WO2004070095A1 - Fibre de carbone fine presentant diverses structures - Google Patents

Fibre de carbone fine presentant diverses structures Download PDF

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Publication number
WO2004070095A1
WO2004070095A1 PCT/JP2004/001400 JP2004001400W WO2004070095A1 WO 2004070095 A1 WO2004070095 A1 WO 2004070095A1 JP 2004001400 W JP2004001400 W JP 2004001400W WO 2004070095 A1 WO2004070095 A1 WO 2004070095A1
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WO
WIPO (PCT)
Prior art keywords
fine carbon
carbon fiber
cross
axial direction
fiber according
Prior art date
Application number
PCT/JP2004/001400
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English (en)
Japanese (ja)
Inventor
Takayuki Tukada
Kazuhiro Osato
Kunio Nishimura
Kojuro Takahashi
Morinobu Endo
Fuminori Munekane
Syuji Tsuruoka
Original Assignee
Bussan Nanotech Research Institute Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bussan Nanotech Research Institute Inc. filed Critical Bussan Nanotech Research Institute Inc.
Publication of WO2004070095A1 publication Critical patent/WO2004070095A1/fr

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Classifications

    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols

Definitions

  • the present invention relates to fine carbon fibers having a variety of structures and formed of a cylindrical laminate of fine carbon sheets.
  • Carbon fiber is a well-known fibrous carbon, but in recent years, fine carbon fiber has attracted attention.
  • fine carbon fibers There are several types of fine carbon fibers depending on the fiber diameter, and are called vapor-grown carbon fibers, carbon nanofibers, and carbon nanotubes.
  • carbon nanotubes are the finest, with a fiber diameter of less than 100 nm, and their unique physical properties are expected to be widely applied to nanoelectronic materials, composite materials, catalyst support for fuel cells, etc., and gas absorption. Have been.
  • Carbon nanotubes include a sheet of carbon atoms bonded in a net shape (Dalaphen sheet) Single carbon nanotube (S WNT) with one layer of cylinder ⁇ Multilayer force with multiple layers of graphene sheet cylinders nested Monobon nanotubes (MWNT) are known.
  • the geometry of the diameter and the winding of the sheet is determined by the chiral index, which indicates the properties of the metal or semiconductor.
  • These carbon nanotubes are produced by the arc discharge method using a carbon electrode, the laser-oven method, the method of chemically and thermally decomposing hydrocarbon gas using transition metal fine particles as a catalyst (chemical vapor deposition (CVD) method, It is synthesized by catalytic chemical vapor deposition (CC VD).
  • CVD chemical vapor deposition
  • C VD catalytic chemical vapor deposition
  • Hyperion's patent U.S. Pat.
  • carbon nanotubes described in 174018 which are fibrils consisting of a continuous multi-layer of carbon atoms having a substantially graphite structure, each of which consists of multiple layers of regularly arranged carbon atoms, The core and the core are arranged substantially concentrically with the cylindrical axis of the fibril, and each layer of carbon atoms is a fibril made of graphite whose C axis is substantially perpendicular to the cylindrical axis of the fibril.
  • substantially used by Hyperion refers to "measured along the axis of the structure, in a plane, or by volume,” according to the patent application of Hyperion, JP-T-2000-511864. 95% of the value of physical properties at the time should be within V-10% of the average value.
  • a graphite crystal lattice draws points or lines at lattice points determined by black reflection. If the graphite structure is imperfect, these points will be lines, otherwise the lattice points (1 12) will not be clearly visible. Therefore, it is not Graphite if at least the point or line at grid point (1 12) does not appear clearly.
  • the Magnetoresistance value it is determined whether or not a graphite-like structure is included using the electromagnetic properties of graphite. Specifically, at a certain temperature, the Magnetoresistance is measured with respect to the magnetic flux density. When the specimen contains graphite, the Magnetoresistance value increases as the magnetic flux density increases. When no graphite is included, the value decreases with a negative value. In the case of imperfect graphite, the value temporarily becomes negative and gradually increases to a positive value as the magnetic flux density increases. Also, the higher the measurement temperature, the larger the value.
  • the present invention provides a novel structure characterized by having preferable physical properties as a composite material filler, that is, having high dispersibility in a matrix material in a composite material, and having as small a thickness as possible and relatively linear.
  • the present invention provides fine carbon fibers, preferably having a maximum fiber diameter of 100 nm or less. Disclosure of the invention
  • the fine carbon fiber of the present invention has a structure in which a discontinuous surface having a non-circular cross section perpendicular to the axial direction of the cylinder is provided over a part of the length in the axial direction.
  • the fine carbon fiber of the present invention is hardly bent and can be provided with elasticity, that is, the property of trying to return to the original shape even after being deformed. Can be understood. Therefore, the entangled structure in the aggregated structure is difficult to remove, and can be easily dispersed when mixed with the matrix material.
