the first reforming step ST11 is preferably 200 ⁇ m or less. Thereby, since the liquid substance L can be efficiently sprayed on the carbon nanotubes 12, the conductivity and light transmittance of the modified carbon nanotube sheet 14B are further improved.
- the size of the liquid particles is preferably 5 nm or more, more preferably 7.5 nm or more, further preferably 10 nm or more, more preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less. Considering the above, the size of the liquid particles is preferably 5 nm to 200 ⁇ m, more preferably 7.5 nm to 100 ⁇ m, and still more preferably 10 nm to 50 ⁇ m.
- the particle diameter of the liquid particles of the liquid substance L can be measured using, for example, an optical microscope (trade name: ultra-high magnification USB microscope CCD, SH140CCD-R (3W), manufactured by Matsudensha).
- the particle diameter of the liquid particles on the carbon nanotube sheet 14 can be measured by capturing and recording an image of the liquid particles of the liquid substance L in the atmosphere at room temperature and analyzing the recorded image.
- the particle diameter of the liquid particles is an average value of the particle diameters of 20 liquid particles extracted at random.
- the liquid particles of the liquid substance L are preferably formed by either or both of an aerosol of the liquid substance L and ejection of the liquid substance L by inkjet. Thereby, since the liquid substance L can be efficiently sprayed on the carbon nanotubes 12, the conductivity and light transmittance of the modified carbon nanotube sheet 14B are further improved.
- the unmodified carbon nanotube sheet 14A can be discharged to the liquid particles of the liquid substance L by ink jet or exposed to the aerosol of the liquid substance L, and conventionally known production techniques are used. Can be used.
- the unmodified carbon nanotube sheet 14A can be continuously modified by sequentially winding the produced modified carbon nanotube sheet 14B.
- bundling can be caused only in a portion where liquid particles are discharged by partially discharging liquid particles in a plan view to the unmodified carbon nanotube sheet 14A. It is easy to selectively perform the densification process in the area in plan view.
- the first modification step ST11 improves the conductivity of the modified carbon nanotube sheet 14B after the modification, and also allows the light transmittance to be 70% or more.
- the modified carbon nanotube sheet 14B used can be realized.
- the light transmittance of the modified carbon nanotube sheet 14B is preferably 70% or more, and more preferably 80% or more.
- the light transmittance of the unmodified carbon nanotube sheet 14A may vary depending on manufacturing conditions. However, through the first modification step ST11, the light transmittance of the modified carbon nanotube sheet 14B tends to increase to a high level regardless of the light transmittance of the unmodified carbon nanotube sheet 14A. Therefore, it is possible to obtain the modified carbon nanotube sheet 14B having such a high light transmittance through the first modification step ST11.
- FIG. 7 is a diagram showing an example of the first reforming step ST11 according to the present embodiment.
- the modified carbon nanotube sheet 14B in the first reforming step ST11, can be obtained by stacking two or more unmodified carbon nanotube sheets 14A and at most four layers and densifying them. Good. Thereby, since the modified carbon nanotube sheet 14B can be obtained in a state where a plurality of unmodified carbon nanotube sheets 14A are laminated, the strength of the obtained modified carbon nanotube sheet 14B is further improved and the electrical conductivity is increased. Further improvement.
- the lamination step ST12 at least two modified carbon nanotube sheets 14B are laminated to form a laminated body of the modified carbon nanotube sheets 14B.
- the stacking step ST12 at least two modified carbon nanotube sheets 14B and one or more unmodified carbon nanotube sheets 14A may be stacked to form a stacked body of the carbon nanotube sheets 14A and 14B.
- the number of unmodified carbon nanotube sheets 14A included in the laminated carbon nanotube sheets 14 is four or less from the viewpoint of keeping the light transmittance of the laminated body 32 that has undergone the second modified step ST13 obtained to a high level. Is more preferable, it is more preferably 2 layers or less, and still more preferably 0 layer.
- the first modified step ST11 is performed on the unmodified carbon nanotube sheet 14A drawn out from the carbon nanotube forest 13 and held on the jig 16, and then the unmodified carbon nanotube sheet 13A is pulled out from the carbon nanotube forest 13 separately. It is possible to obtain a laminate of unmodified carbon nanotube sheets 14B by holding the modified carbon nanotube sheet 14A on the jig 16 and laminating it after performing the first modification step ST11. Become.
- the modified carbon nanotube sheet 14B used in the lamination step ST12 may be a modified carbon nanotube sheet 14B obtained by laminating two or more unmodified carbon nanotube sheets 14A and densifying them.
- the direction in which one carbon nanotube 12 of the carbon nanotube sheets 14 to be stacked is aligned and the direction in which the carbon nanotubes 12 of the other carbon nanotube sheet 14 are aligned are substantially in the same direction. It is preferable that For example, when the carbon nanotube sheet 14 is obtained by pulling out from the carbon nanotube forest 13, it is preferable that the pulling direction of one carbon nanotube sheet 14 and the pulling direction of the other carbon nanotube sheet 14 are substantially the same direction. . Thereby, since the carbon nanotubes 12 between the respective layers of the carbon nanotube sheet 14 are aligned in the same direction, the light transmittance, strength, and conductivity of the laminate of the carbon nanotube sheet 14 can be improved.
- the substantially same direction here includes a deviation in the orientation direction of the carbon nanotubes 12 between the respective layers as long as the effect of the present invention is achieved.
- the displacement in the orientation direction of each layer is preferably within a range of 15 ° or less, more preferably within a range of 10 ° or less, and further preferably within a range of 5 ° or less.
- ⁇ Second reforming step> In the second modification step ST13, either the vapor of the liquid substance L or the liquid particles generated by the sprayer 17 or the like in a free standing state on the laminated body of the modified carbon nanotube sheet 14B obtained in the lamination step ST12. A layered product of the modified carbon nanotube sheet 14B is obtained by modification by densification treatment in contact with one or both.
- the liquid substance L the same material as in the first reforming step ST11 can be used.
- the particle diameter of the liquid particles of the liquid substance L the same conditions as in the first reforming step ST11 can be used.
- the spraying of the liquid substance L from the sprayer 17 can be performed under the same conditions as in the first reforming step ST11.
- FIG. 8 is a diagram showing an example of the second reforming step ST13 according to the present embodiment.
- the second reforming step ST13 at least two or more layers are reformed in the stacking step ST12.
