WO2005082528A1 - 触媒構造体およびこれを用いたカーボンナノチューブの製造方法 - Google Patents
触媒構造体およびこれを用いたカーボンナノチューブの製造方法 Download PDFInfo
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- WO2005082528A1 WO2005082528A1 PCT/JP2004/019538 JP2004019538W WO2005082528A1 WO 2005082528 A1 WO2005082528 A1 WO 2005082528A1 JP 2004019538 W JP2004019538 W JP 2004019538W WO 2005082528 A1 WO2005082528 A1 WO 2005082528A1
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- Prior art keywords
- catalyst
- crystal growth
- growth surface
- carbon
- carbon nanotubes
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- 239000003054 catalyst Substances 0.000 title claims abstract description 208
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 122
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 110
- 239000013078 crystal Substances 0.000 claims abstract description 109
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000000956 alloy Substances 0.000 claims description 24
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 238000010884 ion-beam technique Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000007420 reactivation Effects 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
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- 239000000758 substrate Substances 0.000 description 48
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 14
- 229910003481 amorphous carbon Inorganic materials 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
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- 230000015572 biosynthetic process Effects 0.000 description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 239000004215 Carbon black (E152) Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- 229910002696 Ag-Au Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- VAWNDNOTGRTLLU-UHFFFAOYSA-N iron molybdenum nickel Chemical compound [Fe].[Ni].[Mo] VAWNDNOTGRTLLU-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C01B32/162—Preparation characterised by catalysts
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to a catalyst structure and a method for producing carbon nanotubes using the same.
- the present invention relates to a catalyst structure for producing carbon nanotubes having a controlled shape and a large fiber length, and a method for producing carbon nanotubes using the same.
- Patent Document 1 discloses that a vapor-grown carbon fiber is generated in a floating state by heating a mixed gas of an organic transition metal compound gas, a carrier gas and an organic compound gas to 800 to 1300 ° C. A method is suggested!
- Patent Document 2 discloses a step of forming a catalytic metal film on a substrate, a step of etching the catalytic metal film to form separated nano-sized catalytic metal particles, and a thermochemical vapor deposition apparatus. Supplying a carbon source gas into the inside, growing carbon nanotubes for each nano-sized catalyst metal particle separated by thermal chemical vapor deposition, and forming a plurality of vertically aligned carbon nanotubes on the substrate.
- the step of forming the separated and nano-sized catalytic metal particles includes a gas etching method in which one of an etching gas selected from the group consisting of ammonia gas, hydrogen gas, and hydride gas is thermally decomposed and used. Has proposed a method for synthesizing carbon nanotubes.
- Patent Document 3 discloses that a hydrocarbon gas is sent together with a carrier gas onto a substrate in which catalyst fine particles are dispersed and supported on a heat-resistant porous carrier, and a single-layer carbon is produced by utilizing thermal decomposition of the hydrocarbon gas. A method for vapor phase synthesis of nanotubes has been proposed.
- Patent Document 4 discloses a method of producing a carbon nanotube on the surface of a metal by flowing a gas serving as a carbon source to a heated metal by a chemical vapor deposition method. A method has been proposed, characterized in that a treatment for forming fine irregularities on the metal surface is performed by generating microcrystals of the rough oxidized product.
- One of the causes of variations in the diameter of carbon nanotubes is variation in the size of catalyst particles.
- the catalyst particles are formed by a chemical method such as a thermal decomposition method, it is difficult to control the shape of the catalyst particles, so that the catalyst particles themselves vary in form.
- the morphology also varies due to the aggregation of the catalyst particles.
- the shape of the carbon nanotube tends to vary due to the variation in the growth rate of carbon crystals from the catalyst particles.
- Patent Document 1 JP-A-60-54998
- Patent Document 2 JP 2001-20071 A
- Patent Document 3 JP-A-2002-255519
- Patent Document 4 Patent No. 3421332
- the present invention solves the above-mentioned problems, and provides a catalyst structure capable of obtaining a carbon nanotube having a desired shape and a large fiber length stably and with high purity, and a carbon nanotube using the same. It is an object of the present invention to provide a method for producing the same.
- the present invention relates to a catalyst structure used for producing carbon nanotubes composed of carbon crystals by vapor phase growth, wherein the catalyst material has a ring shape or a spiral shape on the crystal growth surface.
- the present invention relates to a catalyst structure formed as follows.
