WO2006064970A1 - 円筒状炭素構造体及びその製造方法、並びに、ガス吸蔵材料、複合材料及びその強化方法、摺動材料、フィールドエミッション、表面分析装置、塗装材料 - Google Patents
円筒状炭素構造体及びその製造方法、並びに、ガス吸蔵材料、複合材料及びその強化方法、摺動材料、フィールドエミッション、表面分析装置、塗装材料 Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- 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
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- 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
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- 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
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Definitions
- Cylindrical carbon structure and manufacturing method thereof gas storage material, composite material and reinforcing method thereof, sliding material, field emission, surface analyzer, coating material
- the present invention relates to a cylindrical carbon structure and a method for producing the same, and further includes a gas storage material, a composite material and a method for strengthening the same, a sliding material, a field emission, and a surface analysis apparatus using the cylindrical carbon structure. , And coating materials.
- Carbon nanotubes have a cylindrical shape with a graph ensheet, and can be used as a hydrogen gas storage body using its internal space, or dispersed in composite materials to improve strength. It is used in the field.
- Carbon nanotubes have a single-walled carbon nanotube (hereinafter sometimes referred to as “single-walled carbon nanotube”), and a multi-layered tube with multiple graph-enclosed tubes. Some have a structure, and can be selected appropriately according to the application.
- single-walled carbon nanotubes are usually in the form of bundles of several tens to several hundreds (pandles) and easily aggregate.
- single-walled carbon nanotubes have a particularly large aspect ratio, and therefore the van der Waalska is likely to work effectively, and there is a bias of valence electrons due to the curvature of the surface. For this reason, single-walled carbon nanotubes aggregate together after synthesis. Easy to form a bundle that is stable in terms of energy.
- Bundled single-walled carbon nanotubes do not function as a gas storage site because the macropores between the tubes are closed to about 0.3 3 5 A, improving gas storage performance and composite strength Noh is not enough. For this reason, gas storage materials and composite materials using bundle-like carbon nanotubes could not exhibit sufficient performance.
- the Young's modulus of single-walled carbon nanotubes is estimated to be several thousand GPa, and it has been confirmed experimentally that it is 100 GPa.
- single-walled carbon nanotubes are also expected as high-strength materials, and for example, composite materials of carbon nanotubes and metals or resins have been proposed (see, for example, Patent Documents 1 and 2).
- these composite materials using conventional single-walled carbon nanotubes are inferior in dispersibility, cracking of materials such as cracks tends to proceed starting from the agglomerated part, and as a result, sufficient strength cannot be obtained. There was a problem.
- a composite material of carbon nanotube and metal or resin for brake discs and brake pads.
- the carbon nanotubes in the solid phase matrix were not bundled and dispersed, and it was difficult to obtain the expected mechanical properties and heat dissipation.
- a field emission display (FED) using a field emission cathode array which is expected as a next-generation display, also has a single layer on the substrate.
- a substrate (emission) on which carbon nanotubes are oriented is used.
- the carbon nanotubes generated on the substrate are bundled together, and the orientation is lowered, resulting in an increase in the electron emission voltage.
- the number of bundles of carbon nanotubes can be reduced to some extent, but the number of pandles cannot be reduced to 10 or less.
- Patent Document 1 JP 2002-2 73 74 1
- Patent Document 2 Japanese Unexamined Patent Application Publication No. 2004-1 07534
- Patent Document 3 Japanese Patent Laid-Open No. 2004-2 1 56
- Patent Document 4 Japanese Patent Laid-Open No. 2003-29280 1
- Patent Document 5 JP 2000-8 6 2 1 9
- Patent Document 6 Japanese Patent Application Laid-Open No. 2001-111344
- Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-26221
- Non-Patent Document 1 T. Fukushima et al., Science, 300.2072-2074 (2003) Disclosure of the Invention Problems to be solved by the invention
- the present invention is not easily agglomerated, can be isolated and dispersed, and has a cylindrical carbon structure excellent in various properties such as gas occlusion, conductivity, and strength, and its It is an object of the present invention to provide a manufacturing method, and a gas storage material, a composite material and a reinforcing method thereof, a sliding material, a field emission, a surface analysis device, and a coating material using the cylindrical carbon structure.
- a cylindrical carbon structure having a rugged outer surface and a diameter of 0.5 nm or more and 100 nm or less and having a single-layer structure.
- the interval between cylindrical carbon structures (hereinafter also referred to as “between tubes”) can be made larger than that of carbon nanotubes.
- the cohesive strength based on Van der Luska is proportional to the sixth power of the distance between tubes. For this reason, even a very small distance of several A has a great effect on the Van der Waals force. That is, the cylindrical carbon structure of the present invention can maintain a distance from other structures by the HQ-like portion, so that the van der Waals force between the tubes is weakened and the cohesive force is reduced. Therefore, it can be easily separated and dispersed.