- the laminated body 31 in which the carbon nanotube sheets 14B are laminated together is made into a laminated body 32 that is further modified by performing a densification treatment with one or both of the vapor of the liquid substance L and the liquid particles.
- the assembly of the carbon nanotubes 12 proceeds efficiently, so the laminated body 32 of the modified carbon nanotube sheet 14B after the lamination is formed.
- the conductivity, light transmittance and strength are further improved.
- the densification process may be performed on the stacked body in which the unmodified carbon nanotubes 14A and the modified carbon nanotubes 14B are stacked.
- a laminated body of the modified carbon nanotube sheet 14B may be obtained by alternately repeating the lamination step ST12 and the second modification step ST13.
- the resistance of the laminate 32 is preferably 500 ⁇ / ⁇ or less, more preferably 400 ⁇ / ⁇ or less, still more preferably 300 ⁇ / ⁇ or less, and particularly preferably 200 ⁇ / ⁇ or less.
- the resistance of the modified carbon nanotube sheet 14B and the unmodified carbon nanotube sheet 14A may vary depending on the manufacturing conditions of the unmodified carbon nanotube sheet 14A. However, as the number of stacked layers is increased, the resistance is remarkably lowered. Therefore, it is possible to obtain such a low-resistance stacked body by increasing the number of stacked layers.
- the light transmittance of the laminate 32 is preferably 70% or more, and more preferably 80% or more.
- the non-modified carbon nanotube sheet 14A is brought into contact with the liquid substance in the free standing state and densified, so that the carbon nanotubes 12 can be efficiently assembled.
- a modified carbon nanotube sheet 14B having a light transmittance of 70% or more and a resistance of 500 ⁇ / ⁇ or less and excellent conductivity and light conductivity.
- the light transmittance of the modified carbon nanotube sheet 14B is, for example, optical transmission using a visible-ultraviolet light source (trade name: L10290, manufactured by Hamamatsu Photonics) and a spectroscope (trade name: USB2000, manufactured by Ocean Optics). It can be measured by rate.
- the light transmittance is calculated as an average value of the transmittance in the visible light region (380 nm to 760 nm).
- FIG. 9 is a flowchart of an example of the carbon nanotube sheet manufacturing method according to the second embodiment of the present invention.
- the method of manufacturing a carbon nanotube sheet according to the present embodiment twists a free-standing unmodified carbon nanotube sheet 14A in which a plurality of carbon nanotubes 12 are aligned in a predetermined direction,
- a twisting step ST21 for obtaining a linear carbon nanotube 12 in which the carbon nanotubes 12 are gathered in a fibrous form, and a high density in which the linear carbon nanotubes 12 are arranged substantially in parallel and the filamentous carbon nanotubes 12 are arranged.
- FIG. 10A is an explanatory diagram of the twisting step ST21 in the method of manufacturing the carbon nanotube sheet 14 according to the present embodiment
- FIG. 10B is an explanatory diagram of the arranging step ST22 in the method of manufacturing the carbon nanotube sheet according to the present embodiment. It is.
- a predetermined number of ends of a carbon nanotube forest 13 in which a plurality of carbon nanotubes 12 provided on a substrate 11 such as a silicon wafer are arranged by a catalytic chemical vapor deposition method or the like is formed.
- the unmodified carbon nanotubes 14A having a predetermined width are pulled out using a jig.
- the drawn unmodified carbon nanotube sheet 14A is converged through a metal ring 100 having a diameter smaller than the width of the unmodified carbon nanotube sheet 14A.
- the bundled unmodified carbon nanotube sheet 14A is oscillated and moved in the axial direction of the rotating shaft 101 while the bundled unmodified carbon nanotube sheet 14A is applied to the outer peripheral surface of the rubber roll 102 having the rotating shaft 101.
- the carbon nanotube sheet 14A is slid on the rubber roll 102.
- the carbon nanotubes 12 of the bundled unmodified carbon nanotube sheet 14A are twisted by friction generated by sliding, and a ribbon-like linear body in which a plurality of carbon nanotubes 12 are gathered into a fibrous shape. It becomes the carbon nanotube 14C.
- the linear carbon nanotube 14 ⁇ / b> C is wound around the bobbin 103.
- the ends of the linear carbon nanotubes 14C wound around the bobbin 103 and twisted to a predetermined width d are pulled out and fixed on the outer peripheral surface of the rubber roll 102 so that the adhesive surface faces outward. Fix to the end of the adhesive sheet 104.
- the rubber roll 102 is moved at a constant speed in a direction parallel to the axial direction of the rotating shaft 101 while winding the linear carbon nanotubes 14 ⁇ / b> C drawn out from the bobbin 103 by rotating the rubber roll 102.
- the linear carbon nanotubes 14 ⁇ / b> C are wound around the rubber roll 102 so as to draw a spiral with a substantially equal width I.
- the adhesive sheet 104 is cut together with the linear carbon nanotubes 14 ⁇ / b> C along a direction parallel to the axial direction of the rotation shaft 101 of the rubber roll 102, and the filamentous carbon nanotubes 14 ⁇ / b> C are arranged in parallel on the adhesive sheet 104.
- a carbon nanotube sheet 1B as a conductive sheet fixed is obtained.
- the manufacturing method of the carbon nanotube sheet is not limited to this method.
- the carbon nanotube sheet can be manufactured, for example, by performing a spinning step ST21 'of the carbon nanotubes 12 in place of the twisting step ST21.
- the spinning of the carbon nanotubes 12 can be performed, for example, by a manufacturing method described in US 2013/0251619 (Japanese Patent Laid-Open No. 2012-126635).
- the carbon nanotube 12 is spun by, for example, preparing a dispersion in which the carbon nanotube 12 is dispersed in a first solvent that is a mixed solvent containing only water or an organic solvent and water by using a surfactant.
- the carbon nanotubes can be agglomerated and spun by injecting the dispersion liquid in which the carbon nanotubes are dispersed into the aggregating liquid that is a second solvent different from the first solvent.
- the plurality of carbon nanotubes 12 contained in the linear body are maintained in a preferentially aligned state in a predetermined direction, and carbon nanotubes are also present in the carbon nanotube sheet 14C obtained in the placement step ST22.
- a state in which they are preferentially aligned in one direction in the plane is maintained.
