WO2010092787A1 - カーボンナノチューブ配向集合体の製造装置 - Google Patents
カーボンナノチューブ配向集合体の製造装置 Download PDFInfo
- Publication number
- WO2010092787A1 WO2010092787A1 PCT/JP2010/000743 JP2010000743W WO2010092787A1 WO 2010092787 A1 WO2010092787 A1 WO 2010092787A1 JP 2010000743 W JP2010000743 W JP 2010000743W WO 2010092787 A1 WO2010092787 A1 WO 2010092787A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- gas
- unit
- environment
- furnace
- Prior art date
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
- B01J15/005—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/22—Stationary reactors having moving elements inside in the form of endless belts
-
- 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
- C01B32/159—Carbon nanotubes single-walled
-
- 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
- C01B32/16—Preparation
-
- 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
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/46—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for heating the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/0009—Coils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00121—Controlling the temperature by direct heating or cooling
- B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00132—Controlling the temperature using electric heating or cooling elements
- B01J2219/00135—Electric resistance heaters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00139—Controlling the temperature using electromagnetic heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00139—Controlling the temperature using electromagnetic heating
- B01J2219/00148—Radiofrequency
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
-
- 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
Definitions
- the present invention relates to an apparatus for producing an aligned carbon nanotube aggregate, and more particularly to an apparatus for producing an aligned carbon nanotube aggregate capable of significantly improving production efficiency without quality deterioration during continuous production.
- a carbon nanotube (hereinafter also referred to as CNT) is a carbon structure having a structure in which a carbon sheet formed by arranging carbon atoms in a hexagonal shape in a plane is closed in a cylindrical shape.
- CNT carbon nanotube
- single-walled CNTs have electrical characteristics (very high current density), thermal characteristics (thermal conductivity comparable to diamond), optical characteristics (light emission in the optical communication band wavelength region), hydrogen storage capacity, and metals.
- electrical characteristics very high current density
- thermal characteristics thermal conductivity comparable to diamond
- optical characteristics light emission in the optical communication band wavelength region
- hydrogen storage capacity and metals.
- metals In addition to being excellent in various properties such as catalyst supporting ability, and having both properties of a semiconductor and a metal, it has attracted attention as a material for nanoelectronic devices, nanooptical elements, energy storage bodies, and the like.
- a bundle, a film, or a mass of aggregates in which a plurality of CNTs are aligned in a specific direction are formed. It is desirable to exhibit any optical functionality. Moreover, it is desirable that the length (height) of the CNT aggregate is much larger. If such an aligned CNT aggregate is created, the application field of CNT is expected to expand dramatically.
- a chemical vapor deposition method (hereinafter also referred to as a CVD method) is known (refer to Patent Document 1).
- This method is characterized in that a gas containing carbon (hereinafter referred to as a raw material gas) is brought into contact with metal fine particles of the catalyst in a high temperature atmosphere of about 500 ° C. to 1000 ° C., and the type and arrangement of the catalyst or the carbon compound It is possible to produce CNTs in various ways such as the type and the reaction conditions, and is attracting attention as being suitable for producing a large amount of CNTs.
- this CVD method can produce both single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT), and by using a substrate carrying a catalyst, a large number of CNTs oriented perpendicular to the substrate surface. It has the advantage that it can be manufactured.
- the CNT synthesis process in the CVD method may be divided into two processes, a formation process and a growth process.
- the metal catalyst supported on the substrate in the formation process is reduced by being exposed to a high-temperature hydrogen gas (hereinafter referred to as a reducing gas), and in the subsequent growth process, the source gas containing the catalyst activator is used.
- CNT is grown by contacting with a catalyst.
- the synthesis is generally performed in a low carbon concentration atmosphere in which the volume fraction of the source gas during CVD is suppressed to about 0.1 to 1%. Since the supply amount of source gas is proportional to the production amount of CNT, synthesis in an atmosphere with a carbon concentration as high as possible directly leads to an improvement in production efficiency.
- Non-patent document 1 a catalyst activation material such as water is brought into contact with the catalyst together with a raw material gas to thereby significantly increase the activity and life of the catalyst (hereinafter referred to as super growth method.
- the catalyst activator is considered to have an effect of removing the carbon-based impurities covering the catalyst fine particles to clean the catalyst background, and it is considered that the activity of the catalyst is remarkably improved and the life is extended. Therefore, the catalytic activity is not lost even in a high carbon concentration environment where the catalyst is normally deactivated (the volume fraction of the source gas during CVD is about 2 to 20%), and the production efficiency of CNTs is significantly improved. Has succeeded.
- the CNT synthesized by applying the super-growth method to the substrate carrying the catalyst has a high specific surface area and forms an aggregate in which each CNT is aligned in a regular direction. In addition, it has a feature that the bulk density is low (hereinafter referred to as an aligned CNT aggregate).
- a CNT aggregate is a one-dimensional elongated flexible material with a very high aspect ratio, and because of the strong van der Waals force, it is disordered, non-oriented and has a small specific surface area. Easy to configure. And since it is extremely difficult to reconstruct the orientation of the aggregate once disordered and non-oriented, it was difficult to produce a CNT aggregate having a high specific surface area orientation with molding processability. .
- the super-growth method makes it possible to produce aligned CNT aggregates that have a high specific surface area, have orientation properties, and can be processed into various shapes and shapes. It is considered that it can be applied to various uses such as capacitor electrodes and heat transfer / heat dissipation materials with directivity.
- carbon-based by-products other than CNT adhere to the inner wall surface of the furnace. This is due to the fact that the raw gas environment in the super growth method is a high carbon concentration environment, but the adhesion of this carbon fouling becomes more prominent by continuous production. It has been empirically known that when a certain amount of carbon fouling accumulates in the furnace due to continuous production, the production amount of the aligned CNT aggregate decreases and the quality deteriorates.
- such air heating cleaning is effective when the furnace wall is made of quartz, but cannot be performed due to a problem when it is made of a metal such as a heat-resistant alloy. This is because air heating cleaning oxidizes the furnace wall surface and causes generation of metal oxide scale. In particular, the oxidation resistance of a heat-resistant alloy that has been carburized once is significantly reduced. Since the growth process condition of the super-growth method is a high carbon environment, the surface of the furnace wall is more easily carburized and its oxidation resistance is significantly reduced. When air-cleaning is performed on the carburized furnace wall, carbon by-products such as amorphous carbon and graphite are gasified and removed, but the furnace wall surface is oxidized and the scale of the metal oxide becomes the furnace wall surface.
- Quartz is stable at high temperatures and emits less impurities, so it is often used as a wall material for CNT synthesis furnaces, but its processing accuracy and flexibility are not high, and it is easily damaged by impact. Has the disadvantages.
- Increasing the size of the synthesis furnace is an effective way to further improve the production efficiency of CNTs, but quartz has the problems described above, so it is very difficult to increase the size of the apparatus. It is.
- a metal is used as the wall material, air heating cleaning cannot be applied, and thus the problem of reduction in production amount and quality deterioration of the aligned CNT aggregate during continuous production cannot be solved.
- the carbon dirt adhering to the chemical reaction furnace wall of the catalyst activator and carbon dirt in the growth process comes into contact with the catalyst activator in the growth process. Under a high temperature of about 800 ° C., the carbon fouling and the catalyst activator cause a chemical reaction to generate an oxygen-containing compound having a low carbon number such as carbon monoxide or carbon dioxide. Accumulation of carbon fouling adhering to the furnace wall also increases the amount of catalyst activator that chemically reacts with carbon fouling, and the gas composition in the raw material gas environment deviates from the optimum conditions for CNT growth, resulting in CNT aligned assembly. It causes a decrease in production volume and quality of the body.
- the present invention has been devised to eliminate such disadvantages of the prior art, and its main purpose is to prevent a decrease in the production amount and quality of the aligned CNT aggregate in continuous production, as well as an apparatus.
- An object of the present invention is to provide a manufacturing apparatus capable of improving the manufacturing efficiency of the aligned CNT aggregate by facilitating the enlargement.
- an apparatus for producing an aligned carbon nanotube assembly uses a reducing gas environment as an environment surrounding a catalyst formed on a substrate surface, and the catalyst and the reduction. After the heating of at least one of the gases, the surrounding environment of the catalyst is made a source gas environment and at least one of the catalyst and the source gas is heated to grow the aligned carbon nanotube assembly.
- the material of at least one of the apparatus parts exposed to the reducing gas and the apparatus parts exposed to the source gas is a heat-resistant alloy, and the surface thereof is subjected to a molten aluminum plating treatment. It is characterized by being.
- An apparatus for producing an aligned aggregate of carbon nanotubes as an exemplary aspect of the present invention uses a surrounding environment of a catalyst formed on a substrate surface as a reducing gas environment and heats at least one of the catalyst and the reducing gas. Then, an apparatus for producing an aligned carbon nanotube assembly, in which the surrounding environment of the catalyst is set as a source gas environment and at least one of the catalyst and the source gas is heated to grow an aligned carbon nanotube assembly, Of the device parts exposed to the reducing gas and the device parts exposed to the raw material gas, the material of at least one of the device parts is a heat-resistant alloy, and the surface thereof is polished to an arithmetic average roughness Ra ⁇ 2 ⁇ m. It is characterized by that.
- the ambient environment of the catalyst formed on the substrate surface is set as the reducing gas environment, and after heating at least one of the catalyst and the reducing gas, the ambient environment of the catalyst is set as the source gas environment.
- an apparatus for producing an aligned carbon nanotube aggregate that grows an aligned carbon nanotube aggregate by heating at least one of the catalyst and the source gas the apparatus being exposed to the reducing gas and the source gas.
- the material of at least one device component among the device components to be manufactured is a heat-resistant alloy, and the surface thereof is subjected to hot dip aluminum plating.
- the amount of hydrocarbon gas (mainly methane gas) generated by the chemical reaction between the carbon fouling and the reducing gas during the formation process is reduced, and the formation process is not hindered.
- the catalyst activator that causes a chemical reaction with the carbon fouling during the growth process is also reduced, the gas composition of the raw material gas environment in the growth process can be maintained at an optimum condition. Therefore, it is possible to prevent a decrease in the production amount and quality of the aligned CNT aggregate.
- the size of the device can be easily increased, and the production efficiency of the aligned CNT aggregate can be improved. .
- the ambient environment of the catalyst formed on the substrate surface is set as a reducing gas environment and at least one of the catalyst and the reducing gas is heated, and then the ambient environment of the catalyst is changed to a raw material gas environment.
- an apparatus for producing an aligned carbon nanotube assembly that grows an aligned carbon nanotube aggregate by heating at least one of the catalyst and the source gas, the apparatus component being exposed to the reducing gas, and the source gas The material of at least one device component among the device components exposed to is a heat-resistant alloy, and the surface thereof is polished to an arithmetic average roughness Ra ⁇ 2 ⁇ m.
- the size of the device can be easily increased, and the production efficiency of the aligned CNT aggregate can be improved.
- the aligned CNT aggregate produced in the present invention refers to a structure in which a large number of CNTs grown from a substrate are aligned in a specific direction.
- the preferred specific surface area of the aligned CNT aggregate is 600 m 2 / g or more when the CNT is mainly unopened, and 1300 m 2 / g or more when the CNT is mainly opened.