- the cylinder since the ratio P of the uneven width (W) to the diameter (D) of the cylindrical carbon structure is not less than 0.05 and less than 0.5, the cylinder The cohesive force can be reduced while maintaining the internal space.
- cylindrical carbon structure of ⁇ 3> above since many 5-membered and 7-membered rings exist in the molecules constituting the structure, there are many local electrical separations, and the outer surface It is easy to chemically bond various functional groups according to various uses. This gives the cylindrical carbon structure functions according to various applications, such as improving the wettability to the dispersion medium and increasing the dispersibility by appropriately selecting the molecular chain length of the functional group. Can do.
- ⁇ 4> A cylindrical carbon structure according to ⁇ 1> to ⁇ 3>, in which a granular material is supported on the outer surface.
- cylindrical carbon structure not only the internal space of the cylindrical carbon structure but also the macropores between the tubes can be maintained in a suitable range. Thereby, it can be suitably used as a support for granular materials such as catalysts, nanoparticles, and hydrogen storage materials.
- a raw carbon nanotube is immersed in a solution containing an acid or an alkali, and a dipping step for introducing defects into the raw carbon nanotube, and a raw material single-bonn nanotube into which defects have been introduced in the dipping step.
- the cylindrical carbon structure of the present invention can be efficiently produced in a stable state.
- the gas storage material ⁇ 6> above since the cylindrical carbon structure constituting the gas storage material is isolated and dispersed, the spacing between the tubes can be maintained, and the pores of the macropores Capacity can be 0.001 ml / g or more and 1. Oml / g or less. Thereby, the amount of gas occlusion per unit volume can be increased.
- the cylindrical carbon structure of the present invention is uniformly isolated and dispersed in the organic solid phase such as plastic or the inorganic solid phase such as aluminum. Therefore, the strength such as Young's modulus and hardness can be improved uniformly as a whole. As a result, desired performance such as strength, thermal conductivity, electrical conductivity and heat dissipation can be imparted (improved), and the use of the composite material can be expanded.
- a composite material obtained by isolating and dispersing a cylindrical carbon structure in an organic or inorganic solid phase in a vacuum or in an inert atmosphere at 100 ° C or higher This is a method for strengthening a composite material that is heated at 2 0 0 0 ° C or lower.
- the cylindrical carbon structure of the present invention contained in the composite material is heated in a dispersed state in a solid phase, whereby the cylindrical carbon structure is The crystallinity can be enhanced in a state where is dispersed. Thereby, the strength of the composite material itself can be improved.
- a sliding material containing the cylindrical carbon structure of ⁇ 1> to ⁇ 4> According to the sliding material of ⁇ 9>, by using the cylindrical carbon structure of the present invention as a base fiber or the like, the thermal conductivity can be increased due to its high dispersibility. Thereby, the thermal stability of the sliding material is improved, and the friction coefficient and the friction resistance in the high temperature region can be improved.
- ⁇ 1 1> A surface analyzer using a needle-like structure composed of a cylindrical carbon structure of ⁇ 1> to ⁇ 4>.
- Examples of ⁇ 1 1> surface analyzers include STM (Scanning Tunneling Microscope) and AFM (A tomic Force Microscopy). Contamination tends to adhere to the probes provided in these analyzers.
- the cylindrical carbon structure of the present invention having a concavo-convex shape on the surface can be used as a probe for these analyzers. A certain distance between the minion and the probe can be secured, and the van der Waals force acting between them can be reduced. As a result, adhesion between the probe and the contamination can be suppressed, and as a result, the accuracy of the measured value can be increased.
- a coating material containing a cylindrical carbon structure of ⁇ 1> to ⁇ 4> is included in the coating material ⁇ 1 2>. According to the coating material ⁇ 1 2>, the inclusion of the cylindrical carbon structure of the present invention with excellent dispersibility improves conductivity, and further improves the finish of the coating by preventing paint surface failure after painting. Can be made. The invention's effect
- a cylindrical carbon structure that is difficult to aggregate can be isolated and dispersed, and has various properties such as gas storage properties, electrical conductivity, and strength, and a method for producing the same, and A gas storage material, a composite material and a method for strengthening the same, a sliding material, a field emission, a surface analysis device, and a coating material using a cylindrical carbon structure can be provided.
- FIG. 1 is a schematic view for explaining a cylindrical carbon structure of the present invention.
- Fig. 2 is a schematic diagram for explaining a conventional carbon nanotube.
- FIG. 3 is a schematic diagram for explaining a conventional single-walled carbon nanotube.
- FIG. 4 is a schematic view for explaining the cylindrical carbon structure of the present invention.
- FIG. 5A is a schematic diagram of a field emission using a cylindrical carbon structure of the present invention for comparison with a field emission using a conventional single-walled carbon nanotube.