- a linear carbon nanotube sheet in which the carbon nanotubes 12A are gathered in a fiber shape with a predetermined diameter d by twisting and spinning the unmodified carbon nanotube sheet 14A. 14C, the linear carbon nanotubes 14C are arranged at a predetermined interval width I to provide the densified portion P1 and the densified portion P2, so that the light transmittance is 70% or more and the resistance is low. It becomes easy to obtain a carbon nanotube sheet excellent in light transmittance and conductivity of 500 ⁇ / ⁇ or less.
- the particle diameter of the liquid particles sprayed on the carbon nanotube sheet was measured using an optical microscope (trade name: ultra-high magnification USB microscope CCD SH140CCD-R (3W), manufactured by Matsudensha Co., Ltd.). An image of liquid particles was captured and recorded in the air at room temperature, and the particle diameter of the liquid particles on the carbon nanotube sheet was measured by analyzing the recorded image. The particle diameter of the liquid particles was the average of the particle diameters of 20 liquid particles extracted at random.
- the light transmittance of the carbon nanotube sheet was measured by optical transmittance using a visible-ultraviolet light source (trade name: L10290, manufactured by Hamamatsu Photonics) and a spectroscope (trade name: USB2000, manufactured by Ocean Optics).
- the intensity of light emitted from the light source ⁇ is I 0 ( ⁇ )
- the intensity of light transmitted through the carbon nanotube sheet is I ( ⁇ )
- the intensity of the light is measured using a spectroscope.
- the transmittance T ( ⁇ ) at the wavelength ⁇ was calculated from the ratio (I / I 0 ).
- the optical axis was adjusted so that light from the light source was perpendicularly incident on the carbon nanotube sheet.
- the light transmittance was calculated by the average value of the transmittance in the visible light region (380 nm to 760 nm).
- Example 1> (Preparation of carbon nanotube forest) Carbon nanotube forests were formed by catalytic chemical vapor deposition on a 6-inch silicon wafer divided in advance using a thermal CVD apparatus including three furnaces using argon gas as a carrier gas and acetylene as a carbon source. The height of the carbon nanotube forest was 300 ⁇ m.
- a carbon nanotube sheet was generated by twisting the end of the carbon nanotube forest and pulling it out with tweezers. Free-standing carbon, in which the carbon nanotube sheet is locked to two parallel support bars (copper bar, 2 mm in diameter) with a spacing of 45 mm by self-adhesion, and the excess part is cut and stretched between the two support bars A nanotube sheet was obtained. Furthermore, using a jig having two parallel support bars (copper bars, diameter 2 mm) with a spacing of 30 mm, the free-standing carbon nanotube sheet stretched between the support bars is transferred between the support bars of the jig. Thus, a free-standing carbon nanotube sheet (unmodified carbon nanotube sheet) was obtained.
- Example 2 (Lamination of modified carbon nanotube sheets) Example 1 except that a jig having two parallel support bars (copper bar, diameter 2 mm) having a distance of 20 mm was used instead of the jig having two parallel support bars having a distance of 30 mm. Similarly, a modified carbon nanotube sheet was obtained. The obtained modified carbon nanotube sheet and the modified carbon nanotube sheet, which was obtained in the same manner as in Example 1, and was fixed to a jig having two parallel support bars with a distance of 30 mm, were pulled out from each other. By superimposing the directions in the same direction, a laminated body in which two modified carbon nanotube sheets were laminated was obtained.
- modified carbon nanotube sheet obtained in the same manner as in Example 1 was further laminated on the obtained laminate, and 4, 6, 8, 10, and 12 modified carbon nanotube sheets were laminated. A laminate was obtained. These laminates were subjected to light transmittance measurement and conductivity evaluation. The results are also shown in Table 1 below.
- Example 3 (Exposure of laminate to aerosol) The laminate obtained by laminating the 12-layer modified carbon nanotube sheets obtained in Example 2 was exposed to aerosol in the same manner as in Example 1. Thereafter, the laminate was subjected to light transmittance measurement and conductivity evaluation. The results are also shown in Table 1 below.
- Example 4 A modified carbon nanotube sheet was obtained in the same manner as in Example 1 except that instead of ethanol aerosol using air as a dispersion medium, water aerosol using air as a dispersion medium was used. The particle diameter of the water liquid particles was 15 ⁇ m.
- the unmodified carbon nanotube sheet and the modified carbon nanotube sheet before and after exposure to the aerosol were subjected to light transmittance measurement and conductivity evaluation. The results are also shown in Table 1 below.
- Example 5 A modified carbon nanotube sheet was obtained in the same manner as in Example 1 except that an aerosol of isopropyl alcohol (IPA) using air as a dispersion medium was used instead of the ethanol aerosol using air as a dispersion medium.
- the particle diameter of the liquid particles of isopropyl alcohol was 15 ⁇ m.
- the unmodified carbon nanotube sheet and the modified carbon nanotube sheet before and after exposure to the aerosol were subjected to light transmittance measurement and conductivity evaluation. The results are also shown in Table 1 below.
- Example 6 Instead of exposing the unmodified carbon nanotube sheet to aerosol, ethanol was ejected to the modified carbon nanotube sheet by inkjet printing using a printing apparatus (trade name: Deskjet 1000, manufactured by Hewlett-Packard Company). Obtained a modified carbon nanotube sheet in the same manner as in Example 1. The particle diameter of ethanol was 15 ⁇ m. The unmodified carbon nanotube sheet and the modified carbon nanotube sheet before and after exposure to the aerosol were subjected to light transmittance measurement and conductivity evaluation. The results are also shown in Table 1 below.
- Example 7 In the same manner as in Example 1, a carbon nanotube sheet was prepared.
- Two-layer carbon nanotubes are formed by superimposing unmodified carbon nanotube sheets pulled out from the carbon nanotube forest on the unmodified carbon nanotube sheets in a free standing state held by a jig so that the respective drawing directions are the same direction.
- a laminate of unmodified carbon nanotube sheets laminated with sheets was obtained.
- this operation was further repeated to obtain a carbon nanotube sheet in which three-layer and four-layer carbon nanotube sheets were laminated.
- ethanol was ejected by inkjet printing in the same manner as in Example 6 to obtain modified carbon nanotube sheets.
- Measurement of light transmittance and evaluation of electrical conductivity were performed on the unmodified or modified carbon nanotube sheets of each number of laminated layers before and after ethanol ejection or the laminated body thereof. The results are shown in Table 1 below.