- An unopened one having a specific surface area of 600 m 2 / g or more, and an open one having a specific surface area of 1300 m 2 / g or more are preferable because impurities such as metals or carbon impurities are less than several tens percent (about 40%) of the weight.
- the weight density is preferably 0.002 g / cm 3 or more and 0.2 g / cm 3 or less. If the weight density is 0.2 g / cm 3 or less, the CNTs constituting the aligned CNT aggregate are weakly linked, so it is easy to uniformly disperse the aligned CNT aggregate in a solvent or the like. become. Further, when the weight density is 0.002 g / cm 3 or more, the integrity of the aligned CNT aggregate is not impaired, and it is possible to suppress the variation, thereby facilitating handling.
- the aligned CNT aggregate oriented in a specific direction preferably has a high degree of orientation.
- High degree of orientation means 1.
- a diffraction peak pattern showing the presence of anisotropy appears when X-ray diffraction intensity is measured (Laue method) using a two-dimensional diffraction pattern image obtained by X-ray incidence from a direction perpendicular to the longitudinal direction of CNT. To do.
- Hermann's orientation coefficient is greater than 0 and less than 1 using the X-ray diffraction intensity obtained by the ⁇ -2 ⁇ method or the Laue method. More preferably, it is 0.25 or more and 1 or less.
- the height (length) of the aligned CNT aggregate is preferably in the range of 10 ⁇ m to 10 cm. If the height is 10 ⁇ m or more, the orientation is improved. Moreover, since the thing whose height is 10 cm or less can be produced
- the base material is a member capable of supporting a carbon nanotube catalyst on its surface, and any suitable material can be used as long as it can maintain the shape even at a high temperature of 400 ° C. or higher and can be used for the production of CNTs. .
- Materials include iron, nickel, chromium, molybdenum, tungsten, titanium, aluminum, manganese, cobalt, copper, silver, gold, platinum, niobium, tantalum, lead, zinc, gallium, indium, gallium, germanium, arsenic, indium, Examples include metals such as phosphorus and antimony, and alloys and oxides containing these metals, or nonmetals such as silicon, quartz, glass, mica, graphite, and diamond, and ceramics.
- Metal materials are preferred because they are less expensive than silicon and ceramics, and in particular, Fe—Cr (iron-chromium) alloys, Fe—Ni (iron-nickel) alloys, Fe—Cr—Ni (iron-chromium— Nickel) alloys and the like are preferred.
- the substrate may be in the form of a thin film, block, or powder in addition to the flat plate, but is particularly advantageous in the case of producing a large amount of the surface area with respect to the volume.
- a carburization prevention layer may be formed on at least one of the front surface and the back surface of the base material. Of course, it is desirable that a carburizing prevention layer is formed on both the front and back surfaces.
- This carburizing prevention layer is a protective layer for preventing the base material from being carburized and deformed in the carbon nanotube production process.
- the carburizing prevention layer is preferably made of a metal or a ceramic material, and particularly preferably a ceramic material having a high carburizing prevention effect.
- the metal include copper and aluminum.
- the ceramic material include aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, titanium oxide, silica alumina, chromium oxide, boron oxide, calcium oxide, zinc oxide and other oxides, and nitrides such as aluminum nitride and silicon nitride.
- aluminum oxide and silicon oxide are preferable because they have a high effect of preventing carburization.
- a catalyst is supported on the base material or the carburizing prevention layer.
- Any suitable catalyst can be used as long as it can produce CNTs, such as iron, nickel, cobalt, molybdenum, and chlorides and alloys thereof, and further, aluminium, alumina, It may be combined with titania, titanium nitride, or silicon oxide, or may be layered.
- iron-molybdenum thin film, alumina-iron thin film, alumina-cobalt thin film, alumina-iron-molybdenum thin film, aluminum-iron thin film, aluminum-iron-molybdenum thin film and the like can be exemplified.
- the amount of the catalyst may be any amount that can produce CNTs.
- the film thickness is preferably 0.1 nm or more and 100 nm or less, more preferably 0.5 nm or more and 5 nm or less, Particularly preferred is 0.8 nm or more and 2 nm or less.
- the formation of the catalyst on the substrate surface may be performed by either a wet process or a dry process. Specifically, a sputtering vapor deposition method or a liquid coating / firing method in which metal fine particles are dispersed in an appropriate solvent can be applied.
- the catalyst can be formed into an arbitrary shape by using patterning using well-known photolithography, nanoimprinting, or the like.
- the shape of the aligned CNT aggregate such as a thin film, a column, a prism, and other complicated shapes depending on the patterning of the catalyst formed on the substrate and the CNT growth time.
- a thin-film aligned CNT aggregate has an extremely small thickness (height) dimension compared to its length and width dimension, but the length and width dimension can be arbitrarily controlled by patterning the catalyst.
- the thickness dimension can be arbitrarily controlled by the growth time of each CNT constituting the aligned CNT aggregate.
- the reducing gas is generally a gas that is gaseous at the growth temperature and has at least one of the effects of reducing the catalyst, promoting atomization suitable for the growth of the CNT of the catalyst, and improving the activity of the catalyst.
- any suitable gas can be used as long as it can be used for the production of CNTs.
- it is a gas having reducing properties, such as hydrogen gas, ammonia, water vapor, and a mixture thereof. Gas can be applied.
- a mixed gas obtained by mixing hydrogen gas with an inert gas such as helium gas, argon gas, or nitrogen gas may be used.
- the reducing gas is generally used in the formation process, but may be appropriately used in the growth process.
- any material can be used as long as it can be used for the production of CNTs.
- it is a gas having a raw material carbon source at the growth temperature.
- hydrocarbons such as methane, ethane, ethylene, propane, butane, pentane, hexane, heptanepropylene, and acetylene are preferable.
- a lower alcohol such as methanol and ethanol, an oxygen-containing compound having a low carbon number such as acetone and carbon monoxide may be used. Mixtures of these can also be used.
- the source gas may be diluted with an inert gas.
- the inert gas may be any gas that is inert at the temperature at which CNTs grow and does not react with the growing CNTs, and any suitable gas can be used as long as it can be used for the production of CNTs.
- Argon, nitrogen, neon, krypton, hydrogen, chlorine and the like, and mixed gas thereof can be exemplified, and nitrogen, helium, argon and mixed gas thereof are particularly preferable.
- a chemical reaction with hydrogen may occur. In that case, it is necessary to reduce the amount of hydrogen to such an extent that the growth of CNTs is not hindered.
- the hydrogen concentration is preferably 1% or less.
- a catalyst activator may be added. By adding the catalyst activator, the production efficiency and purity of the carbon nanotube can be further improved.
- the catalyst activator used here is generally a substance containing oxygen and may be any substance that does not cause great damage to the CNT at the growth temperature.
- water for example, hydrogen sulfide, oxygen, ozone, acidic Gas, nitrogen oxides, carbon monoxide, and carbon dioxide-containing oxygen-containing compounds, or alcohols such as ethanol and methanol, ethers such as tetrahydrofuran, ketones such as acetone, aldehydes, esters, Nitric oxide, as well as mixtures thereof, are effective.
- ethers such as water, oxygen, carbon dioxide, carbon monoxide, and tetrahydrofuran are preferable, and water is particularly preferable.
- the amount of the catalyst activator added is 10 ppm to 10000 ppm, preferably 50 ppm to 1000 ppm, more preferably 100 ppm to 700 ppm.
- the mechanism of the function of the catalyst activator is presumed as follows at present. During the CNT growth process, if amorphous carbon, graphite, or the like generated as a secondary material adheres to the catalyst, the catalyst is deactivated and the growth of the CNT is inhibited. However, in the presence of a catalyst activator, it is gasified by oxidizing amorphous carbon, graphite, etc. to carbon monoxide, carbon dioxide, etc., so that the catalyst is cleaned, increasing the activity of the catalyst and extending the active life. It is considered that (catalyst activation action) is expressed.
- this catalyst activator increases the activity of the catalyst and extends its life.
- the growth of CNTs completed in about 2 minutes at most is continued for several tens of minutes by addition, and the growth rate is increased 100 times or more, and further 1000 times.
- an aligned CNT aggregate whose height is remarkably increased is obtained.
- the high carbon concentration environment means a growth atmosphere in which the ratio of the raw material gas to the total flow rate is about 2 to 20%.
- the chemical vapor deposition method that does not use a catalyst activator, if the carbon concentration is increased, carbon-based impurities generated during the CNT synthesis process cover the catalyst fine particles, the catalyst is easily deactivated, and CNT cannot be efficiently grown.
- the synthesis is performed in a growth atmosphere (low carbon concentration environment) in which the ratio of the source gas to the total flow rate is about 0.1 to 1%.
- the catalytic activity is remarkably improved. Therefore, even in a high carbon concentration environment, the catalyst does not lose its activity, and CNT can be grown for a long time and the growth rate is remarkably improved.
- a larger amount of carbon contamination adheres to the furnace wall or the like than in a low carbon concentration environment.
- the pressure in the furnace is preferably 10 2 Pa or more and 10 7 Pa (100 atm) or less, more preferably 10 4 Pa or more and 3 ⁇ 10 5 Pa (3 atmospheric pressure) or less.
- reaction temperature The reaction temperature for growing CNTs is appropriately determined in consideration of the metal catalyst, raw material carbon source, reaction pressure, etc., but a catalyst activator is added to eliminate by-products that cause catalyst deactivation.
- a catalyst activator is added to eliminate by-products that cause catalyst deactivation.
- the catalyst activator when water is used as the catalyst activator, it is preferably 400 ° C. or higher and 1000 ° C. or lower.
- the effect of the catalyst activation material can be sufficiently expressed at 400 ° C. or higher, and the reaction of the catalyst activation material with CNT can be suppressed at 1000 ° C. or lower.
- the temperature is more preferably 400 ° C. or higher and 1100 ° C. or lower.
- the effect of the catalyst activation material can be sufficiently exhibited at 400 ° C. or higher, and the reaction of the catalyst activation material with CNT can be suppressed at 1100 ° C. or lower.
- the formation process means a process in which the ambient environment of the catalyst supported on the substrate is set as a reducing gas environment and at least one of the catalyst and the reducing gas is heated.
- this step at least one of the effects of reducing the catalyst, promoting atomization in a state suitable for the growth of the catalyst CNT, and improving the activity of the catalyst appears.
- the catalyst is an alumina-iron thin film
- the iron catalyst is reduced into fine particles, and a large number of nanometer-sized iron fine particles are formed on the alumina layer.
- the catalyst is prepared as a catalyst suitable for the production of the aligned CNT aggregate.
- the growth process means that the surrounding environment of the catalyst that has been made suitable for the production of the aligned CNT aggregate by the formation process is used as a raw material gas environment, and at least one of the catalyst or the raw material gas is heated to thereby align the aligned CNT aggregate. It means the process of growing.
- a cooling process means the process of cooling an aligned CNT aggregate, a catalyst, and a base material under an inert gas after a growth process. Since the aligned CNT aggregate, the catalyst, and the substrate after the growth step are in a high temperature state, they may be oxidized when placed in an oxygen-existing environment. In order to prevent this, the aligned CNT aggregate, catalyst, and substrate are cooled to, for example, 400 ° C. or lower, more preferably 200 ° C. or lower, under an inert gas environment.