- FIG. 5B is a schematic view of field emission using conventional single-walled carbon nanotubes for comparison with field emission using the cylindrical carbon structure of the present invention.
- FIG. 6 is a schematic diagram showing a probe in the surface analyzer of the present invention.
- Fig. 7 is a graph showing the measurement results of the coefficient of friction ( ⁇ ) in the example.
- FIG. 8 is a graph showing the wear rate (cm 3 / kgm) in the example.
- the cylindrical carbon structure of the present invention has an uneven outer surface, a diameter of 0.5 nm or more and 100 nm or less, and has a single layer structure.
- the cylindrical carbon structure of the present invention can reduce the contact surface between the tubes and maintain the distance between the tubes due to the uneven shape of the outer surface. As a result, the van der Waals force acting between the tubes can be reduced, so that the aggregation of each tube can be suppressed to prevent bundling and can be easily isolated and dispersed. Therefore, the cylindrical carbon structure of the present invention is excellent in dispersibility, and can effectively exhibit various properties such as gas storage properties, electrical conductivity, and strength.
- the cylindrical carbon structure of the present invention is a cylindrical (tubular) structure composed of carbon atoms. While conventional carbon nanotubes mainly have a 6-membered ring structure, the cylindrical carbon structure of the present invention has many 5-membered and 7-membered ring structures in addition to the 6-membered ring. Since the 5-membered ring and 7-membered ring are arranged at an angle with respect to the horizontal direction of the graphite sheet, a convex shape is formed on the outer surface.
- FIG. 1 is a schematic diagram for explaining a cylindrical carbon structure of the present invention
- FIG. 2 is a schematic diagram for explaining a conventional carbon nanotube.
- “having an uneven outer surface” means that the surface of the graph enclosure constituting the cylindrical carbon structure is concave and convex. That is, the conventional single-walled carbon nanotube 20 shown in FIG. 2 has a substantially constant distance (D 4 , D 5 , D 6 ) from the straight line B passing through the center of the opening 22 to the outer surface. 1 ⁇ to 0 3 shown in 1 Opening of cylindrical carbon structure 1 0 1 2 A straight line passing through the center of 2 The distance from A is not constant, but there are different places.
- the degree of the structure diameter D (see Fig. 1
- the P value in the cylindrical carbon structure of the present invention is preferably not less than 0.1 and less than 0.5, and more preferably not less than 0.1 and less than 0.5. If the P value is less than 0.01, the ratio of the diameter and the convex width of a normal carbon nanotube is close to that of the normal carbon nanotube, and the effect of the present invention for reducing the van der Waals force may not be sufficiently exhibited. is there. Further, when the P value is 0.5 or more, the degree of unevenness increases, and the inner diameter of the cylindrical carbon structure may be significantly reduced.
- Diameter D used in the calculation of the above P value means an average value obtained by averaging the diameters of arbitrary 10 points for one carbon nanotube non-nanotube.
- the diameter of the carbon nanotube is a dimension measured in a direction perpendicular to the center line of the carbon nanotube.
- the carbon nanotube has an extremely large aspect ratio (length-to-diameter ratio). Even if the surface of the carbon nanotube has some unevenness, the carbon nanotube has an unevenness compared to the length of the carbon nanotube. Since the width is quite small, the center line can be defined as having no surface irregularities.
- the “diameter D” can be measured by, for example, TEM observation, AFM, SEM observation, or the like.
- the “convex width W” means the maximum value of the uneven width, and can be measured by, for example, TEM observation, AFM, SEM observation or the like.
- the diameter of the cylindrical carbon structure of the present invention is 0.5 nm or more and lOO nm or less, preferably 0.5 nm or more and 50 nm or less, and 0.5 nm or more and 10 nm is further preferable.
- the diameter is synonymous with the diameter D described above. If the diameter of the cylindrical carbon structure is less than 0.5 nm, a sufficient internal space cannot be maintained, and the desired hydrogen storage capacity and the like cannot be exhibited. In addition, when the diameter of the cylindrical carbon structure exceeds 1 OO nm, the interaction between the internal hydrogen molecules and the carbon structure is weakened, so that the desired hydrogen storage function can be exhibited also in this diameter range. Can not.
- the cylindrical carbon structure of the present invention has a single-layer structure composed of one graph ensheet.
- the cylindrical carbon structure of the present invention is used as a hydrogen storage material.
- the front and back of one graph ensheet can be used as a gas adsorption site, so that sufficient adsorption performance can be obtained.
- a functional group can be bonded to the outer surface of the cylindrical carbon structure of the present invention.
- the functional group may be bonded to the inner surface of the cylindrical carbon structure as desired.
- the cylindrical carbon structure of the present invention has many 5-membered and 7-membered rings, it has an electrical bias and has the property that functional groups are easily attached.