- ⁇ Comparative example 2> Instead of exposing the unmodified carbon nanotube sheet to the aerosol, the same procedure as in Example 1 was performed except that 6 ⁇ l of ethanol was dropped and infiltrated onto the unmodified carbon nanotube sheet in a free standing state with a micropipette. Densified. As a result, the carbon nanotube sheet was destroyed and the densification process could not be performed. For Comparative Example 2, since the modified carbon nanotube sheet could not be obtained, the light transmittance measurement and the conductivity evaluation were not performed.
- Example 1 the modified carbon nanotube sheet modified by the densification treatment in contact with one or both of the vapor of the liquid substance and the liquid particles in a free standing state drawn from the carbon nanotube forest. It can be seen that both the transmittance and the conductivity evaluation are good (Examples 1 and 4-6). This effect was also obtained in the same manner when the densification treatment was performed after laminating unmodified carbon nanotube sheets (Example 7). Comparing Example 4 and Example 5, the light transmittance before the first reforming step was about the same, but Example 5 using an organic solvent in the first reforming step was light transmittance. Rose significantly. In Example 2, as the number of laminated layers of modified carbon nanotube sheets increased, the resistance of the laminated body decreased while the light transmittance decreased.
- Example 3 in which the second modification step was further performed on the laminate, the light transmittance was significantly increased as compared to Example 2 in which the second modification step was not performed.
- the laminate of the carbon nanotube sheet of Example 3 shows a high light transmittance even though the number of laminations is larger than any of the laminates obtained in Example 7, and is higher by increasing the number of laminations. Conductivity is also obtained.
- Example 8> Using a thermal CVD apparatus equipped with three furnaces using argon gas as a carrier gas and acetylene as a carbon source, a carbon nanotube forest having a height of 300 ⁇ m was obtained by catalytic chemical vapor deposition on a 50 mm wide silicon wafer. .
- a part of the end of the obtained carbon nanotube forest was picked, and the carbon nanotube sheet was drawn out with a width of 7 mm.
- the drawn carbon nanotube sheet was bundled through a metal ring having a diameter of 5 mm.
- the bundled carbon nanotube sheet was placed on a rubber roll having a diameter of 3 cm, the rubber roll was vibrated in the axial direction of the roll, and the bundled carbon nanotube sheet was slid on the rubber roll.
- the bundled carbon nanotube sheets were twisted into a ribbon shape by friction generated by sliding, and the twisted ribbon-like linear carbon nanotubes were wound around a bobbin. In this way, the carbon nanotube sheet was pulled out from the carbon nanotube forest, the carbon nanotube sheet was focused, the carbon nanotubes were twisted, and the carbon nanotubes in the form of a linear body were continuously wound.
- a releasable pressure-sensitive adhesive sheet (manufactured by MeCanimaging, product name: MTAR) was wound around the outer peripheral surface of the rubber roll and fixed so that the pressure-sensitive adhesive surface faced outward without wrinkles.
- the carbon nanotubes of the linear body are fed out, and the rubber roll is gradually rolled up while rotating the rubber roll. Were moved at a constant speed in a direction parallel to the axial direction of the roll, and wound on a rubber roll so that the linear carbon nanotubes spiraled at equal intervals.
- the adhesive sheet is cut together with the linear carbon nanotubes, and the conductive sheet in which the linear carbon nanotubes are aligned and fixed in parallel to the adhesive sheet Obtained.
- the diameter d of the linear bodies was 20 ⁇ m, and the interval 1 between the arranged linear bodies was 1700 ⁇ m. The results are shown in Table 2 below.