- the production apparatus used in the practice of the present invention must include a synthesis furnace for receiving the catalyst and the supported substrate and heating means, but the structure and configuration of each other part are not particularly limited, CVD furnace, thermal heating furnace, electric furnace, drying furnace, thermostat, atmosphere furnace, gas replacement furnace, muffle furnace, oven, vacuum heating furnace, plasma reactor, microplasma reactor, RF plasma reactor, electromagnetic heating reactor Known devices such as a microwave irradiation reaction furnace, an infrared irradiation heating furnace, an ultraviolet heating reaction furnace, an MBE reaction furnace, an MOCVD reaction furnace, and a laser heating apparatus can be used.
- FIG. A tubular synthesis furnace 304 that receives the base material 301 carrying the catalyst is provided, and a heater 305 provided so as to surround the synthesis furnace 304.
- the heater one that can be heated in a range of 400 ° C. or higher and 1100 ° C. or lower is preferable, and examples thereof include a resistance heater, an infrared heater, and an electromagnetic induction heater.
- a base material holder 302 for holding the base material 301 is provided at a lower position in the synthesis furnace 304, and a gas injection unit 303 is provided above the base material holder 302.
- a reducing gas, a raw material gas, an inert gas, a catalyst activation material, or the like is injected from the gas injection unit 303 toward the base material.
- a check valve, a flow rate control valve, a flow rate sensor, and the like are installed upstream of the gas injection unit 303, and the reducing gas is controlled by appropriately opening and closing each flow rate control valve by the control device.
- the flow rates of the raw material gas, the inert gas, the catalyst activation material, and the like can be controlled, and the gases are mixed and injected from the gas injection unit 303.
- the ejected gas is naturally exhausted from the outlet to the outside of the synthesis furnace.
- an inert gas is injected from the gas injection unit 303.
- the inside of the furnace is replaced with inert gas from air.
- reducing gas is injected from the gas injection unit 303 and the interior of the synthesis furnace 304 is heated by the heater 305.
- the raw material gas and the catalyst activation material are injected from the gas injection unit 303 and the inside of the synthesis furnace 304 is heated by the heater 305, and the aligned CNT aggregate is manufactured on the substrate 301.
- an inert gas is injected from the gas injection unit 303 and the heating of the heater 305 is stopped, and the synthesis furnace 304 is cooled to 200 ° C. or lower.
- the means for supplying the catalyst activator is not particularly limited. For example, supply by a bubbler, supply by vaporizing a solution containing the catalyst activator, supply as a gas, and liquefying the solid catalyst activator -Evaporation supply etc. are mentioned,
- the supply system using various apparatuses, such as a vaporizer, a mixer, a stirrer, a diluter, a sprayer, a pump, and a compressor, can be constructed
- a catalyst activation material concentration measuring device may be provided in a catalyst activation material supply pipe or the like. By performing feedback control using this output value, it is possible to supply a stable catalyst activation material with little change over time.
- the shower head provided with the several injection hole provided in the position which faces the catalyst formation surface of a base material.
- the position facing each other is provided such that the angle between each ejection hole and the normal line of the substrate is 0 or more and less than 90 °. That is, the direction of the gas flow ejected from the ejection holes provided in the shower head is set to be substantially orthogonal to the substrate.
- the reducing gas When the reducing gas is injected using such a shower head, the reducing gas can be uniformly sprayed on the substrate, and the catalyst can be reduced efficiently. As a result, the uniformity of the aligned CNT aggregates grown on the substrate can be improved, and the amount of reducing gas consumed can be reduced.
- the raw material gas When the raw material gas is injected using such a shower head, the raw material gas can be uniformly dispersed on the substrate, and the raw material gas can be consumed efficiently. As a result, the uniformity of the aligned CNT aggregates grown on the substrate can be improved, and the consumption of the raw material gas can be reduced.
- the catalyst activation material When a catalyst activation material is injected using such a showerhead, the catalyst activation material can be uniformly sprayed on the substrate, and the activity of the catalyst is increased and the lifetime is extended. It becomes possible to make it.
- FIG. 2 shows an apparatus for producing an aligned CNT aggregate according to the present invention.
- the production apparatus of the present invention is generally composed of an inlet purge unit, a formation unit, a growth unit, a transport unit, a gas mixing prevention means, a connection unit, a cooling unit, and an outlet purge unit. Each configuration will be described below.
- the inlet purge section is a set of apparatuses for preventing external air from being mixed into the apparatus furnace from the substrate inlet. It has a function of replacing the surrounding environment of the substrate conveyed into the apparatus with a purge gas.
- a furnace or a chamber for holding the purge gas, an injection unit for injecting the purge gas, and the like can be mentioned.
- the purge gas is preferably an inert gas, and nitrogen is particularly preferable from the viewpoints of safety, cost, purgeability, and the like.
- the substrate inlet is always open, such as a belt conveyor type, it is preferable to use a gas curtain device that injects purge gas in a shower shape from above and below as the purge gas injection unit to prevent external air from entering from the device inlet.
- the formation unit is a set of devices for realizing the formation process.
- the formation environment is a reducing gas environment around the catalyst formed on the surface of the substrate, and at least one of the catalyst and the reducing gas is heated. It has a function.
- a formation furnace for holding the reducing gas, a reducing gas injection unit for injecting the reducing gas, a heater for heating at least one of the catalyst and the reducing gas, and the like can be mentioned.
- the heater one that can be heated in the range of 400 ° C. to 1100 ° C. is preferable, and examples thereof include a resistance heater, an infrared heater, and an electromagnetic induction heater.
- the growth unit is a set of devices for realizing the growth process.
- the environment surrounding the catalyst which is in a state suitable for the production of the aligned CNT aggregate by the formation process, is used as the raw material gas environment, and the catalyst and the raw material. It has a function of growing an aligned CNT aggregate by heating at least one of the gases. Examples thereof include a growth furnace for maintaining a source gas environment, a source gas injection unit for injecting source gas, and a heater for heating at least one of a catalyst and source gas.
- the heater one that can be heated in the range of 400 ° C. to 1100 ° C. is preferable, and examples thereof include a resistance heater, an infrared heater, and an electromagnetic induction heater. Furthermore, it is good to have a catalyst activator addition part.
- the catalyst activator adding part is a set of devices for adding the catalyst activator to the raw material gas or for directly adding the catalyst activator to the ambient environment of the catalyst in the growth furnace space.
- the means for supplying the catalyst activator is not particularly limited.
- a supply using a bubbler a supply obtained by vaporizing a solution containing the catalyst activator, a supply as a gas, and a solid catalyst activator are used. Examples include liquefied / vaporized supply, and a supply system using various devices such as a vaporizer, a mixer, a stirrer, a diluter, a sprayer, a pump, and a compressor can be constructed.
- a catalyst activation material concentration measuring device may be provided in a catalyst activation material supply pipe or the like. By performing feedback control using this output value, it is possible to supply a stable catalyst activation material with little change over time.
- the transport unit is a set of apparatuses necessary for transporting a substrate from at least the formation unit to the growth unit. Specifically, a mesh belt in a belt conveyor system, a driving device using an electric motor with a speed reducer, and the like can be given.
- the gas mixing prevention means is a set of devices for realizing a function of preventing gas from being mixed into the furnace space of each unit, which is installed at a connection portion where the inside of each unit is spatially connected to each other. That is.
- a gate valve device that mechanically shuts off the spatial connection of each unit during a time other than during the movement of the substrate from unit to unit
- a gas curtain device that shuts off by inert gas injection, a connecting portion, and a connecting portion of each unit
- An exhaust device that discharges nearby gas to the outside of the system may be used.
- the shutter and the gas curtain are preferably used in combination with an exhaust device.
- the gas mixing prevention means to function so as to keep the number concentration of carbon atoms in the reducing gas environment in the formation furnace preferably at 5 ⁇ 10 22 atoms / m 3 or less, more preferably at 1 ⁇ 10 22 atoms / m 3 or less. There is.
- the exhaust amount Q of the plurality of exhaust units cannot be determined independently of each other. It is necessary to adjust the gas supply amount (reducing gas flow rate, raw material gas flow rate, cooling gas flow rate, etc.) of the entire apparatus.
- the necessary condition for satisfying the gas mixing prevention can be expressed by the following equation.
- D is the diffusion coefficient of the gas to be prevented from mixing
- S is the cross-sectional area of the boundary to prevent gas mixing
- L is the length of the exhaust part (furnace length direction).
- N A Carbon atom number concentration
- the production amount and quality of CNTs can be kept good.
- the number concentration of carbon atoms By setting the number concentration of carbon atoms to 5 ⁇ 10 22 atoms / m 3 or less, effects such as reduction of the catalyst, promotion of atomization suitable for the growth of the CNT of the catalyst, and improvement of the activity of the catalyst are obtained in the formation process.
- the production amount of CNTs in the growth process can be improved, and the quality can be improved.
- a furnace or a chamber that can block the environment around the base material and the outside air and pass the base material from unit to unit can be used.
- the cooling unit is a set of devices necessary for cooling the substrate on which the aligned CNT aggregate has grown. It has a function of preventing oxidation and cooling of the aligned CNT aggregate, catalyst, and substrate after the growth process.
- a cooling furnace for holding an inert gas a water-cooled cooling pipe arranged so as to surround the cooling furnace space in the case of a water cooling type, and an injection unit that injects an inert gas into the cooling furnace space in the case of an air cooling type Etc.
- a water cooling method and an air cooling method may be combined.
- the outlet purge section is a set of apparatuses for preventing external air from being mixed into the apparatus furnace from the substrate outlet. It has a function to make the surrounding environment of the substrate a purge gas environment.
- a furnace or chamber for maintaining a purge gas environment, an injection unit for injecting purge gas, and the like can be given.
- the purge gas is preferably an inert gas, and nitrogen is particularly preferable from the viewpoints of safety, cost, purgeability, and the like.
- the base material outlet is always open, such as a belt conveyor type, it is preferable to use a gas curtain device that injects purge gas in a shower shape from above and below as the purge gas injection unit to prevent external air from entering from the device outlet.
- a shower head provided with a plurality of ejection holes provided at a position facing the catalyst formation surface of the substrate may be used as an injection part for the reducing gas, the raw material gas, and the catalyst activation material.
- the position facing each other is provided such that the angle between each ejection hole and the normal line of the substrate is 0 or more and less than 90 °. That is, the direction of the gas flow ejected from the ejection holes provided in the shower head is set to be substantially orthogonal to the substrate.
- the reducing gas can be uniformly sprayed on the substrate, and the catalyst can be efficiently reduced.
- the uniformity of the aligned CNT aggregates grown on the substrate can be improved, and the amount of reducing gas consumed can be reduced.
- the raw material gas can be uniformly dispersed on the substrate, and the raw material gas can be consumed efficiently.
- the uniformity of the aligned CNT aggregates grown on the substrate can be improved, and the consumption of the raw material gas can be reduced.
- the catalyst activation material can be uniformly dispersed on the substrate, and the activity of the catalyst is increased and the life is extended. It can be continued. This is the same even when a catalyst activator is added to the raw material gas and a shower head is used as an injection section.
- the formation unit 102, the growth unit 104, and the cooling unit 105 each include a formation furnace 102a, a growth furnace 104a, and a cooling furnace 105a
- the transport unit 107 includes a mesh belt 107a and a belt driving unit 107b. ing.
- Each furnace is spatially connected by a connection.
- the base material (catalyst substrate) 111 is transported by the transport unit 107 in the order of formation, growth, and cooling in each furnace space.