- the type of the functional group is appropriately selected according to the desired purpose, such as improving the wettability with respect to the dispersion medium, improving the dispersibility when producing a composite material, and improving the supporting ability of the catalyst. can do.
- the distance between the tubes can be controlled by appropriately adjusting the length of the molecular chain of the functional group to be bonded to the cylindrical carbon structure.
- the functional group examples include a polyvinylpyrrolidone group, a hydroxyl group, a carboxyl group, and a sulfone group.
- the bonding amount of the functional group may be appropriately determined according to the purpose. For example, it is preferably 0.001 to 40.0 mass% with respect to the mass of the cylindrical carbon structure. 0 0 1 to 1.0 0 0% by mass is more preferred.
- the cylindrical carbon structure of the present invention can be used as a granular support.
- the granular material include nanoparticles such as a catalyst and fullerene. Since the cylindrical carbon structure of the present invention has a low cohesive force and is difficult to bundle, a catalyst can be supported between each type. As a result, the amount of catalyst supported per unit volume can be increased, and the catalyst particle size can be reduced.
- the average particle size of the granule varies depending on the purpose, but is usually 0.5 ⁇ ⁇ ! Is preferably about 1 to 100 nm, and more preferably about 0.5 to 2 nm.
- the granular material include a metal catalyst such as Pt, nanoparticles, and a hydrogen storage alloy.
- the method for producing a cylindrical carbon structure of the present invention comprises immersing raw carbon nanotubes in a solution containing an acid or an alkali, A dipping process for introducing defects into the Bonn nanotube;
- the raw carbon nanotube into which defects have been introduced in the dipping process is heated at 100 ° C. to 200 ° C. in a vacuum or an inert atmosphere, so that the outer surface of the raw carbon nanotube is uneven.
- the dipping step defects are introduced into the raw carbon nanotubes, and at the same time, functional groups are attached to the surface thereof, and the carbon dangling bonds (unbonded hands) are terminated.
- functional groups are removed from the surface of the carbon nanotubes, and at the same time, 5-membered or 7-membered ring structures are formed in the structure (carbon nanotubes).
- heat treatment is performed at a high temperature of 100 ° C. to 200 ° C., so that the balance between the 5-membered ring and the 7-membered ring in the structure is achieved and metastable It becomes a state.
- the 5-membered ring and the 7-membered ring are arranged at an angle with respect to the horizontal direction of the graph sheet, irregularities are formed on the outer surface of the structure.
- the dipping step is a step of dipping the raw material carbon nanotubes in a solution containing an acid or an alkali, and introducing defects into the raw material one-bonn nanotubes.
- the diameter of the raw carbon nanotube is preferably, for example, 0.5 nm to 5 Onm, and more preferably 0.5 to 10 nm.
- the raw carbon nanotubes are preferably a mixture of at least two types of carbon nanotubes having different molecular shapes.
- a mixture of at least two types of carbon nanotubes having different molecular shapes as raw material carbon nanotubes, graphite formation of carbon nanotubes in the heating step can be prevented.
- the reason why the carbon nanotubes can be prevented from graphite is presumed as follows. If the molecular shape of the raw carbon nanotubes is uniform, the coalescence of the raw carbon nanotubes proceeds excessively, and the diameter of the carbon nanotubes becomes too large. If the diameter of the carbon nanotube becomes too large, the carbon nanotube will collapse, and as a result, the carbon nanotube The progress of graph-itization progresses. If the molecular shape of the raw carbon nanotubes is made non-uniform, coalescence of the raw carbon nanotubes can be moderately suppressed, and as a result, the graph nanotubes can be prevented from becoming graphite. A mixture of carbon nanotubes can be obtained by mixing at least two types of carbon nanotubes with different molecular shapes.
- the molecular shape in the raw carbon nanotubes can be made non-uniform.
- the molecular shape of the carbon nanotube include an armchair type, a zigzag type, and a chiral type.
- the bulk density of the raw carbon nanotubes is preferably 0.05 g / ml or less.
- the amount of the metal catalyst used in the production of the raw carbon nanotubes contained in the raw carbon nanotubes can be reduced. it can. This is because when the raw carbon nanotubes are heated in a low bulk density state, the metal catalyst with a nano-order particle size melts and then evaporates due to its small particle size. This is because the vapor pressure is high. For this reason, the amount of the metal catalyst can be reduced to about 1 Z 10 by using raw carbon nanotubes having a low bulk density.
- the bulk density of carbon nanotubes means a value obtained by putting 1.0 g of carbon nanotubes into a measuring cylinder and measuring the volume thereof, thereby calculating the mass Z volume.
- Examples of the acid-containing solution (acidic solution) used in the dipping step include hydrochloric acid or nitric acid.
- the concentration of the acidic solution is preferably 1 to 70%, more preferably 5 to 30%.
- Examples of the alkali-containing solution (alkaline solution) include a NaOH solution and a KOH solution.