- Example 9 A conductive sheet was produced in the same manner as in Example 8 except that the carbon nanotubes of the linear bodies were wound around a rubber roll so that the interval 1 between the linear bodies was 800 ⁇ m. The results are shown in Table 2 below.
- Example 10 A conductive sheet was produced in the same manner as in Example 8 except that the carbon nanotubes of the linear bodies were wound around a rubber roll so that the interval 1 between the linear bodies was 200 ⁇ m. The results are shown in Table 2 below.
- Example 1 A conductive sheet was produced in the same manner as in Example 8 except that the carbon nanotubes of the linear body were wound around a rubber roll so that the interval 1 between the linear bodies was 10 ⁇ m. The results are shown in Table 2 below.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
図2は、本発明の第1の実施の形態に係るカーボンナノチューブシートの製造方法のフロー図である。図2に示すように、本実施の形態に係るカーボンナノチューブシートの製造方法は、所定方向に複数のカーボンナノチューブが整列させられたフリースタンディングの未改質のカーボンナノチューブシートを、液体物質の蒸気及び液体粒子のいずれか一方又は両方と接触させる高密度化処理により改質して複数のカーボンナノチューブ12が集合した高密度化部P1と、当該高密度化部P1より相対的にカーボンナノチューブ12の密度が低い低密度化部P2とが設けられたカーボンナノチューブシートを得る第1改質工程ST11と、少なくとも2層の改質されたカーボンナノチューブシートを積層し又は改質されたカーボンナノチューブシート上に少なくとも1層の未改質のカーボンナノチューブシートを積層してカーボンナノチューブシートの積層体とする積層工程ST12と、積層体を液体物質の蒸気及び液体粒子のいずれか一方又は両方と接触させる高密度化処理により改質する第2改質工程ST13とを含む。なお、積層工程ST12及び第2改質工程ST13は、必ずしも実施する必要はなく、製造するカーボンナノチューブシートの性状に応じて適宜実施する。以下、本実施の形態に係るカーボンナノチューブシートの製造方法について詳細に説明する。
図3は、本実施の形態に係るカーボンナノチューブシートの製造方法の説明図である。第1改質工程ST11では、まず、所定方向に複数のカーボンナノチューブ12が整列させられた未改質のカーボンナノチューブシート14A(以下、単に、「未改質カーボンナノチューブシート14A」ともいう)を用意する。未改質カーボンナノチューブシート14Aの製造方法の一例を示すと、図3に示すように、シリコンウエハなどの基板11上に多数のカーボンナノチューブ12が立ち並んだカーボンナノチューブフォレスト13から、一対の支持棒(支持体)15によって引き出すことにより、リボン状の集合体を形成した複数のカーボンナノチューブ12を得る。複数のカーボンナノチューブ12は、カーボンナノチューブフォレスト13から引き出すことによって、その円筒状の形状の軸方向が、引き出し方向に優先的に近づくように整列させられている。その後、引き出したカーボンナノチューブ12を所望の大きさに切断することにより未改質カーボンナノチューブシート14Aが得られる。この場合には、カーボンナノチューブ12がカーボンナノチューブシート14Aの面内の一方向に優先的に整列させられている。支持棒15としては、カーボンナノチューブ12を引き出せるものであれば特に制限はなく、例えば、各種樹脂材料を用いたものが挙げられる。また、カーボンナノチューブ12を引き出す条件は限定されないが、温度が-20℃以上500℃以下であり、常圧の条件で未改質カーボンナノチューブシート14Aとして引き出すことが好ましい。
積層工程ST12では、少なくとも2層の改質カーボンナノチューブシート14Bを積層して改質カーボンナノチューブシート14Bの積層体とする。また、積層工程ST12では、少なくとも2層の改質カーボンナノチューブシート14Bと、1層以上の未改質カーボンナノチューブシート14Aを積層してカーボンナノチューブシート14A,14Bの積層体としてもよい。得られる第2改質工程ST13を経た積層体32の光線透過率を高い程度に保つ観点から、積層するカーボンナノチューブシート14に含める未改質カーボンナノチューブシート14Aの数は、4層以下であることが好ましく、2層以下であることより好ましく、0層であることが更に好ましい。積層工程ST12では、例えば、カーボンナノチューブフォレスト13から引き出して治具16に保持した未改質カーボンナノチューブシート14Aに第1改質工程ST11を行い、その上に、別途カーボンナノチューブフォレスト13から引き出した未改質カーボンナノチューブシート14Aを治具16に保持して、第1改質工程ST11を行った上でこれを積層することにより、未改質カーボンナノチューブシート14B同士の積層体を得ることが可能となる。積層工程ST12に用いる改質カーボンナノチューブシート14Bは、未改質カーボンナノチューブシート14Aを2層以上4層以下積層して高密度化処理することにより得た改質カーボンナノチューブシート14Bであってもよいが、未改質カーボンナノチューブシート14Aを積層せずに高密度化処理することにより得たものであることが好ましい。これにより、後述する第2改質工程ST13による、改質カーボンナノチューブシート14Bの積層体32の導電性、光線透過率及び強度が向上するという効果がより効率的に得られる。
第2改質工程ST13では、積層工程ST12で得られた改質カーボンナノチューブシート14Bの積層体を、フリースタンディングの状態で、噴霧器17などにより発生させた液体物質Lの蒸気及び液体粒子のいずれか一方又は両方と接触させる高密度化処理により改質して改質カーボンナノチューブシート14Bの積層体を得る。液体物質Lとしては、第1改質工程ST11と同様のものを用いることができる。また、液体物質Lの液体粒子の粒子径としては、第1改質工程ST11と同様の条件を用いることができる。さらに、噴霧器17からの液体物質Lの噴霧は、第1改質工程ST11と同様の条件で実施することができる。
次に、本発明の第2の実施の形態について説明する。なお、以下においては、上述した第1の実施の形態との相違点を中心に説明し、説明の重複を避ける。
カーボンナノチューブシート上に噴霧する液体粒子の粒子径は、光学顕微鏡(商品名:超高倍率USBマイクロスコープCCD SH140CCD-R(3W)、松電舎社製)を用いて測定した。室温にて大気中で液体粒子の画像を撮像して記録し、記録した画像を解析することにより、カーボンナノチューブシート上での液体粒子の粒子径を測定した。液体粒子の粒子径は、無作為に抽出した20個の液体粒子の粒子径の平均値をとった。
カーボンナノチューブシートの光線透過率は、可視-紫外光源(商品名:L10290、浜松ホトニクス社製)及び分光器(商品名:USB2000、オーシャンオプティクス社製)を用いた光学透過率により測定した。光源から放出される波長λの光の強度をI0(λ)とし、カーボンナノチューブシートを透過した光の強度をI(λ)として、分光器を用いてそれぞれの値を測定して光の強度の比(I/I0)から波長λにおける透過率T(λ)を算出した。測定時には、光源からの光がカーボンナノチューブシートに対して垂直に入射するように光軸を調整した。光線透過率は、可視光領域(380nm~760nm)の透過率の平均値により算出した。
カーボンナノチューブシートのシート抵抗(Rsheet)は、実施例及び比較例で得られた、カーボンナノチューブシート(銅棒間の間隔L=20mm又は30mm)の抵抗値(R)をデジタルマルチメーター(商品名:U1273A、アジレント社製)により測定し、カーボンナノチューブシートの幅(W)との間隔から下記関係式(1)に基づいて算出した。カーボンナノチューブシートの幅は、写真の画像解析から計算した。
Rsheet=R×W/L ・・・式(1)
(カーボンナノチューブフォレストの調製)
キャリアガスとしてアルゴンガス、炭素源としてアセチレンを用いた3つの炉を備える熱CVD装置を用い、予め分割した6インチシリコンウエハ上に、触媒化学気相蒸着法によりカーボンナノチューブフォレストを形成した。カーボンナノチューブフォレストの高さは300μmであった。