- an inlet purge unit 101 is provided at the apparatus inlet.
- This inlet purge unit 101 sprays purge gas from above and below in the form of a shower to prevent external air from entering the apparatus furnace from the inlet.
- the inlet purge unit 101 and the formation unit 102 are spatially connected by a connection unit, and an exhaust unit 103a serving as a gas mixing prevention unit is disposed.
- the purge gas injected from the inlet purge unit 101 and the reducing gas injection unit 102b are injected.
- the mixed gas with the reduced gas is exhausted. This prevents purge gas from entering the formation furnace space and reducing gas from entering the inlet purge section.
- the formation unit 102 and the growth unit 104 are spatially connected by a connection part, and an exhaust part 103b of a gas mixing prevention means is arranged, so that the reducing gas in the formation furnace space and the raw material gas in the growth furnace space are mixed. The gas is exhausted. Thereby, mixing of the source gas into the formation furnace space and mixing of the reducing gas into the growth furnace space are prevented.
- the growth unit 104 and the cooling unit 105 are spatially connected by a connection part, and an exhaust part 103c of gas mixing prevention means is disposed, and the source gas in the growth furnace space and the inert gas in the cooling furnace space The mixed gas is exhausted. Thereby, mixing of the source gas into the cooling furnace space and mixing of the inert gas into the growth furnace space are prevented.
- an outlet purge unit 106 having a structure substantially similar to that of the inlet purge unit 101 is provided.
- the outlet purge unit 106 injects purge gas from above and below in a shower shape, thereby preventing external air from being mixed into the cooling furnace from the outlet.
- the transport unit 107 is of a belt conveyor type, and a substrate on which a catalyst is formed on the surface, for example, an electric motor with a speed reducer, is formed from the formation furnace space to the growth furnace space. It is conveyed by the mesh belt 107a driven by the used belt drive unit (drive device) 107b.
- the formation furnace space and the growth furnace space, and the growth furnace space and the cooling furnace space are spatially connected by a connecting portion so that the mesh belt 107a on which the substrate is placed can pass. Since the exhaust part of the above-mentioned gas mixing prevention means is provided at these boundaries, the mixing of gases is prevented.
- steel containing Fe as a main component and other alloy concentration of 50% or less and containing about 12% or more of Cr is generally called stainless steel.
- a nickel base alloy the alloy which added Mo, Cr, Fe, etc. to Ni is mentioned.
- SUS310, Inconel 600, Inconel 601, Inconel 625, Incoloy 800, MC alloy, Haynes 230 alloy and the like are preferable from the viewpoints of heat resistance, mechanical strength, chemical stability, and low cost.
- the molten aluminum plating treatment refers to a treatment for forming an aluminum or aluminum alloy layer on the surface of a material to be plated by immersing the material to be plated in a molten aluminum bath.
- the surface of the material to be plated base material
- pretreatment the surface of the material to be plated
- a molten aluminum bath at about 700 ° C. to cause diffusion of the molten aluminum into the surface of the base material.
- An alloy of the base material and aluminum is produced, and aluminum is adhered to the alloy layer when pulled up from the bath.
- the surface alumina layer and the aluminum layer may be subjected to a low temperature thermal diffusion treatment to expose the underlying Fe—Al alloy layer.
- polishing process As a polishing method for making the heat-resistant alloy an arithmetic average roughness Ra ⁇ 2 ⁇ m, mechanical polishing represented by buff polishing, chemical polishing using chemicals, electrolytic polishing in which an electric current is passed in an electrolytic solution, Examples thereof include composite electropolishing that combines mechanical polishing and electropolishing.
- the catalyst is formed on the substrate surface by a film forming apparatus different from the manufacturing apparatus.
- a catalyst film forming unit is provided upstream of the formation unit.
- the manufacturing apparatus may be configured so that the base material passes through the catalyst film forming unit prior to the formation unit.
- each unit is provided in the order of the formation unit, the growth unit, and the cooling unit, and each furnace space is spatially connected at the connection portion.
- a plurality of units that realize processes other than the growth process and the cooling process may be added somewhere, and the in-furnace space of each unit may be spatially connected at the connection portion.
- the conveyor unit has been described using the belt conveyor system, but the present invention is not limited thereto, and for example, a robot arm system, a turntable system, a lifting system, or the like may be used. .
- each of the formation unit, the growth unit, and the cooling unit has been described with two methods of a linear arrangement and an annular arrangement. Instead, for example, they may be sequentially arranged in the vertical direction.
- the specific surface area is a value measured by the Brunauer, Emmett, and Teller method from an adsorption / desorption isotherm of liquid nitrogen measured at 77K.
- the specific surface area was measured using a BET specific surface area measuring device (HM model-1210 manufactured by Mountec Co., Ltd.).
- the G / D ratio is an index generally used for evaluating the quality of CNTs.
- vibration modes called G band (near 1600 cm-1) and D band (near 1350 cm-1) are observed.
- the G band is a vibration mode derived from a hexagonal lattice structure of graphite, which is a cylindrical surface of CNT
- the D band is a vibration mode derived from a crystal defect. Therefore, the higher the peak intensity ratio (G / D ratio) between the G band and the D band, the lower the amount of defects and the higher the quality of the CNT.
- the surface roughness referred to in this application is the arithmetic average roughness Ra.
- the Ra value was measured using a laser microscope (VK-9710 manufactured by Keyence Corporation) under the following measurement conditions.
- Measurement mode Surface shape
- Measurement quality High definition
- Objective lens CF IC EPI Plan 10 ⁇
- Measurement area 1.42mm 2 (1.42mm ⁇ 1.0mm)
- Z direction measurement pitch 0.1 ⁇ m -Ra of the height data obtained by the measurement was obtained by the “surface roughness” measurement function of the analysis software (VK shape analysis application VK-H1A1 manufactured by Keyence Corporation).
- Example 1 In the following, a specific example will be given to explain in more detail the apparatus for producing an aligned CNT aggregate according to the present invention.
- the production conditions for the substrate carrying the catalyst are described below.
- a 40 mm square and 0.3 mm thick Fe—Ni—Cr alloy YEF426 manufactured by Hitachi Metals, 42% Ni, 6% Cr was used as the base material.
- the surface roughness was measured using a laser microscope, the arithmetic average roughness Ra ⁇ 2.1 ⁇ m.
- An alumina film having a thickness of 100 nm was formed on both the front and back surfaces of the substrate using a sputtering apparatus, and then an iron film (catalyst metal layer) having a thickness of 1.0 nm was formed only on the surface using a sputtering apparatus.
- the manufacturing apparatus diagram of this example is shown in FIG. First, the base material carrying the catalyst is placed on the base material holder, and N 2 : 4000 sccm is applied for 4 minutes from the gas injection unit into the synthesis furnace maintained at furnace temperature: room temperature and furnace pressure: 1.02E + 5. The air in the synthesis furnace was replaced with N 2 . Next, N 2 : 400 sccm and H 2 : 3600 sccm were introduced from the gas injection section for 30 minutes and heated at a heating rate of 26 ° C./min until the furnace temperature reached 800 ° C. (formation process).
- the material of the synthesis furnace, the base material holder, and the gas injection part was SUS310S, and the surface thereof was subjected to hot dip aluminum plating.
- the arithmetic average roughness Ra was 3.4 ⁇ m to 8.0 ⁇ m (in the measurement of the surface roughness, the z-direction measurement range was 236 ⁇ m).
- aligned CNT aggregates were continuously produced.
- the characteristics of the aligned CNT aggregate produced by this example depend on the details of the production conditions, but typical values are density: 0.03 g / cm 3, BET-specific surface area: 1100 m 2 / g, average outer diameter: 2 0.9 nm, half width 2 nm, carbon purity 99.9%, Herman orientation coefficient 0.7.
- Table 1 shows the results of the yield, specific surface area, and G / D ratio of the continuously produced aligned CNT aggregates.
- Example 2 The manufacturing conditions of the catalyst substrate will be described below.
- a 90 mm square and 0.3 mm thick Fe—Ni—Cr alloy YEF426 (manufactured by Hitachi Metals, Ni 42%, Cr 6%) was used as the substrate.
- the surface roughness was measured using a laser microscope, the arithmetic average roughness Ra ⁇ 2.1 ⁇ m.
- An alumina film having a thickness of 20 nm was formed on both the front and back surfaces of the substrate using a sputtering apparatus, and then an iron film (catalyst metal layer) having a thickness of 1.0 nm was formed only on the surface using a sputtering apparatus.
- FIG. 2 shows a manufacturing apparatus diagram of this example.
- the manufacturing apparatus includes an inlet purge unit 101, a formation unit 102, a gas mixing prevention means 103, a growth unit 104, a cooling unit 105, an outlet purge unit 106, a transport unit 107, and connection units 108 to 110.
- the catalyst substrate thus produced was placed on the mesh belt of the production apparatus, and the formation process, the growth process, and the cooling process were performed in this order while changing the mesh belt conveyance speed to produce an aligned CNT aggregate. .
- the conditions of the inlet purge section, formation unit, gas mixing prevention means, growth unit, cooling unit, and outlet purge section of the manufacturing apparatus were set as follows.
- Inlet purge unit 101 Purge gas: nitrogen 60000 sccm Formation unit 102 -Furnace temperature: 830 ° C ⁇ Reducing gas: nitrogen 11200 sccm, hydrogen 16800 sccm ⁇ Processing time: 28 minutes Gas mixing prevention means 103 ⁇ Exhaust part 103a displacement: 20 sLm ⁇ Exhaust part 103b displacement: 25 sLm ⁇ Exhaust part 103c displacement: 20 sLm Growth unit 104 -Furnace temperature: 830 ° C -Source gas: nitrogen 16040 sccm, ethylene 1800 sccm, Steam-containing nitrogen 160sccm (water content 16000ppmv) ⁇ Processing time: 11 minutes Cooling unit 105 ⁇ Cooling water temperature: 30 ° C ⁇ Inert gas: 10000sccm of nitrogen Cooling time: 30 minutes Outlet purge unit 106 ⁇ Purge gas: Nitrogen 50000sccm The materials of the furnace / injection unit of the
- the arithmetic average roughness Ra was 3.4 ⁇ m to 8.0 ⁇ m (in the measurement of the surface roughness, the measurement range in the z direction was 316 ⁇ m).
- the method for hot-dip aluminum plating was performed in the same manner as in Example 2.
- the properties of the aligned CNT aggregate produced by this example depend on the details of the production conditions, but as a typical value, density: 0.03 g / cm 3 , BET-specific surface area: 1100 m 2 / g, out of average The diameter was 2.9 nm, the half width was 2 nm, the carbon purity was 99.9%, and the Herman orientation coefficient was 0.7. Table 2 shows the results of the yield, specific surface area, and G / D ratio of the continuously produced aligned CNT aggregates.
- reducing gas during continuous production was sampled from a gas sampling port installed in the vicinity of the reducing gas injection section, and component analysis was performed with an FTIR analyzer (Thermo Fisher Scientific Nicolet 6700 FT-IR). As a result, it was confirmed that the ethylene concentration in the formation furnace was suppressed to 50 ppmv by the gas mixing prevention means. In terms of the carbon atom number concentration, it is about 3 ⁇ 10 21 atoms / m 3 .
- Example 3 The production conditions for the substrate carrying the catalyst are the same as in Example 1.