  • An aspect ratio having a continuous hollow portion connected in the axial direction is 10 5 or less, and a cross section perpendicular to the axis at an arbitrary position in the axial direction shows a contour-like stripe pattern by observation with an electron microscope. Fine carbon fibers with uneven sheet spacing.
  • the fine carbon fiber of the present invention has at least one or more refraction points in the axial direction, and the both sides sandwiching the refraction point are linear, and the length of the linear portion is perpendicular to the axis.
  • the area of the cross section perpendicular to the axis on both sides at the refraction point varies discontinuously, there is a portion where the graph ensheet is discontinuous, and the graph ensheet has a six-membered ring. There are carbocyclic structures that are not.
  • a cross section perpendicular to the axis at an arbitrary position in the axial direction shows a contour-like striped pattern when observed by an electron microscope, and the interval of the daraphen sheet in the cross section extends over the entire fiber length. It consists of a non-graphite multilayer structure with adjacent graph ensheet layers that change, and the value of Magnetoresistance takes a negative value with respect to the change in magnetic flux density. Not clearly. Also, it is a fine carbon fiber in which the maximum diameter of the cross section of the hollow part is 10 nm or less, the variation is 2 nm or less, and the difference between the maximum value and the minimum value of the cross section is 1% or more.
  • amorphous carbon precipitates on the outermost layer surface of the fiber, the maximum thickness is 10 nm or less, and the specific surface area of the fiber is 20 OmVg or less.
  • the fine carbon fiber of the present invention is a fine carbon fiber having an outer diameter of 100 nm or less in a cross section perpendicular to an axis as produced by a CVD or CCVD method at a temperature of 1300 ° C. or less, and preferably further comprises It was obtained by processing at 3000 ° C or less.
  • the present invention further includes an aggregate of fine carbon fibers having a fiber diameter of 100 nm or less containing 0.001% or more of the fine carbon fibers having any one or more of the above structures.
  • an aggregate of fine carbon fibers having a fiber diameter of 100 nm or less containing 0.001% or more of the fine carbon fibers having any one or more of the above structures.
  • the fine carbon fiber of the present invention has the following characteristics.
  • the method of use is broadly classified into a method using as a single fiber and a method using as a powder.
  • a single fiber When used as a single fiber, there are fields that utilize characteristics such as electron emission capability, conductivity, and superconductivity, in addition to FEDs, electron microscope elements, semiconductor elements.
  • a 0-dimensional composite material such as slurry
  • 2) a linearly processed 1-dimensional composite material 3) a sheet
  • 3D composite materials such as 2D composite materials (fabric, film, paper) processed into a shape
  • complex molded objects and blocks By combining these forms with the desired functions, an extremely wide range of applications is possible. The following is an example of a specific example of this for each function.
  • a conductive resin and a conductive resin molded product by being mixed with a resin, for example, for packaging materials, gaskets, containers, resistors, conductive fibers, electric wires, adhesives, inks, paints, and the like. Similar effects can be expected with composite materials added to inorganic materials, especially ceramics and metals, in addition to composite materials with resins.
  • Fine fibers have excellent strength, are flexible, and have excellent properties of the filter constituting the network structure. By utilizing this characteristic, it is possible to contribute to strengthening the electrodes of energy devices such as lithium-ion secondary batteries, lead-acid batteries, capacitors, and fuel cells and improving the cycle characteristics.
  • FIG. 1 is a transmission electron micrograph of the fine carbon fiber of the present invention.
  • FIG. 2 is a transmission electron micrograph of the fine carbon fiber of the present invention.
  • FIG. 3 is a transmission electron micrograph of the fine carbon fiber of the present invention.
  • FIG. 4 is a transmission electron micrograph of the fine carbon fiber of the present invention.
  • FIG. 5 is a transmission electron micrograph of the fine carbon fiber obtained in Example 1.
  • FIG. 6 is a transmission electron micrograph of the fine carbon fiber obtained in Example 2.
  • FIG. 7 is a diagram schematically illustrating the synthesis apparatus according to the first embodiment.
  • FIG. 8 is a diagram schematically showing the high-temperature heat treatment apparatuses of Examples 1 and 2.
  • FIG. 9 is a diagram schematically illustrating the synthesizer according to the second embodiment.
  • FIG. 10 is a photograph showing an X-ray diffraction grating image of the fine carbon fibers obtained in Example 1.
  • FIG. 11 is a diagram showing Magnetoresistance of the fine carbon fibers obtained in Example 1.
  • FIG. 12 is a SEM photograph of a composite material using the fine carbon fibers obtained in Example 1.