- the catalyst structure of the present invention is a columnar body having a crystal growth surface as an upper surface, and has at least a part of a side surface of the columnar body substantially having a catalytic action on growth of a carbon crystal. It is preferred that non-catalytic materials be formed.
- the non-catalytic material is preferably at least one selected from Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt. Including the above.
- the catalyst material power also be at least one selected from the group consisting of Co, Mo, and N, and that the non-catalyst material also has the power of Ag and Z or an Ag-containing alloy.
- the catalyst material is preferably formed to have a multilayer structure.
- the crystal growth surface of the catalyst material has a wavy ring shape.
- the present invention also provides a catalyst structure in which a catalyst material is formed so as to form a ring shape or a spiral shape on a crystal growth surface, and a material gas is brought into contact with the crystal growth surface to cause the crystal growth.
- a catalyst material is formed so as to form a ring shape or a spiral shape on a crystal growth surface, and a material gas is brought into contact with the crystal growth surface to cause the crystal growth.
- the present invention relates to a method for producing carbon nanotubes by growing a carbon crystal in a vapor phase.
- the generation temperature of the carbon nanotube is set to be equal to or lower than the deformation temperature of the non-catalytic material.
- the “deformation temperature” refers to a temperature at which a non-catalytic material is deformed due to a thermal effect so that a desired carbon nanotube cannot be generated.
- the catalyst structure of the present invention can be used as an aggregate composed of a plurality of catalyst structures.
- a through hole can be provided between each catalyst structure.
- a material gas for generating carbon nanotubes be flowed in a direction perpendicular to the crystal growth surface.
- a non-catalytic material is formed in contact with at least a part of the side surface of the columnar aggregate formed by arranging the plurality of catalyst structures, and the non-catalytic material is formed on the crystal growth surface of the plurality of catalyst structures. It is preferable that the variation of the cross-sectional area of the catalyst material is set so that the CV is 10% or less.
- the crystal growth surface of the catalyst structure of the present invention is preferably subjected to sputtering. It is particularly preferable that the sputtering is performed using a cluster ion beam or an ultrashort pulse laser.
- the catalyst material in the present invention is preferably subjected to the reactivation treatment by one or more of chemical polishing, physical polishing, and sputtering.
- the invention's effect is preferably subjected to the reactivation treatment by one or more of chemical polishing, physical polishing, and sputtering.
- FIG. 1A is a diagram showing an example of a conventional catalyst.
- FIG. 1B is a view showing one example of a conventional catalyst.
- FIG. 2A is a view showing one example of a catalyst structure according to the present invention.
- FIG. 2B is a view showing one example of a catalyst structure according to the present invention.
- FIG. 2C is a view showing one example of a catalyst structure according to the present invention.
- FIG. 3 is a view showing a crystal growth surface of a typical catalyst structure according to the present invention.
- FIG. 4 is a view showing a crystal growth surface of a typical catalyst structure according to the present invention.
- FIG. 5 is a view showing a crystal growth surface of a typical catalyst structure according to the present invention.
- FIG. 6 is a view showing a crystal growth surface of a catalyst substrate formed by a plurality of catalyst structures.
- FIG. 7 is a view showing an example of an apparatus for producing carbon nanotubes.
- FIG. 8 is a view showing another example of the apparatus for producing carbon nanotubes.
- the crystal growth surface 12 of the granular catalyst 11 has a solid shape.
- a carbon crystal 13 grows from the entire surface of the crystal growth surface 12 to generate a carbon nanotube 14 having a cap portion.
- the present invention provides a method for producing a carbon nanotube by bringing a catalyst having a ring-shaped or spiral-shaped crystal growth surface into contact with a material gas containing carbon, and growing the carbon crystal in a vapor phase. Is generated.
- a catalyst having a ring-shaped or spiral-shaped crystal growth surface into contact with a material gas containing carbon, and growing the carbon crystal in a vapor phase.
- the catalyst structure of the present invention is preferably a columnar body, and a uniform crystal growth surface can be produced by making the crystal growth surface, which is the upper surface of the columnar body, a smooth surface.
- a region other than the catalyst material at the center of the crystal growth surface it becomes possible to produce carbon nanotubes having no closed cap at the tip and to increase the fiber length of carbon nanotubes.
