WO2007099975A1 - Carbon nanotube assembly, carbon nanotube fiber and process for producing carbon nanotube fiber - Google Patents

Carbon nanotube assembly, carbon nanotube fiber and process for producing carbon nanotube fiber Download PDF

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Publication number
WO2007099975A1
WO2007099975A1 PCT/JP2007/053693 JP2007053693W WO2007099975A1 WO 2007099975 A1 WO2007099975 A1 WO 2007099975A1 JP 2007053693 W JP2007053693 W JP 2007053693W WO 2007099975 A1 WO2007099975 A1 WO 2007099975A1
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Prior art keywords
carbon nanotube
carbon
aggregate
carbon nanotubes
ratio
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PCT/JP2007/053693
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French (fr)
Japanese (ja)
Inventor
Nobuyuki Taniguchi
Kouji Kita
Masaki Nishimura
Tomoyuki Akai
Osamu Suekane
Atsuko Nagataki
Makoto Horiguchi
Hironobu Hori
Yoshikazu Nakayama
Original Assignee
Toyo Boseki Kabushiki Kaisha
Osaka Prefectural Government
Osaka University
The Kansai Electric Power Co., Inc.
Osaka Industrial Promotion Organization
Public University Corporation Osaka Prefecture University
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Priority to JP2006-054203 priority Critical
Priority to JP2006054203 priority
Application filed by Toyo Boseki Kabushiki Kaisha, Osaka Prefectural Government, Osaka University, The Kansai Electric Power Co., Inc., Osaka Industrial Promotion Organization, Public University Corporation Osaka Prefecture University filed Critical Toyo Boseki Kabushiki Kaisha
Publication of WO2007099975A1 publication Critical patent/WO2007099975A1/en

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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127Carbon 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/168After-treatment

Abstract

A carbon nanotube assembly having multiple carbon nanotubes formed on a substrate, characterized in that (1) amorphous carbon is superimposed on the surface of each of the carbon nanotubes with a coating ratio of 55 to 100%; (2) the amorphous carbon has an average thickness of 0.3 to 5 nm; (3) the carbon nanotube assembly has an order parameter of 0.85 to 1.0; (4) the carbon nanotube assembly has a bulk density of 1 to 1000 mg/cm3; (5) the carbon nanotube assembly has an oxygen/carbon atomic number ratio of 0.002 to 0.350; and (6) in the Raman spectrum of carbon nanotube assembly, the area ratio of G-band appearing in the vicinity of 1590 cm-1 to D-band appearing in the vicinity of 1350 cm-1 (G/D ratio) is in the range of 0.45 to 0.75.

Description

Specification

Carbon nanotube aggregate, the method of manufacturing the carbon nanotube fibers and carbon nano tube fibers

Technical field

[0001] The present invention is a carbon nanotube aggregate, the method of manufacturing a carbon nanotube fiber and carbon nanotube fibers.

BACKGROUND

[0002] The carbon nanotubes, electrical properties, has excellent mechanical properties such as, including field emission Dace play or the like, and is expected to be used and applied to various industries.

[0003] In recent years, fiber and carbon nanotube sheet used it consists of carbon nanotubes has been proposed (Non-Patent Document 1, 2).

[0004] I Te, the non-patent literature 1, (also referred to as a "carbon nanotube forest"), high-density and high-aligned carbon nanotube collection has grown to coalesce on the substrate by chemical vapor deposition force carbon a method of forming a nanotube fibers is disclosed.

[0005] In Non-Patent Document 2, a method of forming a carbon nanotube sheet has been proposed a carbon nanotube aggregate grown density and high orientation on a substrate in a chemical vapor deposition method.

[0006] The carbon nanotube fibers and the carbon nanotube sheet, because of its not existing in the form, is expected to use in new applications, application to various industries are expected.