- the concentration of the alkaline solution is preferably 1 to 70%, more preferably 5 to 30%.
- the immersion time in the immersion step is preferably 5 to 200 hours, more preferably 25 to 200 hours, from the viewpoint of sufficiently introducing defects into the raw carbon nanotubes.
- the temperature of the solution containing acid or alkali in the dipping process Is preferably 5 to 100 ° C, more preferably 20 to 30 ° C.
- the raw carbon nanotube into which defects are introduced in the dipping step is heated at 1000 ° C. or higher and 2000 ° C. or lower in a vacuum or an inert atmosphere, and the outer surface of the raw carbon nanotube is uneven. It is the process of providing.
- the heating temperature is less than 1000 ° C., the 5-membered ring structure and the 7-membered ring structure in the structure cannot be balanced while being balanced.
- the heating temperature is higher than 2000 ° C, the raw carbon nanotubes become graphite.
- a preferable range of the heating temperature is 1500 to 1800 ° C.
- the heating time is preferably 1 to 50 hours, more preferably 10 to 50 hours.
- the heating step is performed in a vacuum or in an inert gas atmosphere.
- a vacuum or in an inert gas atmosphere preferably 10 ⁇ X 10- 8 P a is as vacuum, 10 one 7 ⁇ 10 "8 P a is more preferred.
- the heating step an inert gas atmosphere
- preferable inert gas include He, Ar, and N 2 , and among these, He is more preferable.
- the defect-introduced raw material carbon nanotubes obtained by the dipping step are heated at 700 ° C. or higher and lower than 1000 ° C. to remove impurities such as moisture. It is preferable.
- the above-described cylindrical carbon structure of the present invention can be suitably used as a hydrogen storage material (gas storage material).
- the hydrogen storage material (gas storage material) of the present invention is a gas storage material using the cylindrical carbon structure of the present invention, and the pore capacity of the macropores is 0.000 lm l / g. 1. It is characterized by being Om 1 Zg. Since the cylindrical carbon structure of the present invention has a low cohesive force and excellent dispersibility, it is possible to secure a pore capacity between tubes.
- macropores when the conventional carbon nanotubes are compressed, the macropores are crushed, whereas when the cylindrical carbon structure of the present invention is compressed, macropores (diameters of about 10 to 50 O zrn) become micropores (diameter of about 100 nm or less). Since the micropores have a filling effect, they can be used as gas storage sites. The amount of gas occlusion can be improved.
- the pore volume of the black pores of the hydrogen storage material of the present invention is 0.001 to 1. Om l Zg. If the pore volume of the above-mentioned macropores is less than 0.001 m 1 Zg, gas diffusion is not sufficiently performed, and if it exceeds 1. Om 1 / g, it becomes difficult to handle.
- the pore volume of the macropores is preferably 0.001 ml Zg to 0.1 m 1 / g, and more preferably 0.001 ml Zg to 0.005 ml 1 g.
- the hydrogen storage material of the present invention can be formed, for example, by compressing the cylindrical carbon structure of the present invention with a known compression device such as a hand brace.
- a known compression device such as a hand brace.
- the length of the cylindrical carbon structure is usually 0.1 Ai m to l 000; zm, depending on the desired purpose. It is preferably 0.1 ⁇ to 10 m.
- the diameter of the cylindrical carbon structure is preferably 0.5 nm to 100 nm, and more preferably 0.5 nm to 2 nm.
- the above-described cylindrical carbon structure of the present invention can be suitably used as a composite material.
- the composite material of the present invention is obtained by isolating and dispersing the cylindrical carbon structure of the present invention in an organic or inorganic solid phase. Since the cylindrical carbon structure of the present invention has a low cohesive force and can be uniformly dispersed in the solid phase, the strength of the composite material, thermal conductivity, Heat dissipation and conductivity can be improved.
- FIG. 3 is a schematic diagram for explaining a conventional single-walled carbon nanotube
- FIG. 4 is a schematic diagram for explaining a cylindrical carbon structure of the present invention.
- a plurality of single-walled carbon nanotubes 30 are bundled to form a bundle 32.
- the bundle 32 composed of such a plurality of carbon nanotubes 30 is inferior in dispersibility, and causes cracks and the like starting from the agglomerated portion.
- the cylindrical carbon structure 40 is dispersed in an isolated state. Since the cylindrical carbon structure 40 of the present invention is excellent in dispersibility, it is uniformly dispersed in the solid phase, and there is no agglomeration portion or the like. For this reason, there is no material smashing or the like starting from the agglomerated part, and it is possible to stably exhibit the strength, thermal conductivity, heat dissipation and conductivity of the composite material.
- the organic solid phase forming the composite material resins such as polypropylene, nylon, urethane, epoxy, acrylic, and phenol can be used. Further, as the inorganic solid phase forming the composite material, metals such as aluminum, magnesium, iron, and alloys mainly composed of these can be used.