- the production apparatus and production conditions of this example are the same as those of Example 1 except for the materials of the synthesis furnace, the base material holder, the gas injection unit, and the surface treatment thereof.
- aligned CNT aggregates were continuously produced.
- the characteristics of the aligned CNT aggregate produced by this example depend on the details of the production conditions, but typical values are density: 0.03 g / cm 3, BET-specific surface area: 1100 m 2 / g, average outer diameter: 2 0.9 nm, half width 2 nm, carbon purity 99.9%, Herman orientation coefficient 0.7.
- Table 3 shows the results of the yield, specific surface area, and G / D ratio of the continuously produced CNT aggregate.
- Example 4 The production conditions for the substrate carrying the catalyst are the same as in Example 2.
- the manufacturing apparatus and manufacturing conditions of this example are the same as those of Example 2 except for the furnace and injection unit of the formation / growth unit, the exhaust part of the gas mixing prevention means, the mesh belt, the material of the connection part, and the surface treatment thereof.
- the material of the furnace / injection unit of the formation / growth unit, the exhaust unit of the gas mixing prevention means, the mesh belt, and the connection unit is Inconel 601
- aligned CNT aggregates were continuously produced.
- the characteristics of the aligned CNT aggregate produced by this example depend on the details of the production conditions, but typical values are density: 0.03 g / cm 3, BET-specific surface area: 1100 m 2 / g, average outer diameter: 2 0.9 nm, half width 2 nm, carbon purity 99.9%, Herman orientation coefficient 0.7.
- Table 4 shows the results of the yield, specific surface area, and G / D ratio of the aligned CNT aggregates produced continuously.
- reducing gas during continuous production was sampled from a gas sampling port installed in the vicinity of the reducing gas injection section, and component analysis was performed with an FTIR analyzer (Thermo Fisher Scientific Nicolet 6700 FT-IR). As a result, it was confirmed that the ethylene concentration in the formation furnace was suppressed to 50 ppmv by the gas mixing prevention means. In terms of the carbon atom number concentration, it is about 3 ⁇ 10 21 atoms / m 3 .
- Example 1 The production conditions for the substrate carrying the catalyst are the same as in Example 1.
- the production apparatus and production conditions of this comparative example are the same as those in Example 1 except for the materials of the synthesis furnace, the base material holder, the gas injection unit, and the surface treatment thereof.
- the material of the synthesis furnace, the base material holder, and the gas injection part is Inconel 601
- Z-direction measurement range is 364 ⁇ m in surface roughness measurement).
- Table 5 shows the results of the yield, specific surface area, and G / D ratio of the continuously produced CNT aggregate.
- a formation unit that heats at least one of the catalyst and the reducing gas while the surrounding environment of the catalyst is the reducing gas environment, and the periphery of the catalyst
- a growth unit for setting the environment as the source gas environment and heating at least one of the catalyst and the source gas to grow the aligned carbon nanotube aggregate, and transporting the substrate from at least the formation unit to the growth unit And a transport unit.
- a formation unit that heats at least one of the catalyst and the reducing gas while the surrounding environment of the catalyst is the reducing gas environment, and the periphery of the catalyst
- a growth unit for setting the environment as the source gas environment and heating at least one of the catalyst and the source gas to grow the aligned carbon nanotube aggregate, and transporting the substrate from at least the formation unit to the growth unit And a transport unit.
- the present invention prevents the decrease in the production amount and quality of the aligned CNT aggregate in continuous production, and can easily increase the size of the apparatus, so it is suitably used in the fields of electronic device materials, optical element materials, conductive materials, etc. it can.
- inlet purge unit 102 formation unit 102a: formation furnace 102b: reducing gas injection unit 102c: heater 103: gas mixing prevention means 103a to 103c: exhaust unit 104: growth unit 104a: growth furnace 104b: source gas injection unit 104c: Heater 105: Cooling unit 105a: Cooling furnace 105b: Cooling gas injection unit 105c: Water cooling cooling pipe 106: Outlet purging unit 107: Conveying unit 107a: Mesh belt 107b: Belt driving unit 108 to 110: Connection unit 111: Catalyst substrate (base Material) 301: Catalyst substrate (base material) 304: Synthesis furnace 305: Heater 302: Base material holder 303: Gas injection unit 306: Exhaust port
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
フォーメーション工程と成長工程が同一炉内で連続に繰り返し行われるので、成長工程において炉壁に付着した炭素汚れは、フォーメーション工程時においては還元ガスに曝されていることになる。800℃程度の高温下では炭素汚れと還元ガス中の水素が化学反応を起こして炭化水素ガス(主にはメタンガス)を発生させる。炉壁に付着する炭素汚れが増加すると、それによって発生する炭化水素ガスの量も増加するのでCNT成長に必要な触媒の還元を阻害し出し、CNT配向集合体の製造量低下及び品質劣化を引き起こす。
炉壁に付着した炭素汚れは、成長工程時においては触媒賦活物質と接触することになる。800℃程度の高温下では炭素汚れと触媒賦活物質が化学反応を起こして一酸化炭素や二酸化炭素などの低炭素数の含酸素化合物を発生させる。炉壁に付着する炭素汚れが蓄積すると、それによって炭素汚れと化学反応をする触媒賦活物質の量も増加し、原料ガス環境のガス組成はCNT成長に最適な条件から外れてしまい、CNT配向集合体の製造量低下及び品質劣化を引き起こす。
本発明において製造されるCNT配向集合体とは、基材から成長した多数のCNTが特定の方向に配向した構造体をいう。CNT配向集合体の好ましい比表面積は、CNTが主として未開口のものにあっては、600m2/g以上であり、CNTが主として開口したものにあっては、1300m2/g以上である。比表面積が600m2/g以上の未開口のもの、1300m2/g以上の開口したものは、金属などの不純物若しくは炭素不純物を重量の数十パーセント(40%程度)未満と少ないので好ましい。
1.CNTの長手方向に平行な第1方向と、第1方向に直交する第2方向とからX線を入射してX線回折強度を測定(θ-2θ法)した場合に、第2方向からの反射強度が、第1方向からの反射強度より大きくなるθ角と反射方位とが存在し、且つ第1方向からの反射強度が、第2方向からの反射強度より大きくなるθ角と反射方位とが存在すること。
基材はその表面にカーボンナノチューブの触媒を担持することのできる部材であり、400℃以上の高温でも形状を維持できる、CNTの製造に使用可能なものであれば適宜のものを用いることができる。材質としては、鉄、ニッケル、クロム、モリブデン、タングステン、チタン、アルミニウム、マンガン、コバルト、銅、銀、金、白金、ニオブ、タンタル、鉛、亜鉛、ガリウム、インジウム、ガリウム、ゲルマニウム、砒素、インジウム、燐、及びアンチモンなどの金属、並びにこれらの金属を含む合金及び酸化物、又はシリコン、石英、ガラス、マイカ、グラファイト、及びダイヤモンドなどの非金属、並びにセラミックなどが挙げられる。金属材料はシリコンやセラミックと比較して、低コストであるから好ましく、特に、Fe-Cr(鉄-クロム)合金、Fe-Ni(鉄-ニッケル)合金、Fe-Cr-Ni(鉄-クロム-ニッケル)合金等は好適である。
この基材の表面又は裏面の少なくともいずれか一方には、浸炭防止層が形成してもよい。もちろん、表面及び裏面の両面に浸炭防止層が形成されていることが望ましい。この浸炭防止層は、カーボンナノチューブの生成工程において、基材が浸炭されて変形してしまうのを防止するための保護層である。
基材、若しくは浸炭防止層上には、触媒が担持されている。触媒としてはCNTの製造が可能なものであれば適宜のものを用いることができ、例えば、鉄、ニッケル、コバルト、モリブデン、及びこれらの塩化物、及び合金、またこれらが、さらにアムミニウム、アルミナ、チタニア、窒化チタン、酸化シリコンと複合化、また層状になっていてもよい。例えば、鉄-モリブデン薄膜、アルミナ-鉄薄膜、アルミナ-コバルト薄膜、及びアルミナ-鉄-モリブデン薄膜、アルミニウム-鉄薄膜、アルミニウム-鉄-モリブデン薄膜などを例示することができる。触媒の存在量としては、CNTの製造が可能な量であればよく、例えば鉄を用いる場合、製膜厚さは、0.1nm以上100nm以下が好ましく、0.5nm以上5nm以下がさらに好ましく、0.8nm以上2nm以下が特に好ましい。