  • Figure 13 is a SEM photograph of a composite material using conventional fine carbon fibers.
  • the fine carbon fiber having a unique structure of the present invention can be produced by the following method. With the extension of the conventional technology for the production of vapor-grown carbon fiber (VGCF), even the CVD method requires a long synthesis time and does not produce fine materials.
  • VGCF vapor-grown carbon fiber
  • organic compounds such as hydrocarbons are chemically pyrolyzed by CVD method or CCVD method using transition metal ultrafine particles as catalyst, but they are fine carbon fiber nuclei, intermediate products and products in the reactor. Shortening the residence time of the fiber to obtain the fiber and subjecting it to a high-temperature heat treatment is a preferable method for producing a preferable fine carbon fiber.
  • the catalyst and raw material carbon compound are preheated to 300 ° C or more and charged into the furnace in gaseous form.
  • the fiber obtained by the above method is subjected to a high-temperature heat treatment at 3000 ° C or lower by an appropriate method.
  • the As Grown fiber obtained above absorbs many hydrocarbons due to its unique process, and is industrially useful. This hydrocarbon is separated for use. Therefore, for example, heat treatment is performed at a temperature of 1500 ° C. or less to separate the layers. In addition, heat treatment is performed at a processing temperature higher than the synthesis temperature, because the development of crystals is not sufficient with the hydrocarbon separation process alone.
  • high-temperature heat treatment is performed at a temperature of 2000 ° C. or more.
  • a reducing gas or a trace amount of carbon monoxide gas may be added to an inert gas atmosphere to protect the crystal.
  • Fine carbon fibers were synthesized using toluene as a raw material by the CVD method.
  • Figure 7 shows the synthesizer
  • the reaction was carried out in a reducing atmosphere of hydrogen gas using a mixture of Fe-mouth sen and thiophene as a catalyst.
  • the toluene and the catalyst were heated to 375 ° C together with hydrogen gas, supplied to the reactor, and reacted at 1200 ° C with a residence time of 8 seconds. Atmospheric gases were separated by separation and reused.
  • the hydrocarbon concentration in the furnace gas was 7% by volume.
  • the tar content of the synthesized fine carbon fiber of As Grown was 10%.
  • the fiber was heated to 1200, held for 30 minutes to perform a hydrocarbon separation treatment, and further subjected to a high-temperature heat treatment at 280 ° C.
  • Figure 8 shows the equipment for the hydrocarbon separation and high-temperature heat treatment process.
  • Fig. 5 shows an electron micrograph of the obtained fine carbon fiber after the high-temperature heat treatment at 2800 ° C.
  • Benzene is used as a carbon raw material, and the catalysts, huasen and thiophene, are dissolved, vaporized at 380 ° C, and introduced into the reactor.
  • the temperature of the reactor was 1150 ° (The atmosphere in the furnace was a hydrogen gas atmosphere.
  • the residence time of hydrogen gas and raw material gas in the furnace was 7 seconds.
  • As Gro dragon collected downstream of the furnace The tar content of the carbon fibers was 14%.
  • FIG. 6 shows an electron micrograph of the fine carbon fibers after the high-temperature heat treatment at 2800 ° C.
  • Example 1 A diffraction grating image of the fine carbon fiber obtained in Example 1 was taken using an X-ray diffractometer.
  • FIG. 10 shows the obtained diffraction grating image.
  • Example 2 For 1.00 g of the fine carbon fiber obtained in Example 1, a thickener (Susu Co., Ltd.) 19.00 g (5% CNT) and 49.0 g (2.0% CNT) were mixed with 3 pounds of heat-resistant inorganic adhesive made of Ripound and mixed at 2000 rpm for 10 minutes using a centrifugal mixer. The resulting product was linearly adhered in a lmm width on a 125 ⁇ thick polyimide resin (UPILEX S, manufactured by Ube Industries, Ltd.).
  • UPILEX S manufactured by Ube Industries, Ltd.
  • Example 1 The fine carbon fiber obtained in Example 1, methanol, water, and methylcellulose were mixed at a weight ratio of 20: 20: 9: 1, and granulated for 15 minutes by Vertical Granule Yule (manufactured by Parex Co., Ltd.). Thereafter, methanol and water were removed by drying at a temperature of 100 ° C or more by a drier to obtain granules of fine carbon fibers having an average particle diameter of 500 m. Next, 5% by weight of the fine carbon fiber granules were added to the polycarbonate resin, and the mixture was melted and mixed with a vented twin screw extruder (trade name: TEM35, manufactured by Toshiba Machine Co., Ltd.), and the pellets were mixed. Manufactured. Figure 12 shows an SEM photograph of the composite material obtained after melt mixing. Comparative Example 1
  • the conventional fine carbon fiber has a cohesive structure that is not easily unraveled and clings to the central part.
  • the fine carbon fibers of the present invention are hardly entangled in the aggregated structure and are easily dispersed when mixed with the matrix material.
  • the fine carbon fiber of the present invention is used for FED, electron microscope element, semiconductor element, conductive fiber, electric wire, electromagnetic wave shielding material, battery electrode, brake part as composite material, and furthermore, home appliance, vehicle, airplane body and machine housing. It can be suitably used.