- the content of the cylindrical carbon structure of the present invention in the organic or inorganic solid phase is from 0.1 to 50 mass with respect to the total mass of the organic or inorganic solid phase from the viewpoint of improving the above characteristics. %, Preferably 2 to 50% by mass.
- the length of the cylindrical carbon structure is 0. 1 ⁇ ⁇ 1 0 0 0 ⁇ m Preferably, 5 0 0 ⁇ ⁇ ! More preferably, ⁇ 100 ⁇ m.
- the diameter of the cylindrical carbon structure is preferably 0.5 nm to 10 nm, and more preferably 0.5 nm to 1 nm.
- the composite material of the present invention can be improved in strength through a certain process.
- the strength of the cylindrical carbon structure of the present invention increases as the crystallinity increases.
- the five-membered or seven-membered ring structure contained in the cylindrical carbon structure is reduced, and the convexity on the surface of the cylindrical carbon structure is lost.
- the crystallinity of the cylindrical carbon structure of the present invention is improved, the surface irregularities are reduced accordingly, and eventually it becomes close to normal carbon nanotubes.
- cylindrical carbon structure of the present invention contained in the composite material of the present invention is fixed in a dispersed state in the solid phase, surface irregularities are reduced even if the crystallinity is increased by heating. By simply doing this, the dispersed state in the solid phase can be maintained without re-bundling.
- the method for strengthening a composite material of the present invention has the cylindrical carbon structure of the present invention.
- the composite material isolated and dispersed in a machine or an inorganic solid phase is heated at 100 ° C. or more and 200 ° C. or less in a vacuum or an inert atmosphere.
- the method for strengthening a composite material of the present invention can improve crystallinity while maintaining the dispersed state of the cylindrical carbon structure by annealing the cylindrical carbon structure of the present invention in the solid phase.
- the heating temperature of the composite material is not less than 100 ° C. and not more than 200 ° C.
- the heating temperature is less than 100 ° C.
- the crystallinity of the cylindrical carbon structure in the solid phase cannot be sufficiently increased.
- the heating temperature exceeds 200 ° C.
- the cylindrical carbon structure in the solid phase may become graphite.
- the heating time in the method for strengthening a composite material of the present invention is preferably 1 to 20 hours, and more preferably 5 to 20 hours.
- the heat treatment in the strengthening process is carried out in vacuum, preferably 1 0 ⁇ 1 0- 8 P a as a vacuum, 1 0- 7 ⁇ 1 CT 8 P a is more preferred.
- a preferable inert gas include He, Ar, and N 2 , and among these, He is more preferable.
- the cylindrical carbon structure of the present invention and the composite material of the present invention can be suitably used as a sliding friction material for a sliding material such as a brake disk or a brake pad.
- the composite material containing the cylindrical carbon structure of the present invention can be suitably used particularly as a sliding friction material.
- sliding materials the higher the thermal conductivity, the more advantageous is the heat storage relaxation of the friction surface.
- the coefficient of friction and the frictional resistance in a high temperature region around 300 to 400 ° C are obtained as an effect of improving thermal stability brought about by its high thermal conductivity. And can be improved.
- the sliding material of the present invention is not limited to brake-related parts, and can be used in a wide range of fields.
- the length of the cylindrical carbon structure is usually 0.1 m to 100 m, although it depends on the desired purpose. 1 0 0 n! More preferably, ⁇ 100 ⁇ m.
- the diameter of the cylindrical carbon structure is 0.5 ⁇ ⁇ ! It is preferably ⁇ 10 nm, and more preferably 0.5 nm to 5 nm. ⁇ Field Emission ⁇
- the cylindrical carbon structure of the present invention can also be suitably used as a field emission electron emission material for a display that emits electrons by applying a constant voltage.
- the restriction in vacuum is gentle, the current density is high, and the strength is excellent. be able to. For this reason, the conductivity in the direction perpendicular to the growth direction is low, and as a result, electrons can be emitted even with a low voltage.
- FIGS. 5A and B are schematic views for comparing field emission using the cylindrical carbon structure of the present invention and field emission using conventional single-walled carbon nanotubes.
- the single-walled carbon nanotubes 54 aligned on the substrate 56 are bundled and aggregated.
- Feed emission using a cylindrical carbon structure is regularly oriented without agglomeration as shown in Fig. 5A. This is because the cylindrical carbon structure 50 of the present invention has less uneven interaction between the tubes due to the van der Waals due to the uneven shape, and the cohesive force is reduced.
- the cylindrical carbon structure 50 of the present invention is oriented on the substrate 52, it is possible to produce field emission with excellent orientation, so that conventional single-layer carbon The current does not flow in the direction perpendicular to the growth direction as in the case of using a nanotube, and as a result, the electron emission voltage can be lowered.
- the length of the cylindrical carbon structure is 0.1 ⁇ to 1 / m.