- the catalyst structure is formed as a column having the crystal growth surface as the upper surface, and at least a part of the side surface of the column substantially acts as a catalyst for the growth of the carbon crystal.
- a non-catalytic material having no is formed.
- the non-catalytic material prevents the carbon crystal from spreading in the crystal growth plane direction during crystal growth, and the growth direction of the crystal is controlled, so that carbon nanotubes with a more uniform shape can be generated.
- the catalyst structure 21 of the present invention is formed as a columnar body in which the catalyst material has a ring shape on the crystal growth surface 22.
- the catalyst material may be formed to have a spiral shape.
- carbon nanotubes are produced using this catalyst structure 21, carbon nanotubes 24 reflecting the shape of the crystal growth surface 22 can be produced.
- the catalyst structure 21 is preferably formed in a pipe shape having side surfaces as shown in Figs. 2A to 2C.
- the catalyst structure 21 having a ring-shaped cross section serving as a crystal growth surface at least a part of the inner side surface 25 and the outer side surface 26 has a non-catalyst having no substantial catalytic action on the growth of the carbon crystal 23.
- the catalyst material is formed, the carbon nanotubes During the growth of the carbon nanotubes, variations in the form of the carbon nanotubes 24 due to the spread and growth of the carbon nanotubes in the direction of the crystal growth surface 22 are effectively suppressed. Thereby, carbon nanotubes having a uniform outer diameter and inner diameter can be manufactured.
- the shape of the catalyst structure according to the present invention is not limited to FIGS. 3-5, and may be any as long as the crystal growth surface has a ring shape or a spiral shape.
- the “ring shape” refers to any material in which the catalyst material forms a closed shape on the crystal growth surface, and is not limited to a circular shape.
- the crystal growth surface of the catalyst structure shown in FIG. 3 has a multilayer ring shape in which catalyst materials 31 and non-catalyst materials 32 are alternately formed.
- multi-walled carbon nanotubes of a desired shape are manufactured by adjusting the innermost and outermost diameters of the multi-layered ring shape on the crystal growth surface, and the width of the catalyst material and non-catalyst material. can do.
- the crystal growth surface of the catalyst structure shown in FIG. 4 has a spiral shape composed of a catalyst material 41 and a non-catalyst material 42.
- carbon nanotubes having a spiral cross section can be manufactured.
- the crystal growth surface of the catalyst structure shown in FIG. 5 has a corrugated ring shape because the catalytic material 51 surrounds the periphery of the corrugated non-catalytic material 52.
- carbon nanotubes having a corrugated ring-shaped cross section can be produced.
- the present invention it is possible to produce carbon nanotubes having a desired shape by variously changing the shape of the catalyst material on the crystal growth surface.
- the diameter of the ring shape or spiral shape on the crystal growth surface is not particularly limited, and the ring shape or spiral shape diameter may be appropriately selected according to the desired diameter of the carbon nanotube.
- a material gas for growing carbon nanotubes a hydrocarbon-based gas such as ethylene gas and acetylene gas, and an alcohol-based gas such as methyl alcohol gas and ethyl alcohol gas are used.
- Generally used gas can be used.
- catalytic and non-catalytic materials for example, relatively low deformation temperatures!
- carbon nanotubes at lower temperatures An alcohol-based gas that can be generated is preferably used.
- materials generally used in the production of carbon nanotubes can be used, and specific examples include Fe, Co, Mo, N, and alloys containing these. These can be used alone or in combination of two or more. Above all, Fe, Co or Fe-Co alloy materials are suitable in that they do not form an alloy or the like with Ag and do not deteriorate.
- the non-catalytic material of the present invention a material having substantially no catalytic action on the growth of carbon crystals is used, and specifically, Ag, Au, Ru, Rh, Pd, Os, Ir Noble metals such as Pt and Pt or alloys containing these noble metals can be preferably used. These can be used alone or as a combination of two or more. Among them, Ag and Ag-containing alloys are preferable because they are relatively inexpensive, easy to process, and chemically stable. As the Ag-containing alloy, an Ag—Pd alloy, an Ag—Pt alloy, or the like can be used.
- the deformation temperature of the non-catalytic material is preferably higher than the formation temperature of carbon nanotubes. In this case, it is possible to generate a carbon nanotube having a uniform shape, in which deformation of the non-catalytic material during crystal growth hardly occurs.
- the catalyst material and the non-catalyst material be a combination having a small risk of losing the shape of the catalyst due to the formation or reaction of an alloy caused by the mutual contact.