還元ガスは、一般的には、触媒の還元、触媒のCNTの成長に適合した状態の微粒子化促進、触媒の活性向上の少なくとも一つの効果を持つ、成長温度において気体状のガスである。還元ガスとしては、CNTの製造に使用可能なものであれば適宜のものを用いることができるが、典型的には還元性を有したガスであり、例えば水素ガス、アンモニア、水蒸気及びそれらの混合ガスを適用することができる。また、水素ガスをヘリウムガス、アルゴンガス、窒素ガス等の不活性ガスと混合した混合ガスでもよい。還元ガスは、一般的には、フォーメーション工程で用いるが、適宜成長工程に用いてもよい。
本発明においてCNTの生成に用いる原料としては、CNTの製造に使用可能なものであれば適宜のものを用いることができ、例えば、成長温度において原料炭素源を有するガスである。なかでもメタン、エタン、エチレン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタンプロピレン、及びアセチレンなどの炭化水素が好適である。この他にも、メタノール、エタノールなどの低級アルコール、アセトン、一酸化炭素などの低炭素数の含酸素化合物でもよい。これらの混合物も使用可能である。またこの原料ガスは、不活性ガスで希釈されていてもよい。
不活性ガスとしては、CNTが成長する温度で不活性であり、成長するCNTと反応しないガスであればよく、CNTの製造に使用可能であれば適宜のものを用いることができるが、ヘリウム、アルゴン、窒素、ネオン、クリプトン、水素、及び塩素など、並びにこれらの混合ガスが例示でき、特に窒素、ヘリウム、アルゴン及びこれらの混合ガスが好適である。原料ガスの種類によっては水素と化学反応を生じる場合がある。その場合にはCNTの成長が阻害されない程度に水素量を低減する必要が生じる。例えば、原料ガスとしてエチレンを用いる場合、水素濃度は1%以下が好ましい。
CNTの成長工程において、触媒賦活物質を添加してもよい。触媒賦活物質の添加によって、カーボンナノチューブの製造効率や純度をより一層改善することができる。ここで用いる触媒賦活物質としては、一般には酸素を含む物質であり、成長温度でCNTに多大なダメージを与えない物質であればよく、水の他に、例えば、硫化水素、酸素、オゾン、酸性ガス、酸化窒素、一酸化炭素、及び二酸化炭素などの低炭素数の含酸素化合物、あるいはエタノール、メタノールなどのアルコール類、テトラヒドロフランなどのエーテル類、アセトンなどのケトン類、アルデヒドロ類、エステル類、酸化窒素、並びにこれらの混合物が有効である。この中でも、水、酸素、二酸化炭素、及び一酸化炭素、あるいはテトラヒドロフランなどのエーテル類が好ましく、特に水が好適である。
高炭素濃度環境とは、全流量に対する原料ガスの割合が2~20%程度の成長雰囲気のことを言う。触媒賦活物質を用いない化学気相成長法では、炭素濃度を高くするとCNTの合成過程で発生する炭素系不純物が触媒微粒子を被覆し、触媒が容易に失活し、CNTが効率良く成長できないので、全流量に対する原料ガスの割合が0.1~1%程度の成長雰囲気(低炭素濃度環境)で合成を行う。
炉内の圧力は、102Pa以上、107Pa(100気圧)以下が好ましく、104Pa以上、3×105Pa(3大気圧)以下がさらに好ましい。
CNTを成長させる反応温度は、金属触媒、原料炭素源、及び反応圧力などを考慮して適宜に定められるが、触媒失活の原因となる副次生成物を排除するために触媒賦活物質を添加する工程を含む場合は、その効果が十分に発現する温度範囲に設定することが望ましい。つまり、最も望ましい温度範囲としては、アモルファスカーボン及びグラファイトなどの副次生成物を触媒賦活物質が除去し得る温度を下限値とし、主生成物であるCNTが触媒賦活物質によって酸化されない温度を上限値とすることである。
フォーメーション工程とは、基材に担持された触媒の周囲環境を還元ガス環境とすると共に、触媒及び還元ガスのうち少なくとも一方を加熱する工程のことを意味する。この工程により、触媒の還元、触媒のCNTの成長に適合した状態の微粒子化促進、触媒の活性向上の少なくとも一つの効果が現れる。例えば、触媒がアルミナ-鉄薄膜である場合、鉄触媒は還元されて微粒子化し、アルミナ層上にナノメートルサイズの鉄微粒子が多数形成される。これにより触媒はCNT配向集合体の製造に好適な触媒に調製される。
成長工程とは、フォーメーション工程によってCNT配向集合体の製造に好適な状態となった触媒の周囲環境を原料ガス環境とすると共に、触媒又は原料ガスの少なくとも一方を加熱することにより、CNT配向集合体を成長させる工程のことを意味する。
冷却工程とは、成長工程後にCNT配向集合体、触媒、基材を不活性ガス下に冷却する工程のことを意味する。成長工程後のCNT配向集合体、触媒、基材は高温状態にあるため、酸素存在環境下に置かれると酸化してしまうおそれがある。それを防ぐために不活性ガス環境下でCNT配向集合体、触媒、基材を、例えば、400℃以下、さらに好ましくは200℃以下に冷却する。
本発明の実施に用いる製造装置は、触媒と担持した基材を受容する合成炉と加熱手段を備えることが必須であるが、その他各部の構造・構成については特に限定されることはなく、熱CVD炉、熱加熱炉、電気炉、乾燥炉、恒温槽、雰囲気炉、ガス置換炉、マッフル炉、オーブン、真空加熱炉、プラズマ反応炉、マイクロプラズマ反応炉、RFプラズマ反応炉、電磁波加熱反応炉、マイクロ波照射反応炉、赤外線照射加熱炉、紫外線加熱反応炉、MBE反応炉、MOCVD反応炉、レーザー加熱装置等の装置など、公知の装置が使用できる。
図2に本発明に係るCNT配向集合体製造装置を示す。本発明の製造装置は、大略、入口パージ部、フォーメーションユニット、成長ユニット、搬送ユニット、ガス混入防止手段、接続部、冷却ユニット、出口パージ部から構成されている。以下、各構成について説明する。
入口パージ部とは基材入口から装置炉内へ外部空気が混入することを防止するための装置一式のことである。装置内に搬送された基材の周囲環境をパージガスで置換する機能を有する。例えば、パージガスを保持するための炉又はチャンバ、パージガスを噴射するための噴射部等が挙げられる。パージガスは不活性ガスが好ましく、特に安全性、コスト、パージ性等の点から窒素であることが好ましい。ベルトコンベア式など基材入口が常時開口している場合は、パージガス噴射部としてパージガスを上下からシャワー状に噴射するガスカーテン装置とし、装置入口から外部空気が混入することを防止することが好ましい。
フォーメーションユニットとは、フォーメーション工程を実現するための装置一式のことであり、基材の表面に形成された触媒の周囲環境を還元ガス環境とすると共に、触媒と還元ガスとの少なくとも一方を加熱する機能を有する。例えば、還元ガスを保持するためのフォーメーション炉、還元ガスを噴射するための還元ガス噴射部、触媒と還元ガスの少なくとも一方を加熱するためのヒーター等が挙げられる。ヒーターとしては400℃から1100℃の範囲で加熱することができるものが好ましく、例えば、抵抗加熱ヒーター、赤外線加熱ヒーター、電磁誘導式ヒーターなどが挙げられる。
成長ユニットとは、成長工程を実現するための装置一式のことであり、フォーメーション工程によってCNT配向集合体の製造に好適な状態となった触媒の周囲環境を原料ガス環境とすると共に、触媒及び原料ガスのうち少なくとも一方を加熱することでCNT配向集合体を成長させる機能を有する。例えば、原料ガス環境を保持するための成長炉、原料ガスを噴射するための原料ガス噴射部、触媒と原料ガスの少なくとも一方を加熱するためのヒーター等が挙げられる。ヒーターとしては400℃から1100℃の範囲で加熱することができるものが好ましく、例えば、抵抗加熱ヒーター、赤外線加熱ヒーター、電磁誘導式ヒーターなどが挙げられる。更に触媒賦活物質添加部を備えていると良い。
触媒賦活物質添加部は触媒賦活物質を原料ガス中に添加する、あるいは成長炉内空間にある触媒の周囲環境に触媒賦活物質を直接添加するための装置一式のことである。触媒賦活物質の供給手段としては、特に限定されることはないが、例えば、バブラーによる供給、触媒賦活剤を含有した溶液を気化しての供給、気体そのままでの供給、及び固体触媒賦活剤を液化・気化しての供給などが挙げられ、気化器、混合器、攪拌器、希釈器、噴霧器、ポンプ、及びコンプレッサなどの各種の機器を用いた供給システムを構築することができる。さらには、触媒賦活物質の供給管などに触媒賦活物質濃度の計測装置を設けていてもよい。この出力値を用いてフィードバック制御することにより、経時変化の少ない安定な触媒賦活物質の供給を行うことができる。
搬送ユニットとは、少なくともフォーメーションユニットから成長ユニットまで基板を搬送するために必要な装置一式のことである。具体的には、ベルトコンベア方式におけるメッシュベルト、減速機付き電動モータを用いた駆動装置等などが挙げられる。
ガス混入防止手段とは各ユニットの内部が互いに空間的に接続される接続部に設置され、各ユニットの炉内空間内へガスが相互に混入することを防ぐ機能を実現するための装置一式のことである。例えば、基板のユニットからユニットへの移動中以外の時間は各ユニットの空間的接続を機械的に遮断するゲートバルブ装置、不活性ガス噴射によって遮断するガスカーテン装置、接続部、各ユニットの接続部近傍のガスを系外に排出する排気装置、などが挙げられる。ガス混入防止を確実に行うためには、シャッター及びガスカーテンは排気装置と併用することが好ましい。また連続成長を効率的に行う観点から、基板のユニット-ユニット間搬送を途切れなく行うため、また機構の簡素化の観点からは、排気装置を単独で用いることがより好ましい。フォーメーション炉内還元ガス環境中の炭素原子個数濃度を好ましくは5×1022個/m3以下、より好ましくは1×1022個/m3以下に保つように、ガス混入防止手段が機能する必要がある。
ここでDは混入を防止したいガスの拡散係数、Sはガス混入を防止する境界の断面積、Lは排気部の長さ(炉長方向)である。この条件式を満たし、かつ装置全体の給排気バランスを保つように各排気部の排気量は設定される。
原料ガスがフォーメーション炉内空間に混入すると、CNTの成長に悪影響を及ぼす。フォーメーション炉内還元ガス環境中の炭素原子個数濃度を好ましくは5×1022個/m3以下、より好ましくは1×1022個/m3以下に保つように、ガス混入防止手段により原料ガスのフォーメーション炉内への混入を防止すると良い。ここで炭素原子個数濃度は、還元ガス環境中の各ガス種(i=1、2、・・・)に対して、濃度(ppmv)をD1、D2・・・、標準状態での密度(g/m3)をρ1、ρ2・・・、分子量をM1、M2・・・、ガス分子1つに含まれる炭素原子数をC1、C2・・・、アボガドロ数をNAとして
各ユニットの炉内空間を空間的に接続し、基材がユニットからユニットへ搬送される時に、基材が外気に曝されることを防ぐための装置一式のことである。具体的には、基材周囲環境と外気を遮断し、基材をユニットからユニットへ通過させることができる炉又はチャンバなどが挙げられる。
冷却ユニットとは、CNT配向集合体が成長した基材を冷却するために必要な装置一式のことである。成長工程後のCNT配向集合体、触媒、基材の酸化防止と冷却を実現する機能を有する。例えば、不活性ガスを保持するための冷却炉、水冷式の場合は冷却炉内空間を囲むように配置した水冷冷却管、空冷式の場合は冷却炉内空間に不活性ガスを噴射する噴射部等が挙げられる。また、水冷方式と空冷方式を組み合わせても良い。
出口パージ部とは基材出口から装置炉内へ外部空気が混入することを防止するための装置一式のことである。基材の周囲環境をパージガス環境にする機能を有する。例えば、パージガス環境を保持するための炉又はチャンバ、パージガスを噴射するための噴射部等が挙げられる。パージガスは不活性ガスが好ましく、特に安全性、コスト、パージ性等の点から窒素であることが好ましい。ベルトコンベア式など基材出口が常時開口している場合は、パージガス噴射部としてパージガスを上下からシャワー状に噴射するガスカーテン装置とし、装置出口から外部空気が混入することを防止することが好ましい。
還元ガス、原料ガス、触媒賦活物質の噴射部として、基材の触媒形成面を臨む位置に設けられた複数の噴出孔を備えるシャワーヘッドを用いてもよい。臨む位置とは、各噴出孔の、噴射軸線が基板の法線と成す角が0以上90°未満となるように設けられている。つまりシャワーヘッドに設けられた噴出孔から噴出するガス流の方向が、基板に概ね直交するようにされている。
製造装置その1における合成炉、基材ホルダー、ガス噴射部等、製造装置その2におけるフォーメーション炉、還元ガス噴射部、成長炉、原料ガス噴射部、メッシュベルト、ガス混入防止手段の排気部、接続部の炉等の各部品は還元ガス又は原料ガスに曝される。それら部品の材質としては、高温に耐えられ、加工の精度と自由度、コストの点から耐熱合金が好ましい。耐熱合金としては、耐熱鋼、ステンレス鋼、ニッケル基合金等が挙げられる。Feを主成分として他の合金濃度が50%以下のものが耐熱鋼と一般に呼ばれる。また、Feを主成分として他の合金濃度が50%以下であり、Crを約12%以上含有する鋼は一般にステンレス鋼と呼ばれる。また、ニッケル基合金としては、NiにMo、Cr及びFe等を添加した合金が挙げられる。具体的には、SUS310、インコネル600、インコネル601、インコネル625、インコロイ800、MCアロイ、Haynes230アロイなどが耐熱性、機械的強度、化学的安定性、低コストなどの点から好ましい。
溶融アルミニウムめっき処理とは、溶融アルミニウム浴中に被めっき材料を浸漬することによって被めっき材の表面にアルミニウム又はアルミニウム合金層を形成する処理を言う。例えば、その処理方法は、被めっき材(母材)の表面を洗浄した(前処理)後、約700°C溶融アルミニウム浴中に浸漬させることによって、母材表面中へ溶融アルミニウムの拡散を起こさせ、母材とアルミの合金を生成し、浴より引上げ時にその合金層にアルミニウムを付着させる。さらに、その後に、表層のアルミナ層並びにアルミ層を低温熱拡散処理し、その下のFe-Al合金層を露出させる処理を行ってもよい。
耐熱合金を算術平均粗さRa≦2μmにするための研磨処理方法としては、バフ研磨に代表される機械研磨、薬品を利用する化学研磨、電解液中にて電流を流しながら研磨する電解研磨、機械研磨と電解研磨を組み合わせた複合電解研磨などが挙げられる。
算術平均粗さRaの定義は「JIS B 0601:2001」を参照されたい。
比表面積とは液体窒素の77Kでの吸脱着等温線を測定し、この吸脱着等温曲線からBrunauer,Emmett,Tellerの方法から計測した値のことである。比表面積は、BET比表面積測定装置((株)マウンテック製HM model-1210)を用いて測定した。
G/D比とはCNTの品質を評価するのに一般的に用いられている指標である。ラマン分光装置によって測定されるCNTのラマンスペクトルには、Gバンド(1600cm-1付近)とDバンド(1350cm-1付近)と呼ばれる振動モードが観測される。GバンドはCNTの円筒面であるグラファイトの六方格子構造由来の振動モードであり、Dバンドは結晶欠陥由来の振動モードである。よって、GバンドとDバンドのピーク強度比(G/D比)が高いものほど、欠陥量が少なく品質の高いCNTと評価できる。