- the cylindrical carbon structure of the present invention has a surface provided with a metal probe such as STM or AFM. It can be used as a probe for a surface analyzer.
- STM is a device that observes the structure and electronic state of the surface by measuring the tunnel current flowing between the probe and the sample and scanning it in the direction along the surface with a piezoelectric element.
- contamination impurities
- a probe composed of contamination 60 and a cylindrical carbon structure is formed depending on the surface irregularities.
- the number of parts that contact with each other decreases, and the distance from the contamination 60 can be secured to some extent in the recess 64. Since the effect on the van der Waals force is large even at a distance as small as several A, the van der Waalska (cohesive force) generated between the contamination 60 and the probe 6 2 due to the influence of the recess 6 4 And the adhesion of contamination can be suppressed.
- the length of the cylindrical carbon structure is 0.1 ⁇ to 1.
- the cylindrical carbon structure of the present invention can be used by being mixed in a coating material or the like, and can be suitably used for a coating material having functionality such as a conductive paint.
- a coating material containing carbon nanotubes a paint in which single-walled nanotubes described in JP-A No. 2 0 0 1—1 1 3 4 4 are dispersed is disclosed in JP-A 2 0 0 4-1 9 6 9 1 Examples thereof include conductive paints described in No. 2 publication.
- These conventional coating materials using carbon nanotubes have low dispersibility of carbon nanotubes and are bundled and agglomerated, so that the desired performance such as conductivity cannot be sufficiently exhibited, or the painted surface is not coated. There are problems such as unevenness.
- the cylindrical carbon structure of the present invention when used in place of these conventional carbon nanotubes, the dispersibility is high and aggregation is suppressed, so that the conductivity is improved and there is no unevenness. A good coated surface can be obtained.
- the length of the cylindrical carbon structure is preferably 0.1 / m to l 000 m, more preferably 100 ⁇ to 1000 ⁇ . .
- the diameter of the cylindrical carbon structure is 0.5 ⁇ ! It is preferably ⁇ 10 nm, 0.5 ⁇ ! More preferably, ⁇ 5 nm.
- the content of the cylindrical carbon structure of the present invention in the coating material is preferably 0.1 to 10% by mass, although it varies depending on the desired purpose and the type of coating liquid.
- the cylindrical carbon structure of the present invention can be applied in a wide range of fields, and various materials and apparatuses using the cylindrical carbon structure have excellent performance as compared with the case of using ordinary carbon nanotubes. It can be demonstrated.
- High-purity single-walled carbon nanotubes synthesized by the H i P co method (trade name: H i P co (registered trademark), manufactured by CN I, purity of 80% by mass or more) in dry air at 250 ° C 0. Heated for 5 hours.
- H i P co registered trademark
- single-walled carbon nanotubes were taken out from the aqueous hydrochloric acid solution, filtered with suction while thoroughly washing with water, and then dried at 100 ° C for 3 hours in a vacuum.
- the dried single-walled carbon nanotubes were heated in a vacuum at 1000 ° C for 10 hours to remove impurities, and further heated in a vacuum at 1 700 ° C for 10 hours to obtain a cylindrical single-layer structure ( Heating step).
- Example 2 1 g of the cylindrical carbon structure obtained from Example 1 was added to 100 ml of ethanol as a dispersion medium. Thereafter, the mixture was stirred for 1 hour with a stirrer and dried at room temperature in the air.
- the amount of Pt supported on the cylindrical carbon structure obtained by TGA measurement and ICP analysis was estimated.
- the TGA measurement was performed by heating the sample to 1 000 ° C in dry air and counting the residue as Pt.
- the XRD diffraction pattern was diffracted by the Sierra equation to determine the particle size of the catalyst supported on the cylindrical carbon structure.
- Example 3 Pt was changed in the same manner as in Example 3 except that it was changed to a single-walled carbon nanotube (trade name: HiPco (registered trademark), manufactured by CN I). The same measurement was performed with carbon nanotubes. The results are shown in Table 1 below.
- Example 3 Comparative Example 1 Amount of catalyst supported (mass%) 4.8 4.3 Catalyst particle size (nm) 1 i 20, 4 From Table 1, Pt of Example 3 using the cylindrical carbon structure of the present invention (catalyst) The supported amount is larger than the supported amount of the carbon nanotubes of Comparative Example 1, and the particle size of the supported Pt is also as small as about 60%.
- the hydrogen storage characteristics of the obtained hydrogen storage materials were evaluated by the capacity method (temperature 293 K, gas pressure 20 MPa).
- the capacity method compared with a hydrogen storage material using a conventional single-walled carbon nano tube (trade name: Hipco (registered trademark), manufactured by CN I)
- the hydrogen storage capacity of the conventional hydrogen storage material is 0.1 mass. to 0/0 der Tsutano
- the hydrogen storage capacity of the hydrogen storage material of the present invention is 1 5 wt% 0., was improved by about 50%.