カーボンナノチューブフォレストの端部をよじり、ピンセットで引き出すことにより、カーボンナノチューブシートを生成させた。カーボンナノチューブシートを間隔45mmの2本の平行な支持棒(銅棒、直径2mm)に自己粘着性により係止し、余剰部を切断して2本の支持棒間に張られたフリースタンディングのカーボンナノチューブシートを得た。さらに、間隔30mmの2本の平行な支持棒(銅棒、直径2mm)を有する治具を用いて、支持棒間に張られたフリースタンディングのカーボンナノチューブシートを治具の支持棒間に移し替えてフリースタンディングのカーボンナノチューブシート(未改質カーボンナノチューブシート)を得た。
超音波加湿器を用いて空気を分散媒とするエタノールのエアロゾルを発生させた後、フリースタンディングの状態の未改質カーボンナノチューブシートを治具ごと発生させたエアロゾル中に1分間暴露した。エタノールの液体粒子の粒子径は、15μmであった。その後、フリースタンディングの状態の未改質カーボンナノチューブシートを室温で1分間放置して、カーボンナノチューブ同士を集合させた改質カーボンナノチューブシートを得た。エアロゾルへの暴露を行う前後の未改質カーボンナノチューブシート及び改質カーボンナノチューブシートについて光線透過率の測定及び導電性評価を実施した。結果を下記表1に示す。
(改質カーボンナノチューブシートの積層)
間隔30mmの2本の平行な支持棒を有する治具の代わりに、間隔20mmの2本の平行な支持棒(銅棒、直径2mm)を有する治具を用いたこと以外は、実施例1と同様にして改質カーボンナノチューブシートを得た。得られた改質カーボンナノチューブシートと、実施例1と同様にして得られた間隔30mmの2本の平行な支持棒を有する治具に係止された改質カーボンナノチューブシートとを、互いの引き出し方向を同一方向として重ね合わせることにより、2層の改質カーボンナノチューブシートが積層された積層体を得た。また、得られた積層体に実施例1と同様にして得られた改質カーボンナノチューブシートを更に積層することを繰り返し、4、6、8、10、12層の改質カーボンナノチューブシートが積層された積層体を得た。これらの積層体について光線透過率の測定及び導電性評価を実施した。結果を下記表1に併記する。
(積層体のエアロゾルへの暴露)
実施例2で得られた12層の改質カーボンナノチューブシートが積層された積層体に対して、実施例1と同様にしてエアロゾルへの暴露を行った。その後、積層体について光線透過率の測定及び導電性評価を実施した。結果を下記表1に併記する。
空気を分散媒とするエタノールのエアロゾルに代えて、空気を分散媒とする水のエアロゾルを用いたこと以外は、実施例1と同様にして改質カーボンナノチューブシートを得た。水の液体粒子の粒子径は、15μmであった。エアロゾルへの暴露を行う前後の未改質カーボンナノチューブシート及び改質カーボンナノチューブシートについて光線透過率の測定及び導電性評価を実施した。結果を下記表1に併記する。
空気を分散媒とするエタノールのエアロゾルに代えて、空気を分散媒とするイソプロピルアルコール(IPA)のエアロゾルを用いたこと以外は、実施例1と同様にして改質カーボンナノチューブシートを得た。イソプロピルアルコールの液体粒子の粒子径は、15μmであった。エアロゾルへの暴露を行う前後の未改質カーボンナノチューブシート及び改質カーボンナノチューブシートについて光線透過率の測定及び導電性評価を実施した。結果を下記表1に併記する。
未改質カーボンナノチューブシートのエアロゾルへの暴露に代えて、印刷装置(商品名:Deskjet 1000、ヒューレット・パッカード社製)を用いたインクジェット印刷によりエタノールを改質カーボンナノチューブシートに対して吐出したこと以外は、実施例1と同様にして改質カーボンナノチューブシートを得た。エタノールの粒子径は、15μmであった。エアロゾルへの暴露を行う前後の未改質カーボンナノチューブシート及び改質カーボンナノチューブシートについて光線透過率の測定及び導電性評価を実施した。結果を下記表1に併記する。
実施例1と同様にして、カーボンナノチューブシートの調製を行った。
治具に保持されたフリースタンディング状態の未改質カーボンナノチューブシートに、更にカーボンナノチューブフォレストから引き出した未改質カーボンナノチューブシートを、互いの引き出し方向を同一方向として重ね合わせて、2層のカーボンナノチューブシートが積層された未改質カーボンナノチューブシートの積層体を得た。また、さらにこの操作を繰り返し、3層及び4層のカーボンナノチューブシートが積層されたカーボンナノチューブシートを得た。これらのカーボンナノチューブシート又はその積層体に、実施例6と同様にしてインクジェット印刷によるエタノールの吐出を行い、改質カーボンナノチューブシートを得た。エタノールの吐出を行う前後の未改質の又は改質された各積層数のカーボンナノチューブシート又はその積層体について、光線透過率の測定及び導電性評価を実施した。結果を下記表1に示す。
カーボンナノチューブシートを間隔30mmの2本の平行な支持棒に係止する代わりに、基材としてのガラス板上に未改質カーボンナノチューブシートを、カーボンナノチューブシート自体の付着性により貼付したこと以外は、実施例1と同様にしてガラス板上に形成された改質カーボンナノチューブシートを得た。この改質カーボンナノチューブシートは、破壊することなくガラス板から剥離することができなかった。比較例1の改質カーボンナノチューブシートについては、光線透過率が100%のガラス板ごと光線透過率の測定及び導電性評価を実施した。結果を下記表1に併記する。
未改質カーボンナノチューブシートのエアロゾルへの暴露に代えて、マイクロピペットでフリースタンディング状態の未改質カーボンナノチューブシート上に6μlのエタノールを滴下して浸潤させたこと以外は実施例1と同様にして高密度化処理した。その結果、カーボンナノチューブシートが破壊され、高密度化処理を行うことができなかった。比較例2については、改質カーボンナノチューブシートを得られなかったので、光線透過率の測定及び導電性評価を実施しなかった。
キャリアガスとしてアルゴンガス、炭素源としてアセチレンを用いた、3つの炉を備える熱CVD装置を用い、幅50mmのシリコンウエハ上に、触媒化学気相蒸着法により高さ300μmのカーボンナノチューブフォレストを得た。
線状体の間隔lが800μmとなるように線状体のカーボンナノチューブをゴムロールに巻き取ったこと以外は、実施例8と同様にして導電性シートを作製した。結果を下記表2に示す。
線状体の間隔lが200μmとなるように線状体のカーボンナノチューブをゴムロールに巻き取ったこと以外は、実施例8と同様にして導電性シートを作製した。結果を下記表2に示す。
Claims (14)
- 所定方向に複数のカーボンナノチューブが整列させられたフリースタンディングの未改質のカーボンナノチューブシートを、液体物質の蒸気及び液体粒子のいずれか一方又は両方と接触させる高密度化処理で改質して、複数のカーボンナノチューブを所定方向に優先的に整列した状態で含有し、複数の前記カーボンナノチューブが集合した高密度化部と、当該高密度化部より相対的にカーボンナノチューブの密度が低い低密度化部とを有するカーボンナノチューブシートを得る第1改質工程を含むことを特徴とする、カーボンナノチューブシートの製造方法。
- さらに、少なくとも2層の前記改質されたカーボンナノチューブシートを積層してカーボンナノチューブシートの積層体とする積層工程と、前記積層体をフリースタンディングの状態で前記液体物質の蒸気及び液体粒子のいずれか一方又は両方と接触させる高密度化処理により改質する第2改質工程とを含む、請求項1に記載のカーボンナノチューブシートの製造方法。
- 前記積層工程において2層以上25層以下の前記改質されたカーボンナノチューブシートを積層してカーボンナノチューブシートの積層体とする、請求項2に記載のカーボンナノチューブシートの製造方法。
- 前記液体粒子の大きさが200μm以下である、請求項1に記載のカーボンナノチューブシートの製造方法。
- 前記液体粒子が、前記液体物質のエアロゾル及びインクジェットによる前記液体物質の吐出のいずれか一方又は両方によりなる、請求項1に記載のカーボンナノチューブシートの製造方法。
- 前記液体物質が、有機溶剤である、請求項1に記載のカーボンナノチューブシートの製造方法。
- 前記有機溶剤が、アルコール化合物である、請求項6に記載のカーボンナノチューブシートの製造方法。
- 前記アルコール化合物が、メタノール、エタノール及びイソプロピルアルコールからなる群から選択された少なくとも1種である、請求項7に記載のカーボンナノチューブシートの製造方法。
- 請求項1から請求項8のいずれか1項に記載のカーボンナノチューブシートの製造方法により製造されたことを特徴とする、カーボンナノチューブシート。
- 光線透過率が70%以上である、請求項9に記載のカーボンナノチューブシート。
- 抵抗が500Ω/□以下である、請求項9に記載のカーボンナノチューブシート。
- 光線透過率が70%以上であり、抵抗が500Ω/□以下である、請求項9に記載のカーボンナノチューブシート。