[0007] and force while, even if withdraw carbon nanotube fibers and sheets of a carbon nanotube aggregate grown on a substrate, the probability of actually draw (pull-out characteristic) small again. Further, even if it is possible to pull out the carbon nanotube fibers, the efficiency which can produce the pull out Shi carbon nanotube fibers of sufficient length extent that can be used to easily implement the product carbon nanotube fibers are cut in the process is extremely Acre,. Therefore, a problem that it is difficult has occurred a long carbon nanotube fibers and stably producing child the carbon nanotube sheet. [0008] Incidentally, in general, the intensity of each carbon nanotube molecule is defective in the molecule is that the higher being free Ku high crystallinity. Therefore, those who produced from amorphous component (§ mol amorphous carbon) is small aggregate of carbon nanotubes is impurities are said to be higher strength of the carbon nanotube fibers is obtained, et al.

[0009] Therefore, particularly in recent years, to manufacture a carbon nanotube fibers from highly crystallized carbon nanotube aggregate has been actively conducted.

[0010] However, even when producing a carbon nanotube fibers from highly crystallized carbon nanotube aggregate, yet, the drawer characteristics is sufficient Nag also possible to obtain a long force one carbon nanotube fibers is the current situation is difficult.

Non-Patent Document 1: Zhang et al., Science, 306, 1358-1361, 2004

Non-Patent Document 2: Zhang et al., Science, 309, 1215-1219, 2005

Disclosure of the Invention

Problems that the Invention is to you'll solve

[0011] Accordingly, in the present invention, a carbon nanotube aggregate of a high probability can be drawn a long carbon nanotube fibers, and to provide a carbon nanotube fibers obtained from the aggregate.

Means for Solving the Problems

[0012] The present inventors have conducted extensive studies to solve the above problems. As a result, contrary to the method which has been actively carried out in recent years have not been highly crystallized, a carbon nanotube aggregate in a state where the amorphous carbon has a large amount of stacked, further comprising a specific structure by using the aggregate of carbon nanotubes have found that draw a long carbon nanotube fibers with excellent probability, thereby completing the present invention (embodiment 1). Also, without the amorphous carbon has a large amount of stacking, there is subjected to predetermined processing, even cowpea to the use of the aggregate of carbon nanotubes further having a specific structure, elongated excellent probability found that draw carbon nanotube fibers, and have completed the present invention (embodiment 2). That is, the present invention relates to a below.

[0013] Item 1. A carbon nanotube aggregate of carbon nanotubes on the substrate is a plurality of formation, (1) amorphous carbon on the surface of the carbon nanotubes 5 5: 100% coverage It is stacked, (2) the average thickness of the amorphous carbon 0. a 3-5 nm, (3) the order parameter of the aggregate of carbon nanotubes is from 0.85 to 1. 0, (4) the carbon the bulk density of the nanotube assembly is 1~:!. OOOmgZcm 3 der is, (5) and the carbon nanotube atomic ratio of oxygen Z carbon in aggregates 0. 002-0 3 50, (6) the carbon in the Raman spectrum of nanotube aggregate, the area ratio (G / D ratio) is 0.45 to 0.75 of the G band and LSSOcnT D band appearing in the vicinity of 1 appearing in the vicinity of 1590C [pi 1, characterized in that carbon nanotube aggregate.

[0014] Item 2. Carbon nanotube fibers but carbon nanotube aggregate according to claim 1 is a plurality of contiguous from the substrate obtained by drawn et.

[0015] Item 3. twisted by being formed, the carbon nanotube fiber according to claim 2.

[0016] Item 4. further comprising a binder, a carbon nanotube fiber according to claim 2 or 3.

[0017] Item 5. Car carbon nanotubes cross laminate of a carbon nanotube fiber according to any one of claim 2-4.

[0018] Item 6. further comprising a binder, carbon nanotubes cross laminate according to claim 5.