- a combination include a combination in which the catalyst material is an oxide, the non-catalyst material is Ag or an Ag-containing alloy, a combination in which the catalyst material is a nitride, and the non-catalyst material is Ag or an Ag-containing alloy, and the like.
- the catalyst structure of the present invention needs to be prepared in a nanometer-level minute shape according to the desired diameter of the carbon nanotube.
- a method of preparing a catalyst having a minute shape For example, a method of reducing the diameter to the nanometer level by repeatedly extruding, drawing, and fitting a catalyst material in the form of a pipe or a sheet, or a method of reducing the diameter of the catalyst material by repeating the process.
- a method of forming a fine pattern of a catalyst material on a substrate by trilithography or the like can be used.
- a column-shaped catalyst substrate having a columnar aggregate formed by a plurality of catalyst structures in which the directions of crystal growth surfaces are aligned In this case a lot of carbon Nanotubes can be manufactured efficiently.
- the carbon crystal spreads in the direction of the crystal growth surface by using a catalyst substrate in which the non-catalyst material 62 is preferably formed on the side surface of the aggregate formed by the plurality of catalyst structures 61. This prevents carbon nanotubes having a uniform shape from being produced with high production efficiency.
- a tunnel-shaped through-hole 63 is provided inside the catalyst substrate.
- the material gas When flowing the material gas such that the flow direction of the material gas is substantially perpendicular to the crystal growth surface, the material gas passes through the through-hole, thereby preventing the turbulent flow of the material gas near the catalyst substrate. Therefore, it is possible to manufacture carbon nanotubes with small shape irregularities and variations.
- the variation in the cross-sectional area of the catalyst material on the crystal growth surface of each catalyst structure forming the above-mentioned catalyst substrate be 10% or less in CV. If the variation in the cross-sectional area is 10% or less in CV, the shapes of the plurality of catalyst materials in the catalyst substrate are uniform, and the uniformity of the shape of the carbon nanotube to be produced is ensured.
- the cross-sectional area can be calculated, for example, by image analysis based on morphological observation with a scanning tunneling microscope (STM).
- an ion beam such as a cluster ion beam or the like may be used.
- Surface treatment such as chemical etching using a laser such as a short pulse laser or a chemical such as hydrogen peroxide solution can be performed.
- At least the crystal growth surface of the catalyst material is subjected to an oxidizing treatment by a method such as a heat treatment in an oxygen atmosphere.
- a method such as a heat treatment in an oxygen atmosphere.
- the catalytic activity of the catalyst material is reduced by using the catalyst structure of the present invention for the production of carbon nanotubes, at least one of chemical polishing, physical polishing, and sputtering is performed on the crystal growth surface.
- good catalytic activity can be imparted to the crystal growth surface again by reactivating.
- the catalyst structure once prepared can be reused through the reactivation treatment of the crystal growth surface, and as a result, the production cost of carbon nanotubes can be reduced.
- an electric furnace 71 as a heating apparatus, a quartz tube 72 provided with a gas introduction / exhaust system, a growth temperature control system, a vacuum control system, a gas flow meter, etc.
- a material gas such as methyl alcohol or ethyl alcohol and a carrier gas such as argon or nitrogen are caused to flow, and the crystal growth surface force of the catalyst substrate 73 also generates carbon nanotubes.
- a quartz tube provided with an electric furnace 81 as a heating apparatus, a gas introduction / exhaust system, a growth temperature control system, a vacuum control system, a gas flow meter, and the like.
- the catalyst base material 83 is placed in 82. Note that a large number of through holes are provided in the catalyst substrate 83.
- a catalyst substrate support 84 is provided on the periphery of the catalyst substrate 83. The material gas and the carrier gas are flowed in the directions of the arrows, and the surface growth of the crystal of the catalyst substrate 83 also generates carbon nanotubes.
- the crystal growth surface of catalyst base material 83 is substantially perpendicular to the flow direction of the material gas. Therefore, the grown carbon nanotubes are affected by the flow of the material gas 1, and tend to be able to grow stably in a direction perpendicular to the crystal growth surface. Further, in the example of FIG. 8, the presence of the catalyst substrate support 84 suppresses the turbulent flow of the material gas in the vicinity of the catalyst substrate 83, so that the carbon nanotubes can be more stably grown.