Abstract

L'invention concerne une fibre de carbone fine qui contient des matières de type fibre présentant une structure de feuilles de graphène tubulaires empilées radialement par rapport à la direction axiale. Les feuilles formant des tubes comprennent des surfaces discontinues qui forment des lignes droites, ou des lignes courbes sans courbes continues dans les parties de section des tubes perpendiculaires à leur direction axiale, sur des parties de longueur axiale de ceux-ci. Les diamètres maximum des sections des tubes sont inférieurs ou égaux à 100 nm ; les parties creuses continues dans le sens axial se situent au centre des sections ; et le facteur de forme est inférieur ou égal à 105. Cette fibre de carbone fine présente une structure multicouche non graphite ; la section perpendiculaire à l'axe, en tout point axial, présente à l'observation au microscope électronique un motif à bandes de type courbe, et la fibre comporte en section des intervalles variables entre les feuilles de graphène.
PCT/JP2004/001400 2003-02-10 2004-02-10 Fibre de carbone fine presentant diverses structures WO2004070095A1 (fr)

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JP2003032733 2003-02-10
JP2003-032733 2003-02-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105088416A (zh) * 2015-07-10 2015-11-25 中国工程物理研究院化工材料研究所 石墨烯基空心纤维及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02248440A (ja) * 1989-03-22 1990-10-04 Asahi Chem Ind Co Ltd 炭素質繊維集合体
JPH02503334A (ja) * 1988-01-28 1990-10-11 ハイピリオン・カタリシス・インターナシヨナル 炭素フィブリル
WO2001077423A1 (fr) * 2000-04-12 2001-10-18 Showa Denko K.K. Fibre de carbone fine, son procede de production et materiau conducteur contenant ladite fibre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02503334A (ja) * 1988-01-28 1990-10-11 ハイピリオン・カタリシス・インターナシヨナル 炭素フィブリル
JPH02248440A (ja) * 1989-03-22 1990-10-04 Asahi Chem Ind Co Ltd 炭素質繊維集合体
WO2001077423A1 (fr) * 2000-04-12 2001-10-18 Showa Denko K.K. Fibre de carbone fine, son procede de production et materiau conducteur contenant ladite fibre

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105088416A (zh) * 2015-07-10 2015-11-25 中国工程物理研究院化工材料研究所 石墨烯基空心纤维及其制备方法

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