[0019] Item 7. A carbon nanotube aggregate of carbon nanotubes on the substrate is a plurality of formation, (a) is polarized processing is performed, (b) carbon nanotube aggregate of the order parameter There 0. 85: 1. a 0, (c) KasamiHisoka degree of the carbon nanotube aggregate: a ~ 1000mg / cm 3, (d ) the number of oxygen atoms / carbon atoms of the carbon nanotube aggregate ratio from 0.05 to 0. is 35, (e) in Ramansu vector of the aggregate of carbon nanotubes, the area ratio of the D-band appearing in the vicinity of the G band and LSSOcnT 1 appearing near Ι δθΟοπ 1 (G / D ratio) is 0.1 45-0. 60, carbon Nanochi Yubu assembly, characterized in that.

[0020] Item 8. polarization treatment is oxidized, the carbon nanotube assembly according to claim 7.

[0021] Item 9. oxidation treatment is a plasma treatment, a carbon nanotube assembly according to claim 8.

[0022] Item 10. long a method of manufacturing a carbon nanotube fiber, a plurality of bow the carbon nanotube aggregate from the end surface of the carbon nanotube aggregate according to any one of claim 1 and claim 7-9 by out come I, method of manufacturing the carbon nanotube fibers having a step, to form a long carbon nanotube fiber continuously.

[0023] 1. carbon nanotube aggregate (out bear-like 1)

Aggregate of carbon nanotubes is an embodiment 1 of the present invention is a carbon nanotube aggregate of carbon nanotubes is a plurality of formed on a substrate,

(1) the surface amorphous carbon of the carbon nanotubes are laminated in 55-100% coverage,

(2) the average thickness of the amorphous carbon 0. 3-5 nm,

(3) the order parameter is 0. 85-1 aggregate of carbon nanotubes. 0,

(4) the bulk density of the carbon nanotube aggregate is:! A ~ 1000mg / cm 3,

(5) The aggregate of carbon nanotubes atomic ratio of oxygen Z carbon 0.5 of 002-0. Ri 350 der,

In the Raman spectrum of (6) the aggregate of carbon nanotubes, the area ratio of the G band and 1350 cm _ 1 appears in the vicinity of D band current is near 1590 cm _ 1 (G / D ratio) is 0 - 45 to 0.75 , characterized in that. It will be described in detail below.

[0024] <Substrate>

The substrate may be a known or commercially available Nag limited. For example, plastic substrates; glass substrates; silicon substrate; iron, a metal substrate comprising a metal or an alloy thereof, such as copper, or the like can be used. Silicon dioxide film may be laminated on the surface of these substrates. In the present invention, in particular, it is preferable to use an iron coating product layer silicon substrate obtained by iron deposition or sputtering or the like on a silicon substrate having a silicon dioxide film is coated by vapor deposition or thermal oxidation.

[0025] <carbon nanotubes>

Carbon nanotube aggregate of the embodiment 1, the plurality of carbon nanotube on the substrate is bristled with high density and high orientation state. Carbon Nanochi Yubu forming on the substrate, amorphous carbon (amorphous component) are laminated in the covering rate of 55 to 100% on average on the surface, and the average thickness of the amorphous carbon which is the multilayer wherein the is 0. 3-5 nm. These features, on the surface of the carbon Nanochi Yubu of the present invention, hooked has fine irregularities which is a radical 19, when the drawer (during the production of carbon Nanochi Yubu fibers), the frictional force between adjacent carbon nanotubes thereby increasing the force similar. Therefore, it exhibits excellent drawer properties, long carbon nano tube fibers can be easily obtained.

[0026] coverage is preferably 57 to 90%. Thus, physical properties of carbon nanotubes are closed original (high conductivity, high strength, etc.) while suppressing a decrease in, can be force S exhibits excellent drawer properties. The average thickness of the amorphous carbon is preferably 0. 7~2nm. Coverage and average thickness of Amorukabon an image obtained by transmission electron microscope (TEM) (magnification: 6 million times) can be confirmed by observing.