- the formation temperature of the carbon nanotube is not particularly limited, and may be appropriately selected depending on the properties of the applied catalyst material or non-catalyst material, the type of the material gas, and the like. Can be done.
- the apparatus for producing carbon nanotubes used in the present invention may be configured so that the carbon nanotubes can be purified after the carbon nanotubes are generated by, for example, providing a purification gas supply mechanism or the like.
- the carbon nanotubes produced by using the catalyst structure of the present invention have a uniform shape and a large fiber length, and are suitable for various uses such as electronic circuits, high-strength composite materials, electric wire materials, and sealing materials. Can be applied.
- the wire 1 was cut into bundles each having a length of lm, bundled, filled in an Ag pipe having an outer diameter of 60 mm and an inner diameter of 50 mm, and subjected to wire drawing until the outer diameter became 1.2 mm, to obtain a wire 2.
- the aggregate is cut into a length of 10 mm, and a circular cross section serving as a crystal growth surface is polished with an abrasive. Then, a cluster ion beam is used to expose the Fe portion to the crystal growth surface. A surface treatment was performed to prepare a catalyst substrate. A crystal growth surface within a 1 m square area selected at random from the formed catalyst substrate was observed with a scanning tunneling microscope (STM), and the cross-sectional area of the catalyst material in each catalyst structure was calculated. The area variation was determined by the following equation. As a result, the variation of the cross-sectional area of the catalyst material on the crystal growth surface was less than 10% in CV (%).
- STM scanning tunneling microscope
- CV (%) Standard deviation of all measured values Z Average value of all measured values X 100
- carbon nanotubes were produced by the production apparatus shown in FIG.
- the catalyst substrate was placed in a quartz tube in a quartz boat, and the temperature in the electric furnace was set to 600 ° C, which is the temperature at which carbon nanotubes were formed, while flowing argon gas. Thereafter, the supply of argon was stopped, and while the quartz tube was depressurized with a vacuum pump, ethyl alcohol vapor was flowed into the quartz tube. As a result, fibrous carbon was visually observed.
- an iron-cobalt (Fe-Co) alloy pipe with an inner diameter of 20 mm was inserted, and a silver palladium (Ag-Pd) alloy rod with an outer diameter of about 20 mm was inserted inside the pipe.
- the composite metal material was extruded and extruded until the outer diameter became 1 mm, and a wire 1 was obtained.
- Wire 1 was cut into bundles of length lm, bundled, filled into an Ag pipe having an outer diameter of 100mm and an inner diameter of 80mm, and then drawn until the outer diameter became 5mm to obtain a wire 2. .
- An aluminum (A1) rod having an outer diameter of 40mm was inserted into an Ag pipe having an outer diameter of 50mm and an inner diameter of 40mm, and drawn to a diameter of 5mm to obtain a wire rod A1.
- the wire 2 and the wire A1 are cut into pieces each having a length of lm, bundled uniformly so that the wire 2 and the wire A1 are mixed, and filled into an Ag pipe having an outer diameter of 100 mm and an inner diameter of 80 mm.
- the wire was processed to obtain a wire 3.
- the wire 3 was cut into pieces of length lm, bundled, filled into an Ag pipe having an outer diameter of 100mm and an inner diameter of 80mm, and then drawn until the outer diameter of the wire 3 became about 10mm. Then, an aggregate was prepared by bundling a plurality of catalyst structures each having an outer diameter of about 25 nm and an inner diameter of about 12 nm of the Fe—Co alloy.
- the aggregate is cut into a length of about lmm, and the cross section, which is the crystal growth surface, is polished with an abrasive until the length becomes 0.1mm, and A1 is eluted in an aqueous solution of potassium hydroxide. As a result, a through hole having a diameter of about 40 ⁇ m was formed.
- the crystal growth surface is polished with a puff abrasive, and the crystal growth surface is etched with a femtosecond laser so that the Fe—Co alloy portion is exposed on the crystal growth surface.
- the surface of the crystal growth surface was processed with a steam to produce the catalyst substrate shown in FIG.
- carbon nanotubes were produced by the production apparatus shown in FIG.
- the catalyst base and the catalyst base support were placed in a quartz tube, and fixed so that most of the gas flow passed through the through holes in the catalyst base.