本願でいう表面粗さは、算術平均粗さRaである。そのRaの値は、レーザー顕微鏡(株式会社キーエンス製VK-9710)を用いて、下記測定条件で測定した。
・測定モード:表面形状
・測定品質:高精細
・対物レンズ:CF IC EPI Plan 10×
・測定エリア面積:1.42mm2(1.42mm×1.0mm)
・Z方向測定ピッチ:0.1μm
・解析ソフトウェア((株)キーエンス社製VK形状解析アプリケーションVK-H1A1の「表面粗さ」計測機能により、測定で得られた高さデータのRaを求めた。
以下に具体的な実施例を挙げて本発明によるCNT配向集合体の製造装置についてより詳細に説明する。
1.被めっき材料の表面を洗浄・乾燥
2.約710℃の溶融アルミニウム浴中に10~30分浸漬
3.常温まで空冷
4.12%の希塩酸にて酸洗い後、水洗い、乾燥
5.900℃以下で大気中で熱処理
を行った。
触媒基板の製作条件を以下に説明する。基板として90mm角、厚さ0.3mmのFe-Ni-Cr合金YEF426(日立金属株式会社製、Ni42%、Cr6%)を使用した。レーザー顕微鏡を用いて表面粗さを測定したところ、算術平均粗さRa≒2.1μmであった。この基板の表裏両面にスパッタリング装置を用いて厚さ20nmのアルミナ膜を製膜し、次いで表面のみにスパッタリング装置を用いて厚さ1.0nmの鉄膜(触媒金属層)を製膜した。
・パージガス:窒素60000sccm
フォーメーションユニット102
・炉内温度:830℃
・還元ガス:窒素11200sccm、水素16800sccm
・処理時間:28分
ガス混入防止手段103
・排気部103a排気量:20sLm
・排気部103b排気量:25sLm
・排気部103c排気量:20sLm
成長ユニット104
・炉内温度:830℃
・原料ガス:窒素16040sccm、エチレン1800sccm、
水蒸気含有窒素160sccm(水分量16000ppmv)
・処理時間:11分
冷却ユニット105
・冷却水温度:30℃
・不活性ガス:窒素10000sccm
・冷却時間:30分
出口パージ部106
・パージガス:窒素50000sccm
フォーメーション/成長ユニットの炉及び噴射部、ガス混入防止手段の排気部、メッシュベルト、接続部の各材質はSUS310とし、その表面は溶融アルミニウムめっき処理を施した。算術平均粗さRaは3.4μm~8.0μmであった(表面粗さの測定においてz方向測定範囲は316μm)。溶融アルミニウムめっき処理の方法は、実施例2と同様に行った。
触媒を担持した基材の製作条件は実施例1と同様である。本実施例の製造装置及び製造条件は合成炉、基材ホルダー、ガス噴射部の材質及びその表面処理を除いて実施例1と同様である。本実施例において、合成炉、基材ホルダー、ガス噴射部の材質はインコネル601であり、その表面は算術平均粗さRa=1.4~1.9μmとなるように、サンドブラスト処理及びサンドペーパー、研磨剤により研磨処理を行った(表面粗さの測定においてz方向測定範囲は293μm)。
触媒を担持した基材の製作条件は実施例2と同様である。本実施例の製造装置及び製造条件はフォーメーション/成長ユニットの炉及び噴射部、ガス混入防止手段の排気部、メッシュベルト、接続部の材質及びその表面処理を除いて実施例2と同様である。本実施例において、フォーメーション/成長ユニットの炉及び噴射部、ガス混入防止手段の排気部、メッシュベルト、接続部の材質はインコネル601であり、その表面は算術平均粗さRa=1.4~1.9μmとなるように、サンドブラスト処理及びサンドペーパー、研磨剤により研磨処理を行った(表面粗さの測定においてz方向測定範囲は293μm)。
触媒を担持した基材の製作条件は実施例1と同様である。本比較例の製造装置及び製造条件は合成炉、基材ホルダー、ガス噴射部の材質及びその表面処理を除いて実施例1と同様である。本比較例において、合成炉、基材ホルダー、ガス噴射部の材質はインコネル601であり、その表面は算術平均粗さRa=3.2~4.1μmとなるように、サンドブラストによる粗面処理が行われている(表面粗さの測定においてz方向測定範囲は364μm)。
102:フォーメーションユニット
102a:フォーメーション炉
102b:還元ガス噴射部
102c:ヒーター
103:ガス混入防止手段
103a~103c:排気部
104:成長ユニット
104a:成長炉
104b:原料ガス噴射部
104c:ヒーター
105:冷却ユニット
105a:冷却炉
105b:冷却ガス噴射部
105c:水冷冷却管
106:出口パージ部
107:搬送ユニット
107a:メッシュベルト
107b:ベルト駆動部
108~110:接続部
111:触媒基板(基材)
301:触媒基板(基材)
304:合成炉
305:加熱器
302:基材ホルダー
303:ガス噴射部
306:排気口
Claims (4)
- 基材表面に形成された触媒の周囲環境を還元ガス環境とすると共に前記触媒及び前記還元ガスのうち少なくとも一方を加熱した後、前記触媒の周囲環境を原料ガス環境とすると共に前記触媒及び前記原料ガスのうち少なくとも一方を加熱してカーボンナノチューブ配向集合体を成長させるカーボンナノチューブ配向集合体の製造装置であって、
前記還元ガスに曝される装置部品及び前記原料ガスに曝される装置部品のうち少なくとも1つの装置部品の材質が耐熱合金であり、かつその表面が溶融アルミめっき処理されていることを特徴とするカーボンナノチューブ配向集合体の製造装置。 - 前記触媒の周囲環境を前記還元ガス環境とすると共に前記触媒及び前記還元ガスのうち少なくとも一方を加熱するフォーメーションユニットと、
前記触媒の周囲環境を前記原料ガス環境とすると共に前記触媒及び前記原料ガスのうち少なくとも一方を加熱して前記カーボンナノチューブ配向集合体を成長させる成長ユニットと、
少なくとも前記フォーメーションユニットから前記成長ユニットまで前記基材を搬送する搬送ユニットと、
を備えることを特徴とする請求項1に記載のカーボンナノチューブ配向集合体の製造装置。 - 基材表面に形成された触媒の周囲環境を還元ガス環境とすると共に前記触媒及び前記還元ガスのうち少なくとも一方を加熱した後、前記触媒の周囲環境を原料ガス環境とすると共に前記触媒及び前記原料ガスのうち少なくとも一方を加熱してカーボンナノチューブ配向集合体を成長させるカーボンナノチューブ配向集合体の製造装置であって、
前記還元ガスに曝される装置部品及び前記原料ガスに曝される装置部品のうち少なくとも1つの装置部品の材質が耐熱合金であり、かつその表面が算術平均粗さRa≦2μmに研磨処理されていることを特徴とするカーボンナノチューブ配向集合体の製造装置。 - 前記触媒の周囲環境を前記還元ガス環境とすると共に前記触媒及び前記還元ガスのうち少なくとも一方を加熱するフォーメーションユニットと、
前記触媒の周囲環境を前記原料ガス環境とすると共に前記触媒及び前記原料ガスのうち少なくとも一方を加熱して前記カーボンナノチューブ配向集合体を成長させる成長ユニットと、
少なくとも前記フォーメーションユニットから前記成長ユニットまで前記基材を搬送する搬送ユニットと、
を備えることを特徴とする請求項3に記載のカーボンナノチューブ配向集合体の製造装置。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10741067.2A EP2397441B1 (en) | 2009-02-10 | 2010-02-08 | Apparatus for producing oriented carbon nanotube aggregate |
CN2010800071399A CN102307808B (zh) | 2009-02-10 | 2010-02-08 | 取向碳纳米管集合体的制造装置 |
JP2010550447A JP5574265B2 (ja) | 2009-02-10 | 2010-02-08 | カーボンナノチューブ配向集合体の製造装置 |
KR1020117018653A KR101711676B1 (ko) | 2009-02-10 | 2010-02-08 | 카본 나노 튜브 배향 집합체의 제조 장치 |
US13/148,619 US9598285B2 (en) | 2009-02-10 | 2010-02-08 | Apparatus for producing aligned carbon nanotube aggregates |
US15/085,586 US20160207771A1 (en) | 2009-02-10 | 2016-03-30 | Apparatus for producing aligned carbon nanotube aggregates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009029128 | 2009-02-10 | ||
JP2009-029128 | 2009-02-10 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/148,619 A-371-Of-International US9598285B2 (en) | 2009-02-10 | 2010-02-08 | Apparatus for producing aligned carbon nanotube aggregates |
US15/085,586 Continuation US20160207771A1 (en) | 2009-02-10 | 2016-03-30 | Apparatus for producing aligned carbon nanotube aggregates |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010092787A1 true WO2010092787A1 (ja) | 2010-08-19 |
Family
ID=42561637
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/000743 WO2010092787A1 (ja) | 2009-02-10 | 2010-02-08 | カーボンナノチューブ配向集合体の製造装置 |
Country Status (6)
Country | Link |
---|---|
US (2) | US9598285B2 (ja) |
EP (1) | EP2397441B1 (ja) |
JP (1) | JP5574265B2 (ja) |
KR (1) | KR101711676B1 (ja) |
CN (1) | CN102307808B (ja) |
WO (1) | WO2010092787A1 (ja) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012165514A1 (ja) * | 2011-05-31 | 2012-12-06 | 日本ゼオン株式会社 | カーボンナノチューブ配向集合体の製造装置及び製造方法 |
WO2014097624A1 (ja) | 2012-12-20 | 2014-06-26 | 日本ゼオン株式会社 | カーボンナノチューブの製造方法 |
JP2015520717A (ja) * | 2012-04-16 | 2015-07-23 | シーアストーン リミテッド ライアビリティ カンパニー | 炭素酸化物触媒変換器中で金属触媒を使用するための方法 |
WO2016002715A1 (ja) * | 2014-07-01 | 2016-01-07 | 国立研究開発法人宇宙航空研究開発機構 | カーボンナノチューブの表面処理方法 |
JP2016088787A (ja) * | 2014-10-31 | 2016-05-23 | 日本ゼオン株式会社 | カーボンナノチューブ配向集合体の製造方法 |
US9731970B2 (en) | 2012-04-16 | 2017-08-15 | Seerstone Llc | Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides |
US9796591B2 (en) | 2012-04-16 | 2017-10-24 | Seerstone Llc | Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products |
WO2018163957A1 (ja) * | 2017-03-09 | 2018-09-13 | 大陽日酸株式会社 | カーボンナノチューブ、炭素系微細構造物、及びカーボンナノチューブ付き基材、並びにそれらの製造方法 |
JP2018145080A (ja) * | 2017-03-09 | 2018-09-20 | 大陽日酸株式会社 | カーボンナノチューブの製造方法、カーボンナノチューブ、及び配向カーボンナノチューブ付き基材 |
US10106416B2 (en) | 2012-04-16 | 2018-10-23 | Seerstone Llc | Methods for treating an offgas containing carbon oxides |
JP2018184319A (ja) * | 2017-04-26 | 2018-11-22 | 大陽日酸株式会社 | 炭素系微細構造物、及び炭素系微細構造物の製造方法 |
US11752459B2 (en) | 2016-07-28 | 2023-09-12 | Seerstone Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3015425A4 (en) * | 2013-06-27 | 2016-09-07 | Zeon Corp | METHOD FOR PRODUCING CARBON NANOTONES |
FR3050449B1 (fr) | 2016-04-25 | 2018-05-11 | Nawatechnologies | Installation pour la fabrication d'un materiau composite comprenant des nanotubes de carbone, et procede de mise en oeuvre de cette installation |
CN107381539B (zh) * | 2016-05-17 | 2019-10-25 | 北京睿曼科技有限公司 | 一种阵列碳纳米薄膜的制备方法 |
CN107381538B (zh) * | 2016-05-17 | 2019-10-25 | 北京睿曼科技有限公司 | 一种碳纳米管的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006016232A (ja) * | 2004-06-30 | 2006-01-19 | Hitachi Zosen Corp | カーボンナノチューブの連続製造方法およびその装置 |