- 複数のカーボンナノチューブを所定方向に優先的に整列した状態で含有し、複数のカーボンナノチューブが繊維状に集合した高密度化部と、前記高密度化部より相対的にカーボンナノチューブの密度が低い低密度化部とを有し、光線透過率が70%以上であり、抵抗が500Ω/□以下であることを特徴とする、カーボンナノチューブシート。
- 前記高密度化部は、カーボンナノチューブを含む線状体が平行に並べられてなり、前記低密度化部は、前記高密度化部の間に設けられた、請求項13に記載のカーボンナノチューブシート。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2015350963A AU2015350963B2 (en) | 2014-11-21 | 2015-11-20 | Method for producing carbon nanotube sheet, and carbon nanotube sheet |
JP2016560304A JP6894597B2 (ja) | 2014-11-21 | 2015-11-20 | カーボンナノチューブシートの製造方法 |
CN201580062663.9A CN107207263B (zh) | 2014-11-21 | 2015-11-20 | 碳纳米管片的制造方法及碳纳米管片 |
EP15861197.0A EP3222581B1 (en) | 2014-11-21 | 2015-11-20 | Method for producing carbon nanotube sheet and carbon nanotube sheet |
KR1020177013524A KR102431014B1 (ko) | 2014-11-21 | 2015-11-20 | 카본나노튜브 시트의 제조 방법 및 카본나노튜브 시트 |
US15/527,632 US10562775B2 (en) | 2014-11-21 | 2015-11-20 | Method for producing carbon nanotube sheet and carbon nanotube sheet |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201462082852P | 2014-11-21 | 2014-11-21 | |
US62/082,852 | 2014-11-21 | ||
US201562252908P | 2015-11-09 | 2015-11-09 | |
US62/252,908 | 2015-11-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016080526A1 true WO2016080526A1 (ja) | 2016-05-26 |
Family
ID=56014058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/082723 WO2016080526A1 (ja) | 2014-11-21 | 2015-11-20 | カーボンナノチューブシートの製造方法及びカーボンナノチューブシート |
Country Status (8)
Country | Link |
---|---|
US (1) | US10562775B2 (ja) |
EP (1) | EP3222581B1 (ja) |
JP (1) | JP6894597B2 (ja) |
KR (1) | KR102431014B1 (ja) |
CN (1) | CN107207263B (ja) |
AU (1) | AU2015350963B2 (ja) |
TW (1) | TWI704249B (ja) |
WO (1) | WO2016080526A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190002453A (ko) * | 2016-05-02 | 2019-01-08 | 린텍 가부시키가이샤 | 카본 나노튜브 시트의 개질 방법, 개질된 카본 나노튜브 시트, 점착 시트의 제조 방법, 및 점착 시트 |
JP2019127396A (ja) * | 2018-01-24 | 2019-08-01 | ツィンファ ユニバーシティ | テープ装置 |
JP2020524224A (ja) * | 2017-06-20 | 2020-08-13 | リンテック・オヴ・アメリカ,インコーポレイテッド | 熱及び力を使用したナノファイバーシートの圧縮 |
JP2020164384A (ja) * | 2019-03-29 | 2020-10-08 | 古河電気工業株式会社 | カーボンナノチューブ線材 |
WO2021131282A1 (ja) * | 2019-12-27 | 2021-07-01 | トクセン工業株式会社 | カーボンナノチューブ線の製造方法 |
TWI781203B (zh) * | 2017-08-08 | 2022-10-21 | 美商美國琳得科股份有限公司 | 使用邊緣表面改變奈米纖維片之密度 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018118682A1 (en) * | 2016-12-19 | 2018-06-28 | Lintec Of America, Inc. | Nanofiber yarn spinning system |
CN111601702B (zh) * | 2018-01-16 | 2022-03-22 | 琳得科美国股份有限公司 | 纳米纤维片材组装体 |
CN112203977B (zh) * | 2018-07-27 | 2023-09-05 | Lg化学株式会社 | 碳纳米管、其制造方法以及包含该碳纳米管的用于一次电池的正极 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008523254A (ja) * | 2004-11-09 | 2008-07-03 | ボード オブ リージェンツ, ザ ユニバーシティ オブ テキサス システム | ナノファイバーのリボンおよびシートならびにナノファイバーの撚り糸および無撚り糸の製造および適用 |
JP2009167092A (ja) * | 2008-01-11 | 2009-07-30 | Qinghua Univ | カーボンナノチューブ複合材料及びその製造方法 |
WO2009107846A1 (ja) * | 2008-02-29 | 2009-09-03 | 独立行政法人産業技術総合研究所 | カーボンナノチューブ膜構造体及びその製造方法 |
JP2012246210A (ja) * | 2011-05-27 | 2012-12-13 | Qinghua Univ | グラフェン−カーボンナノチューブ複合構造体の製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002076724A1 (en) * | 2001-03-26 | 2002-10-03 | Eikos, Inc. | Coatings containing carbon nanotubes |
CN101239712B (zh) * | 2007-02-09 | 2010-05-26 | 清华大学 | 碳纳米管薄膜结构及其制备方法 |
-
2015
- 2015-11-20 JP JP2016560304A patent/JP6894597B2/ja active Active
- 2015-11-20 CN CN201580062663.9A patent/CN107207263B/zh active Active
- 2015-11-20 KR KR1020177013524A patent/KR102431014B1/ko active IP Right Grant
- 2015-11-20 AU AU2015350963A patent/AU2015350963B2/en not_active Ceased
- 2015-11-20 TW TW104138522A patent/TWI704249B/zh active
- 2015-11-20 EP EP15861197.0A patent/EP3222581B1/en active Active
- 2015-11-20 US US15/527,632 patent/US10562775B2/en active Active
- 2015-11-20 WO PCT/JP2015/082723 patent/WO2016080526A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008523254A (ja) * | 2004-11-09 | 2008-07-03 | ボード オブ リージェンツ, ザ ユニバーシティ オブ テキサス システム | ナノファイバーのリボンおよびシートならびにナノファイバーの撚り糸および無撚り糸の製造および適用 |
JP2009167092A (ja) * | 2008-01-11 | 2009-07-30 | Qinghua Univ | カーボンナノチューブ複合材料及びその製造方法 |