- the temperature in the electric furnace was set to 700 ° C while flowing argon gas. Thereafter, the supply of argon was stopped, and methyl alcohol vapor was flown into the quartz tube while the quartz tube was depressurized by a vacuum pump. As a result, fibrous carbon was visually observed, and it was confirmed that the carbon nanotubes grew from the crystal growth surface of the catalyst substrate. According to TEM (transmission electron microscope) observation, by-products such as amorphous carbon and graphite were hardly generated.
- the wire 1 was cut into bundles each having a length of lm, bundled, and filled into an Ag pipe having an outer diameter of 60 mm and an inner diameter of 50 mm, and then drawn until the outer diameter became 1.2 mm, thereby producing a wire 2.
- the process of obtaining wire 2 from wire 1 was repeated, and finally the outer diameter of Fe was set to about 10 nm, the inner diameter was set to about 8 nm, and the outer diameter of Fe-Co alloy was set to about 6 nm, and the inner diameter was set to about 4 nm
- An aggregate was obtained in which a plurality of catalyst structures were bundled.
- the catalyst base material was cut to a length of 10 mm, and the cross section, which was the crystal growth surface, was polished with an abrasive. Then, a cluster ion beam was used so that the Fe portion and the Fe-Co alloy portion were exposed on the crystal growth surface.
- a catalyst substrate was obtained by subjecting the surface to a surface treatment, and further etching the crystal growth surface with a solution containing hydrogen peroxide and ammonium hydroxide.
- Wire 1 is cut into bundles of length lm, bundled, filled into an Ag pipe having an outer diameter of 60 mm and an inner diameter of 50 mm, and then drawn until the outer diameter becomes 1.2 mm to produce a wire 2. did.
- the obtained aggregate is cut to a length of lm, and a cross section to be a crystal growth surface is polished with an abrasive, and then etched so that the Fe-Ni-Mo alloy portion is exposed on the crystal growth surface.
- Surface treatment was performed by processing. Thereafter, heat treatment was performed at a temperature of 800 ° C. in an oxygen atmosphere.
- the assembly is drawn so that the diameter of the assembly becomes 2Z3, cut to a length of 10 mm so that the polished surface is exposed at the end, and subjected to cluster ion beam processing to obtain a catalyst base material.
- carbon nanotubes were produced by the production apparatus shown in FIG. Put the catalyst substrate in a quartz tube with the quartz boat The temperature inside the electric furnace was set to 850 ° C while flowing Lugon gas. Thereafter, the supply of argon gas was stopped, and ethyl alcohol vapor was flown into the quartz tube while the inside of the quartz tube was depressurized by a vacuum pump. As a result, fibrous carbon was visually observed, and it was confirmed that carbon nanotubes were formed on the crystal growth surface. According to TEM (transmission electron microscope) observation, almost no by-products such as amorphous carbon and graphite were formed.
- TEM transmission electron microscope
- a Fe sheet and an Ag sheet each having a thickness of lmm are tightly wound around the outside of an Ag rod with an outer diameter of 10mm so that there is no gap as much as possible. The gap was empty.
- the composite metal material was drawn by wire drawing to an outer diameter of 1.2 mm to produce a wire 1.
- Wire 1 was cut into bundles of length lm, bundled, filled into an Ag pipe with an outer diameter of 60mm and an inner diameter of 50mm, and then drawn until the outer diameter became 1.2mm to produce wire 2. did.
- the obtained aggregate was cut into a length of 10 mm, and the cross section serving as the crystal growth surface was polished with an abrasive. Then, the surface was irradiated with a cluster ion beam so that the Fe portion was exposed on the crystal growth surface. After treatment, a catalyst substrate was obtained.
- the composite sheet of Fe and Ag is coated with the overall force Fe of the Ag sheet.
- the composite metal rod was subjected to wire drawing until the outer diameter became lmm, thereby producing a wire rod 1.
- the wire 1 was cut into bundles of length lm, bundled, filled into an Ag pipe having an outer diameter of 60 mm and an inner diameter of 50 mm, and then drawn until the outer diameter became 1.2 mm.
- the obtained aggregate is cut into a length of 10 mm, and the cross section serving as a crystal growth surface is polished with an abrasive. Then, the surface is irradiated with a cluster ion beam so that the Fe portion is exposed on the crystal growth surface. After treatment, a catalyst substrate was obtained.
- carbon nanotubes were produced by the production apparatus shown in FIG.