- the obtained composite materials A and B were subjected to a tensile test (test speed 5 mmZm in) in accordance with JISK 7 11 1 3 to evaluate the tensile elastic modulus (Young's modulus) and tensile fracture strength in the MD direction. Went.
- the result is a sample A for comparison, which is molded from 10 g of polypropylene, and 2 g of single-layer carbon nanotubes (trade name: Hi P co (registered trademark), manufactured by CNI) in 10 g of polypropylene.
- Hi P co registered trademark
- the obtained composite materials C and D were subjected to a tensile test (test speed: 5 mm / min) in accordance with JISK 7 11 13 to evaluate the tensile elastic modulus (Young's modulus) in the MD direction.
- the result is a sample C for comparison consisting of 10 g of iron, and argon gas containing 2 g of single-walled carbon nanotubes (trade name: Hi P c 0 (registered trademark), manufactured by CNI) in 10 g of iron.
- Hi P c 0 registered trademark
- Comparative Sample D which was solidified after being dispersed.
- composition using the cylindrical carbon structure obtained from Example 1 as a base fiber was filled in a mold and subjected to binder molding (pressure: 150 kgf Zcm 2 (14.7 MPa), temperature: 170 ° C, pressurization time: 5 minutes).
- Binder Phenol resin 20% by mass
- Friction modifier (palium sulfate) 50% by mass
- test piece A of the present invention was produced using the cylindrical carbon structure obtained from Example 2 and the asbestos fiber (
- FIG. 7 is a graph showing the measurement result of the friction coefficient () in the example
- FIG. 8 is a graph showing the wear rate (cm 3 Zk gm) in the example. From the results shown in FIGS. 7 and 8, it can be seen that the test piece of the present invention has a low coefficient of friction ( ⁇ ) temperature dependency and a low wear rate.
- a Si substrate in which a Co—Mo alloy having a particle size of 10 nm or less was dispersed was heated at 600 ° C. in an ethanol-Z hydrogen atmosphere to produce single-walled carbon nanotubes on the substrate.
- the substrate was immersed and heated under the same conditions as in Example 1 to form the cylindrical carbon structure of the present invention on the substrate.
- the electrical characteristics of the obtained substrate (emitter) were measured, it was confirmed that electrons began to be emitted from the tip of the cylindrical carbon structure when the voltage between the emitter and gate was around 3 V. The emission increased rapidly around 5 V. This voltage was about 10% lower than that of an emitter composed of conventional carbon nanotubes.
- Cylindrical carbon structure obtained from Example 1 was mixed with 0.4 g of water-based paint (trade name: Retan PG 80, manufactured by Kansai Paint Co., Ltd.).
- a coating material of the present invention in which the body was dispersed was produced.
- Comparison of the conductivity of the comparative coating material obtained by stirring and comparison shows that the conductivity of the comparative coating material using the conventional carbon nanotube is 3.0 X 10 3 ⁇ cm
- the conductivity of the coating material of the present invention was improved to 4.2 X 10 3 ⁇ cm.
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CN100402420C (zh) * | 2006-09-18 | 2008-07-16 | 北京大学 | 一种异径单壁碳纳米管的制备方法 |
JP2012009212A (ja) * | 2010-06-23 | 2012-01-12 | Toyota Motor Corp | 燃料電池の製造方法 |
EP3301745A4 (en) * | 2015-10-28 | 2018-05-30 | LG Chem, Ltd. | Conductive material dispersed liquid and lithium secondary battery manufactured using same |
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JP2009041140A (ja) * | 2007-08-09 | 2009-02-26 | National Institute Of Advanced Industrial & Technology | 擬似円筒状単層中空炭素繊維 |
JP5667736B2 (ja) * | 2007-10-11 | 2015-02-12 | 三菱化学株式会社 | 微細中空状炭素繊維の集合体 |
JP5418874B2 (ja) * | 2008-03-11 | 2014-02-19 | 独立行政法人物質・材料研究機構 | ナノ炭素材料複合体の製造方法及びナノ炭素材料複合体を用いた電子放出素子 |
KR101339589B1 (ko) | 2011-12-21 | 2013-12-10 | 주식회사 엘지화학 | 탄소나노구조체의 신규한 2차구조물, 이의 집합체 및 이를 포함하는 복합재 |
US10570016B2 (en) | 2014-11-14 | 2020-02-25 | Toda Kogyo Corp. | Carbon nanotube and process for producing the carbon nanotube, and lithium ion secondary battery using the carbon nanotube |
JPWO2020138379A1 (ja) * | 2018-12-27 | 2021-11-04 | 住友電気工業株式会社 | カーボンナノチューブ集合線、カーボンナノチューブ集合線バンドル及びカーボンナノチューブ構造体 |
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