[0027] Carbon nanotubes preferably has a plurality of bent portions. Preferably about twenty or more per one carbon nanotube, more preferably 50 per one: it is preferably present about 1,000. Accordingly, the bent portion becomes a catch portion, in order to increase the force similar to the frictional forces between adjacent carbon nanotubes, it is possible to further improve the extraction characteristics of the aggregate of carbon nanotubes.

[0028] bent portion, it may also be present in any part to the long axis direction of the carbon nanotube les. Root portion of the carbon nanotubes (around part substrate), (farthest part component from the substrate) tip, and may be present in any portion of the intermediate portion between the root portion and the tip portion.

[0029] the presence or absence and the number of the bent portions of the carbon nanotube, a transmission electron microscope (TEM) more images obtained: can be confirmed by observing the (magnification 40,000 to 120,000 times).

[0030] The average diameter of the carbon nanotubes are limited to nag usually lnm~:! About OOnm, favored properly may be about 5~50nm. The average length is also limiting is the preferably Ι μ ΐη than Nag. Shall apply may be Yogu multi-walled carbon nanotubes have a single-walled carbon nanotubes.

[0031] The carbon nanotubes may also contain other elements other than carbon and oxygen, a carboxyl group, a hydroxyl group, a carbonyl group, which may have a functional group such as ether group.

[0032] <carbon nanotube aggregate (embodiment 1)>

Carbon nanotube aggregate of the embodiment 1 is intended for the carbon nanotube is formed so high orientation and high density on a substrate, the order parameter of the carbon nanotube aggregate 0 - 85: 1. is 0 , bulk density of the carbon nanotube aggregate 1: a 1000 mg / cm 3, the atomic ratio of oxygen / carbon of the carbon nanotube aggregate (i.e., O / C ratio) is 0-002-0 350. in Raman spectrum of the carbon nanotube aggregate, 1590Cm- 1 area ratio of the G band and 1350Cm- D band appearing in the vicinity of 1 appearing in the vicinity (GZD ratio) is 0.45 to 0.75.

[0033] Carbon nanotube aggregate of the embodiment 1, the carbon nanotubes are formed in a state of highly oriented on the substrate. The highly oriented, means that together the carbon nanotubes are bristled vertically adjacent article against et substrate plane. Specifically, the order parameter represented by the following formula (1) (〇_P) is 0. 85: 1.0 (preferably 0.90 to 0 99.) In the range of from

[0034] [number 1]

O = (3 <cos 2 ( 90 - ^)> -1) / 2 (1)

[0035] (where, theta j has a molecular axis of any carbon nanotubes are formed on the substrate, indicating the angle between board. <Cos 2 (90- Θ j )> is on a substrate It shows the average value for all carbon nanotubes are formed.)

Carbon nanotube aggregate of the embodiment 1, the carbon nanotubes are formed at a high density on the substrate. That is, the bulk density of the carbon nanotubes on the substrate:! ~ 1 OOOmg / cm 3 , preferably 10 to 500 mg / cm 3, more preferably 10 to: a 100 mg / cm 3. The range the bulk density is small and weakens the interaction between the molecules of adjacent carbon nanotubes from, there is a risk that the drawer characteristics may deteriorate. Bulk density greater than this range les, that there may not be obtained and long fibers in drawn a large amount of carbon nanotubes Shimare ,, uniform thickness at a time when the drawer.