- the catalyst substrate was placed in a quartz tube in a state of being placed on a quartz boat, and the temperature in the electric furnace was set to the carbon nanotube formation temperature (500 ° C) while flowing argon gas. Thereafter, the supply of argon gas was stopped, and ethyl alcohol vapor was flown into the quartz tube while the inside of the quartz tube was depressurized by a vacuum pump. As a result, fibrous carbon was visually observed, and it was confirmed that the carbon nanotubes had a crystal growth surface force. By TEM (transmission electron microscope) observation, almost no by-products such as amorphous carbon and graphite were generated.
- Example 1 was repeated except that the catalyst structure of Example 1 was replaced with a catalyst material in which Fe fine particles having an average particle size of about 1 Onm generated by thermal decomposition of Fe-mouth oxide were supported on an alumina substrate.
- a catalyst material in which Fe fine particles having an average particle size of about 1 Onm generated by thermal decomposition of Fe-mouth oxide were supported on an alumina substrate.
- the formation of carbon nanotubes was observed.
- a large amount of by-products such as amorphous carbon and graphite were generated.
- the Fe fine particles were observed with a TEM (transmission electron microscope) and analyzed by image analysis.
- the CV (%) showed a large variation of 200% or more in a 1 ⁇ m square visual field arbitrarily selected.
- Example 2 Same as Example 2 except that the catalyst material of Example 2 was replaced with a catalyst material in which Fe fine particles having an average particle diameter of about 7 nm generated by thermal decomposition of Fe When carbon nanotubes were grown by the above method, the formation of carbon nanotubes was observed. A large amount of by-products such as amorphous carbon and graphite were generated.
- Example 3 The same as Example 3, except that the catalyst material of Example 3 was replaced by a catalyst material in which Fe fine particles having an average particle size of about 10 ⁇ m produced by thermal decomposition of Fe When carbon nanotubes were grown by the above method, the formation of carbon nanotubes was observed. A large amount of by-products such as amorphous carbon and graphite were generated.
- Example 4 Same as Example 4, except that the catalyst material of Example 4 was replaced with a catalyst material in which Fe fine particles having an average particle diameter of about 10 ⁇ m generated by thermal decomposition of Fe When the carbon nanotubes were grown by the method described in (1), the formation of carbon nanotubes was observed at the same time that a large amount of by-products such as amorphous carbon and graphite were generated.
- Example 5 Same as Example 5, except that the catalyst material of Example 5 was replaced with a catalyst material in which Fe fine particles having an average particle size of about 10 ⁇ m generated by thermal decomposition of Fe When carbon nanotubes were grown by the above method, the formation of carbon nanotubes was observed. A large amount of by-products such as amorphous carbon and graphite were generated.
- Example 6 instead of the catalyst substrate of Example 6, the average particle size of about 10 ⁇ Carbon nanotubes were grown in the same manner as in Example 6 except that a catalyst material in which m Fe particles were supported on an alumina substrate was used. A large amount of by-products such as aite were also produced.
- the catalyst material formed a hollow shape on the crystal growth surface, thereby almost producing by-products such as amorphous carbon and graphite. Is that carbon nanotubes with a large fiber length can be stably manufactured.
- carbon nanotubes having a desired shape and a large fiber length can be stably produced with high purity.