WO2007141558A2 (en) * | 2006-06-09 | 2007-12-13 | Statoilhydro Asa | Carbon nano-fibre production |
WO2008096699A1 (ja) * | 2007-02-05 | 2008-08-14 | National Institute Of Advanced Industrial Science And Technology | 配向カーボンナノチューブの製造装置および製造方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5747119A (en) * | 1993-02-05 | 1998-05-05 | Kabushiki Kaisha Toshiba | Vapor deposition method and apparatus |
US5711821A (en) * | 1995-04-13 | 1998-01-27 | Texas Instruments Incorporated | Cleansing process for wafer handling implements |
US6303501B1 (en) * | 2000-04-17 | 2001-10-16 | Applied Materials, Inc. | Gas mixing apparatus and method |
JP4717179B2 (ja) * | 2000-06-21 | 2011-07-06 | 日本電気株式会社 | ガス供給装置及び処理装置 |
JP2002222767A (ja) * | 2001-01-26 | 2002-08-09 | Seiko Epson Corp | 真空装置用治具の形成方法 |
JP3768867B2 (ja) | 2001-12-03 | 2006-04-19 | 株式会社リコー | カーボンナノチューブの作製方法 |
CA2492597A1 (en) * | 2002-07-17 | 2004-01-22 | Hitco Carbon Composites, Inc. | Continuous chemical vapor deposition process and process furnace |
GB0329460D0 (en) * | 2003-12-19 | 2004-01-28 | Oxford Instr Plasma Technology | Apparatus and method for plasma processing |
US20050238810A1 (en) * | 2004-04-26 | 2005-10-27 | Mainstream Engineering Corp. | Nanotube/metal substrate composites and methods for producing such composites |
ATE526437T1 (de) | 2005-06-28 | 2011-10-15 | Univ Oklahoma | Verfahren zur züchtung und entnahme von kohlenstoffnanoröhren |
US20080274036A1 (en) | 2005-06-28 | 2008-11-06 | Resasco Daniel E | Microstructured catalysts and methods of use for producing carbon nanotubes |
JP2007091556A (ja) | 2005-09-30 | 2007-04-12 | Hitachi Zosen Corp | カーボン系薄膜の連続製造装置 |
JP4832046B2 (ja) | 2005-09-30 | 2011-12-07 | 日立造船株式会社 | 連続熱cvd装置 |
US8128750B2 (en) * | 2007-03-29 | 2012-03-06 | Lam Research Corporation | Aluminum-plated components of semiconductor material processing apparatuses and methods of manufacturing the components |
US8568555B2 (en) * | 2007-03-30 | 2013-10-29 | Tokyo Electron Limited | Method and apparatus for reducing substrate temperature variability |
US8016945B2 (en) * | 2007-12-21 | 2011-09-13 | Applied Materials, Inc. | Hafnium oxide ALD process |
-
2010
- 2010-02-08 CN CN2010800071399A patent/CN102307808B/zh active Active
- 2010-02-08 US US13/148,619 patent/US9598285B2/en active Active
- 2010-02-08 JP JP2010550447A patent/JP5574265B2/ja active Active
- 2010-02-08 WO PCT/JP2010/000743 patent/WO2010092787A1/ja active Application Filing
- 2010-02-08 EP EP10741067.2A patent/EP2397441B1/en active Active
- 2010-02-08 KR KR1020117018653A patent/KR101711676B1/ko active IP Right Grant
-
2016
- 2016-03-30 US US15/085,586 patent/US20160207771A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006016232A (ja) * | 2004-06-30 | 2006-01-19 | Hitachi Zosen Corp | カーボンナノチューブの連続製造方法およびその装置 |
WO2007141558A2 (en) * | 2006-06-09 | 2007-12-13 | Statoilhydro Asa | Carbon nano-fibre production |
WO2008096699A1 (ja) * | 2007-02-05 | 2008-08-14 | National Institute Of Advanced Industrial Science And Technology | 配向カーボンナノチューブの製造装置および製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2397441A4 * |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2716600A4 (en) * | 2011-05-31 | 2015-03-04 | Zeon Corp | APPARATUS AND METHOD FOR MANUFACTURING AN ORIENTED CARBON NANOTUBE AGGREGATE |
CN103562131A (zh) * | 2011-05-31 | 2014-02-05 | 日本瑞翁株式会社 | 取向碳纳米管集合体的制造装置及制造方法 |
US20140154416A1 (en) * | 2011-05-31 | 2014-06-05 | National Institute Of Advanced Industrial Science And Technology | Apparatus and method for producing oriented carbon nanotube aggregate |
WO2012165514A1 (ja) * | 2011-05-31 | 2012-12-06 | 日本ゼオン株式会社 | カーボンナノチューブ配向集合体の製造装置及び製造方法 |
US9731970B2 (en) | 2012-04-16 | 2017-08-15 | Seerstone Llc | Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides |
US9796591B2 (en) | 2012-04-16 | 2017-10-24 | Seerstone Llc | Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products |
US10106416B2 (en) | 2012-04-16 | 2018-10-23 | Seerstone Llc | Methods for treating an offgas containing carbon oxides |
JP2015520717A (ja) * | 2012-04-16 | 2015-07-23 | シーアストーン リミテッド ライアビリティ カンパニー | 炭素酸化物触媒変換器中で金属触媒を使用するための方法 |
US20150321917A1 (en) * | 2012-12-20 | 2015-11-12 | Zeon Corporation | Method of manufacturing carbon nanotubes |
US9815698B2 (en) | 2012-12-20 | 2017-11-14 | Zeon Corporation | Method of manufacturing carbon nanotubes |
WO2014097624A1 (ja) | 2012-12-20 | 2014-06-26 | 日本ゼオン株式会社 | カーボンナノチューブの製造方法 |
JP2016013943A (ja) * | 2014-07-01 | 2016-01-28 | 国立研究開発法人宇宙航空研究開発機構 | カーボンナノチューブの表面処理方法 |
WO2016002715A1 (ja) * | 2014-07-01 | 2016-01-07 | 国立研究開発法人宇宙航空研究開発機構 | カーボンナノチューブの表面処理方法 |
JP2016088787A (ja) * | 2014-10-31 | 2016-05-23 | 日本ゼオン株式会社 | カーボンナノチューブ配向集合体の製造方法 |
US11752459B2 (en) | 2016-07-28 | 2023-09-12 | Seerstone Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
US11951428B2 (en) | 2016-07-28 | 2024-04-09 | Seerstone, Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
WO2018163957A1 (ja) * | 2017-03-09 | 2018-09-13 | 大陽日酸株式会社 | カーボンナノチューブ、炭素系微細構造物、及びカーボンナノチューブ付き基材、並びにそれらの製造方法 |
JP2018145080A (ja) * | 2017-03-09 | 2018-09-20 | 大陽日酸株式会社 | カーボンナノチューブの製造方法、カーボンナノチューブ、及び配向カーボンナノチューブ付き基材 |
JP2018184319A (ja) * | 2017-04-26 | 2018-11-22 | 大陽日酸株式会社 | 炭素系微細構造物、及び炭素系微細構造物の製造方法 |
JP7015641B2 (ja) | 2017-04-26 | 2022-02-15 | 大陽日酸株式会社 | 炭素系微細構造物、及び炭素系微細構造物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2397441B1 (en) | 2022-11-09 |
US9598285B2 (en) | 2017-03-21 |
KR20110116028A (ko) | 2011-10-24 |
JP5574265B2 (ja) | 2014-08-20 |
US20160207771A1 (en) | 2016-07-21 |
CN102307808A (zh) | 2012-01-04 |
EP2397441A1 (en) | 2011-12-21 |
JPWO2010092787A1 (ja) | 2012-08-16 |
EP2397441A4 (en) | 2015-12-02 |
CN102307808B (zh) | 2013-07-10 |
US20110308462A1 (en) | 2011-12-22 |
KR101711676B1 (ko) | 2017-03-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5574265B2 (ja) | カーボンナノチューブ配向集合体の製造装置 | |
JP5471959B2 (ja) | カーボンナノチューブ配向集合体の製造装置及び製造方法 | |
JP5649225B2 (ja) | カーボンナノチューブ配向集合体の製造装置 | |
JP5590603B2 (ja) | カーボンナノチューブ配向集合体の製造装置 | |
JP5574264B2 (ja) | カーボンナノチューブ配向集合体生産用基材及びカーボンナノチューブ配向集合体の製造方法 | |
JP5622101B2 (ja) | カーボンナノチューブ配向集合体の製造方法 | |
WO2012165514A1 (ja) | カーボンナノチューブ配向集合体の製造装置及び製造方法 | |
JP5505785B2 (ja) | カーボンナノチューブ配向集合体の製造装置 | |
JP5700819B2 (ja) | カーボンナノチューブ配向集合体の製造方法 | |
JP2012126598A (ja) | 噴出装置、カーボンナノチューブ配向集合体の製造装置及び製造方法 | |
JP2012218953A (ja) | カーボンナノチューブ配向集合体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080007139.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10741067 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2010550447 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13148619 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20117018653 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010741067 Country of ref document: EP |