[0036] Carbon nanotube aggregate of the embodiment 1 is the atomic ratio of oxygen Z carbon (OZC ratio) is from 0.002 to 0.350. Preferably ί In addition, it is 0.002 to 0.27. The present invention Te per cent Rere, 〇 / C ratio in the spectrum obtained by the photoelectron spectroscopy (ESCA), the peak area of ​​carbon atoms of the bond energy one 282~298EV, and the peak areas of the oxygen atoms of 526~540eV determined by consideration of the sensitivity correction value and the like of these peak areas and each element can be calculated. [0037] The aggregate of carbon nanotubes embodiment 1, the area ratio of the G band and LSSOcnT D band appearing in the vicinity of 1 appearing in the vicinity of 1590Cm- 1 in the Raman spectrum (G / D ratio) is 0 • 45~0. 75 It is in the range of. G / Di upper ί or 0.75, and preferably ί or 0.60, more preferably 0.56. The GZD ratio With this range, minute irregularities of the carbon nanotube surface derived from the introduced defects and amorphous components on the surface of the carbon nanotube becomes caught, a force similar to the frictional forces between adjacent carbon nanotubes can this and force S to increase. Therefore, it exhibits excellent drawer properties, long carbon nanotube fibers can be easily obtained. When G / D ratio exceeds 0.75, caught it becomes insufficient, which may pull out Shi characteristic is deteriorated. On the other hand, if the G / D ratio is less than 0.45, declining strength of the carbon nanotube fibers pulled out, long carbon nanotube fibers is likely not to give al.

[0038] absorption peak area of G-band and D-band of the present invention, Ramansu Bae Kutonore 800 to 2000 cm _ 1 wavenumber region Niore Te, a line connecting the both ends of the spectrum in a straight line as a base line, 1350 cm _ 1 D band absorption peak appearing in the vicinity of the absorption peak appearing in the vicinity of 1590 cm _ 1 as G band, which is determined by performing a waveform separation by these two absorption peaks curve fitting using Lorentz function it is. It shows an example of the scan Bae Tatonore obtained by Raman light method in FIG. Absorption peak area of ​​D band hatched portion minutes, the absorption peak area of ​​G band are indicated by vertical line portion. The area of ​​the G-band and D-band can be calculated using commercially available software (e.g., Microcal Software. Inc made origin Ver6 etc.). Value absorption peak area of ​​(vertical line portion) obtained by dividing the absorption peak area of ​​D-band (shaded area) of the G band is G / D ratio.

[0039] <method of manufacturing the carbon nanotube aggregate (embodiment 1)>

Method for producing a carbon nanotube aggregate of the embodiment 1 is nag limited in particular example, kill in the production by adjusting the 〇 / C ratio and G / D ratio and the like within the above range. More specifically, by performing chemical vapor deposition method using a hydrocarbon gas such as acetylene, it can be suitably produce the desired aggregate of carbon nanotubes on the substrate.

[0040] substrate include those described above, preferably iron laminated film silicon substrate obtained by depositing an iron or sputtering or the like on a silicon substrate in which a silicon dioxide film is coated by vapor deposition or thermal oxidation. Thus, during the chemical vapor deposition, in the iron coating crowded take carbon, to fine particles on the substrate surface with a suitable particle size and density, the carbon nanotube aggregate formed in a state of high density and high orientation as possible out it is possible to more reliably manufactured.

[0041] temperature is not limited but is preferably 600 to 1000. About C, more preferably about 650 to 750 ° C.

[0042] The pressure is not limited, usually, atmospheric pressure (preferably, 0. 8: 1 about 2 atm) in the row Ebayoi.

[0043] introducing gases include, but are not limited to as long as it has a carbon atom, a hydrocarbon of acetylene or the like can be preferably used. A rare gas such as helium may be used in combination as a carrier gas.

[0044] In the present invention, in particular, it is preferable to control low rate of increase in the concentration of the acetylene gas supplied onto the substrate in the early stages of the synthesis reaction of carbon nanotubes. More thereto, at a substrate material such as iron incorporating carbon, it becomes easier to fine particles on the substrate surface in an optimum particle size and density, wear carbon nanotube aggregate of the present invention in a preferred manufacture. Rate of increase, the force for example from 0.01 to 0 can be set as appropriate in accordance with manufacturing conditions. 45 v ol%, preferably about, may be set to 0. 05-0. 20vol% approximately.