WO2009107846A1 (ja) * | 2008-02-29 | 2009-09-03 | 独立行政法人産業技術総合研究所 | カーボンナノチューブ膜構造体及びその製造方法 |
JP2012246210A (ja) * | 2011-05-27 | 2012-12-13 | Qinghua Univ | グラフェン−カーボンナノチューブ複合構造体の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3222581A4 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190002453A (ko) * | 2016-05-02 | 2019-01-08 | 린텍 가부시키가이샤 | 카본 나노튜브 시트의 개질 방법, 개질된 카본 나노튜브 시트, 점착 시트의 제조 방법, 및 점착 시트 |
EP3453675A4 (en) * | 2016-05-02 | 2019-12-25 | LINTEC Corporation | METHOD FOR MODIFYING SHEET OF CARBON NANOTUBES, MODIFIED SHEET OF CARBON NANOTUBES, METHOD FOR MANUFACTURING ADHESIVE SHEET AND ADHESIVE SHEET |
US10774243B2 (en) | 2016-05-02 | 2020-09-15 | Lintec Corporation | Method for modifying carbon nanotube sheet, modified carbon nanotube sheet, method for manufacturing adhesive sheet, and adhesive sheet |
KR102392846B1 (ko) | 2016-05-02 | 2022-04-29 | 린텍 가부시키가이샤 | 카본 나노튜브 시트의 개질 방법, 개질된 카본 나노튜브 시트, 점착 시트의 제조 방법, 및 점착 시트 |
JP2020524224A (ja) * | 2017-06-20 | 2020-08-13 | リンテック・オヴ・アメリカ,インコーポレイテッド | 熱及び力を使用したナノファイバーシートの圧縮 |
US11155959B2 (en) | 2017-06-20 | 2021-10-26 | Lintec Of America, Inc. | Densifying a nanofiber sheet using heat and force |
TWI781203B (zh) * | 2017-08-08 | 2022-10-21 | 美商美國琳得科股份有限公司 | 使用邊緣表面改變奈米纖維片之密度 |
JP2019127396A (ja) * | 2018-01-24 | 2019-08-01 | ツィンファ ユニバーシティ | テープ装置 |
JP2020164384A (ja) * | 2019-03-29 | 2020-10-08 | 古河電気工業株式会社 | カーボンナノチューブ線材 |
JP7214537B2 (ja) | 2019-03-29 | 2023-01-30 | 古河電気工業株式会社 | カーボンナノチューブ線材 |
WO2021131282A1 (ja) * | 2019-12-27 | 2021-07-01 | トクセン工業株式会社 | カーボンナノチューブ線の製造方法 |
JP2021107596A (ja) * | 2019-12-27 | 2021-07-29 | トクセン工業株式会社 | カーボンナノチューブ線の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN107207263A (zh) | 2017-09-26 |
EP3222581B1 (en) | 2021-04-14 |
EP3222581A4 (en) | 2018-05-23 |
KR20170087459A (ko) | 2017-07-28 |
AU2015350963A1 (en) | 2017-07-06 |
EP3222581A1 (en) | 2017-09-27 |
KR102431014B1 (ko) | 2022-08-09 |
TWI704249B (zh) | 2020-09-11 |
US20170362089A1 (en) | 2017-12-21 |
TW201627518A (zh) | 2016-08-01 |
US10562775B2 (en) | 2020-02-18 |
JPWO2016080526A1 (ja) | 2017-09-28 |
CN107207263B (zh) | 2020-03-03 |
JP6894597B2 (ja) | 2021-06-30 |
AU2015350963B2 (en) | 2018-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2016080526A1 (ja) | カーボンナノチューブシートの製造方法及びカーボンナノチューブシート | |
US9573812B2 (en) | CNT-infused metal fiber materials and process therefor | |
JP5701907B2 (ja) | 強化送電線のセルフシールドワイヤとしてのcnt浸出繊維 | |
US7704480B2 (en) | Method for making carbon nanotube yarn | |
JP5229732B2 (ja) | 微細炭素繊維撚糸の製造装置及び製造方法 | |
JP5180266B2 (ja) | カーボンナノチューブ線状構造体の製造方法 | |
CN107429438B (zh) | 碳纳米管集合体的制造方法 | |
US20140065447A1 (en) | Hybrid capacitor-battery and supercapacitor with active bi-functional electrolyte | |
US20110171469A1 (en) | Cnt-infused aramid fiber materials and process therefor | |
US20130101495A1 (en) | Systems and methods for continuously producing carbon nanostructures on reusable substrates | |
JP2013509504A5 (ja) | ||
JP2014508370A5 (ja) | ||
US20140099493A1 (en) | Carbon nanostructure layers and methods for making the same | |
JP2013511465A (ja) | 炭素‐炭素複合材料におけるcnt浸出繊維 | |
CN104176722A (zh) | 一种高取向高强度的阵列牵伸碳纳米管薄膜及其制备方法 | |
TWI391323B (zh) | 奈米碳管線狀結構的製備方法 | |
Zhou et al. | Growth and characterization of aligned ultralong and diameter-controlled silicon nanotubes by hot wire chemical vapor deposition using electrospun poly (vinyl pyrrolidone) nanofiber template | |
Sharma et al. | Mechanical Properties of CNT Network-Reinforced Polymer Composites | |
TWI402210B (zh) | 奈米碳管線狀結構及其製備方法 | |
JP2006225246A (ja) | ナノカーボン材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15861197 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016560304 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15527632 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20177013524 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015861197 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2015350963 Country of ref document: AU Date of ref document: 20151120 Kind code of ref document: A |