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Abstract
Description
Claims
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CN2004800420110A CN1917958B (zh) | 2004-02-27 | 2004-12-27 | 催化剂结构体和用其制备碳纳米管的方法 |
CA2551739A CA2551739C (en) | 2004-02-27 | 2004-12-27 | Catalyst structure and method of manufacturing carbon nanotube using the same |
EP04807893A EP1719556A4 (en) | 2004-02-27 | 2004-12-27 | STRUCTURE OF CATALYST AND METHOD FOR MANUFACTURING CARBON NANOTUBE USING THE SAME |
US10/590,011 US8592338B2 (en) | 2004-02-27 | 2004-12-27 | Catalyst structure and method of manufacturing carbon nanotube using the same |
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JP2004052896A JP4834957B2 (ja) | 2004-02-27 | 2004-02-27 | 触媒構造体およびこれを用いたカーボンナノチューブの製造方法 |
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US (1) | US8592338B2 (ja) |
EP (1) | EP1719556A4 (ja) |
JP (1) | JP4834957B2 (ja) |
KR (1) | KR101006262B1 (ja) |
CN (1) | CN1917958B (ja) |
CA (1) | CA2551739C (ja) |
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US20090123649A1 (en) * | 2006-06-15 | 2009-05-14 | Telecommunications Research Institute | Method of manufacturing silicon nanotubes using doughnut-shaped catalytic metal layer |
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JP4379247B2 (ja) * | 2004-04-23 | 2009-12-09 | 住友電気工業株式会社 | カーボンナノ構造体の製造方法 |
JP4604563B2 (ja) * | 2004-06-08 | 2011-01-05 | 住友電気工業株式会社 | カーボンナノ構造体の製造方法 |
KR100773151B1 (ko) * | 2006-04-05 | 2007-11-02 | 금호전기주식회사 | 탄소나노계 물질을 이용한 전계방출램프용의 음극선제조방법 |
JP2010099572A (ja) * | 2008-10-22 | 2010-05-06 | Sumitomo Electric Ind Ltd | 触媒基材およびこれを用いたカーボンナノ構造体の製造方法 |
GB0913011D0 (en) * | 2009-07-27 | 2009-09-02 | Univ Durham | Graphene |
US9371232B2 (en) * | 2012-10-29 | 2016-06-21 | Bryan Edward Laubscher | Trekking atom nanotube growth |
CN103022422A (zh) * | 2012-11-26 | 2013-04-03 | 同济大学 | 一种活化碳纳米管/氧化铁锂离子电池电极材料的制备方法 |
JP2013126942A (ja) * | 2013-01-28 | 2013-06-27 | Ulvac Japan Ltd | カーボンナノチューブの作製方法 |
EP3129135A4 (en) | 2013-03-15 | 2017-10-25 | Seerstone LLC | Reactors, systems, and methods for forming solid products |
US20160030925A1 (en) * | 2013-03-15 | 2016-02-04 | Seerstone Llc | Methods and systems for forming catalytic assemblies, and related catalytic assemblies |
US9586823B2 (en) | 2013-03-15 | 2017-03-07 | Seerstone Llc | Systems for producing solid carbon by reducing carbon oxides |
US9783416B2 (en) | 2013-03-15 | 2017-10-10 | Seerstone Llc | Methods of producing hydrogen and solid carbon |
WO2014151119A2 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Electrodes comprising nanostructured carbon |
JP6376009B2 (ja) * | 2015-03-16 | 2018-08-22 | 日本ゼオン株式会社 | 再利用基材の製造方法、カーボンナノチューブ生成用触媒基材の製造方法およびカーボンナノチューブの製造方法 |
WO2018022999A1 (en) | 2016-07-28 | 2018-02-01 | Seerstone Llc. | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
CN109449138B (zh) * | 2018-09-28 | 2022-09-02 | 杭州电子科技大学 | 一种差分多比特硅通孔结构及其制备方法 |
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- 2004-02-27 JP JP2004052896A patent/JP4834957B2/ja not_active Expired - Fee Related
- 2004-12-27 KR KR1020067014341A patent/KR101006262B1/ko active IP Right Grant
- 2004-12-27 US US10/590,011 patent/US8592338B2/en not_active Expired - Fee Related
- 2004-12-27 WO PCT/JP2004/019538 patent/WO2005082528A1/ja active Application Filing
- 2004-12-27 CA CA2551739A patent/CA2551739C/en not_active Expired - Fee Related
- 2004-12-27 EP EP04807893A patent/EP1719556A4/en not_active Ceased
- 2004-12-27 CN CN2004800420110A patent/CN1917958B/zh not_active Expired - Fee Related
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Publication number | Publication date |
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KR101006262B1 (ko) | 2011-01-06 |
CA2551739C (en) | 2012-03-27 |
CN1917958B (zh) | 2011-04-13 |
EP1719556A4 (en) | 2010-10-20 |
JP4834957B2 (ja) | 2011-12-14 |
US20070172409A1 (en) | 2007-07-26 |
EP1719556A1 (en) | 2006-11-08 |
KR20070004577A (ko) | 2007-01-09 |
CA2551739A1 (en) | 2005-09-09 |
TW200535093A (en) | 2005-11-01 |
JP2005238142A (ja) | 2005-09-08 |
CN1917958A (zh) | 2007-02-21 |
US8592338B2 (en) | 2013-11-26 |
TWI345554B (ja) | 2011-07-21 |
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