[0045] Further, by controlling the reaction time, can be controlled coverage § mode Rufasu carbon laminated on the surface of the carbon nanotubes and the average thickness, and the like. The reaction time can be more depending on suitably set manufacturing conditions, for example, 3 seconds to 2 hours, preferably about may be set to 15 seconds to about 30 minutes.

[0046] 2. The carbon nanotube aggregate (out bear-like 2)

Carbon nanotube aggregate of the embodiment 2, the carbon nanotube is a carbon nanotube aggregate formed several double on the substrate,

(A) polar processing has been performed,

(B) the order parameter is 0. 85-1 aggregate of carbon nanotubes. 0,

(c) the bulk density of the carbon nanotube aggregate: a ~ 1000mg / cm 3,

(D) the atomic ratio of oxygen Z carbon in aggregates of carbon nanotubes from 0.05 to 0. Is 35,

(e) in the Raman spectrum of the carbon nanotube aggregate, the area ratio of the G band and 1350 cm _ 1 appears in the vicinity of D band current is around 1590 cm _1 (G / D ratio) is 0-45 to 0.60, it is characterized in.

[0047] substrate include the same as described above in embodiment 1. All the measurement methods and the like are the same 1 and the embodiment.

[0048] <carbon nanotube aggregate (embodiment 2)>

Carbon nanotube aggregate of the embodiment 2, the polarization treatment is applied. The polarity processing refers carboxyl group into the carbon nanotube, a hydroxyl group, a carbonyl group, to the process of introducing a functional group such as ether group. Specific examples of the polar treatment is you later. Embodiment 2 This polarization treatment is performed, and because of its specific structure, exhibits excellent drawer characteristics in the production of carbon nanotubes fibers, it is possible to obtain a long carbon Nanochi Yubu fibers.

[0049] The average diameter of the carbon nanotubes constituting the assembly of embodiment 2 is not limited, usually lnm~:! About OOnm, preferably yo be about 5~50nm les. The average length is also preferably limiting the nag is 1 μ ΐη more. Even single-walled carbon nanotubes may be Yogu multi-walled carbon nanotubes. Also, other elements other than carbon and oxygen may be free Ndei. Carbon nanotubes, carboxyl group, hydroxyl group, carboxy group, may have a functional group such as ether group. Further, the same as the reason as Embodiment 1 described above, it is preferable to have a plurality of bent portions. Preferably about twenty or more per one carbon nanotube, more preferably 50 per one: it is preferably present about 1,000.

[0050] Carbon nanotube aggregate of the embodiment 2 is for the carbon nanotubes are formed in a state of high orientation and high density on a substrate, the order parameter of the carbon nanotube aggregate 0.1 85: 1. 0 (preferably 0.90 to 0 99.), and the bulk density of the carbon nanotube aggregate is:! ~ lOOOmgZcm 3 (preferably 10~500MgZcm 3, yo Ri preferably 10-100 mg / cm 3) is there. Intermolecular interaction forces one carbon nanotube adjacent than this range and low bulk density is weakened, there is a risk that the drawer characteristics decline. May not be obtained and long fibers in drawn a large amount of carbon nanotubes Shimare ,, uniform thickness at a time when the drawer and the bulk density is larger than this range. [0051] Carbon nanotube aggregate of the embodiment 2 is the atomic ratio of oxygen / carbon (i.e., O / Ci) forces SO. 05-0. Is 35. Preferably ί In addition, it is 0.09 to 0.27.

[0052] Carbon nanotube aggregate of the embodiment 2, the area ratio G / D ratio of G band and l S SOcnT D band appearing in the vicinity of 1 appearing in the vicinity of 1590Cm- 1 in the Raman spectrum is 0.45 to 0.60 range (preferably from 0.47 to 0.60) in. G / D]: Within this range the spoon, fine irregularities of the force one carbon nanotube surface derived from the introduced defects and amorphous components on the surface of the carbon nanotube becomes caught, adjacent carbon nanotubes thereby increasing the force similar to the frictional force between. Therefore, it exhibits excellent drawer properties, long carbon nanotube fibers can be easily obtained.

[0053] <method of manufacturing the carbon nanotube aggregate (embodiment 2)>

Method for producing a carbon nanotube aggregate of the embodiment 2 is not limited as long as the polarity treatment.

[0054] polar processing, as long as it is possible to impart polarity to carbon nanotubes, les, such is intended to be particularly limited constant but oxidation treatment. The oxidation treatment, for example, plasma treatment, acid treatment, electrolytic oxidation treatment, and a dry oxidation process or the like.

[0055] 1) For example, when performing the plasma treatment, the atmosphere is limited Nag example, oxygen, Al Gon, nitrogen, hydrogen, ammonia, methane, ethylene, and the like. More preferably oxygen, argon and the like. Good record, even with these gases in a mixture also Yogu two or more of them used alone.

[0056] The pressure is not limited, the preferred device specifically is carried out at reduced pressure, 0. 01~: Ι ΟΟΤο rr about (particularly 0 ·:! ~ LTorr) preferably carried out in.

[0057] The processing time of the plasma treatment, the equipment used, the plasma pretreatment of OZC ratio, GZD ratio appropriately determined Surebayore depending on coverage etc. § molar amorphous carbon, but for example: ~ 60 minutes, preferably it may be set to 5 to 20 minutes. Do Les preferable because the effect of treatment with extremely shorten the processing time is reduced. On the other hand, when extremely long processing time, only damage of carbon nanotubes is increased, high-strength, preferably Do Re for high conductivity, and the like are rope considerably loss with the carbon nanotubes.

[0058] Output of the plasma treatment equipment used, OZC ratio before plasma treatment, G / D ratio may be appropriately determined depending on the amorphous carbon covering rate, etc., for example. 10 to: 100 0w, preferably 100 it may be set to ~500w. It is not preferable because the effect of treatment with extremely low output is reduced. On the other hand, when excessively increasing the output, too large damage carbon nanotubes, high strength, preferably Do Re for high conductivity and the like may be impaired significantly with the carbon nanotubes.

When performing the [0059] plasma treatment, the carbon nanotubes grown on the high density and high orientation on a substrate in a chemical vapor deposition method is preferably performed while holding the substrate. By irradiating the plasma from the vertical direction the top of the carbon nanotubes retained on the substrate, be applied to the upper surface portion of the car carbon nanotube aggregate (most distant carbon nanotubes portion from the substrate) the polar process effectively it can. As a result, it is possible to generate a stronger force similar to the friction force between the carbon nanotubes which are adjacent on the surface portion, it is possible to exhibit excellent drawer properties.

[0060] 2) When performing acid treatment, a method of acid treatment nag limited in particular example, it is possible to apply the known methods such as treatment with nitric acid / sulfuric acid mixture.

[0061] 3) When performing electrolytic oxidation treatment, an anionic species which is a radical-generating source can be used nitrate ion as a radical generating source if example embodiment Nag limiting. Electric quantity to be supplied during the electrolytic oxidation treatment 〇 / C ratio before electrolytic oxidation, G / D ratio may be appropriately selected depending on the amorphous carbon coverage like. When the electrical quantity is extremely small it is not preferable because the effect of the treatment is small fence. On the other hand, when excessively increasing the amount of electricity, damage of the carbon nanotubes is increased, unfavorably high strength possessed by the carbon nanotubes, high conductivity, etc. are impaired.

[0062] 4) When performing dry oxidation process, the method of dry oxidation treatment is not particularly limited, for example, can be applied a known method such as ozone promotes oxidation.

[0063] Polarization pretreatment of the carbon nanotube aggregate can be prepared, for example, the aggregate in the same way of Embodiment 1.

[0064] 3. carbon nanotube fibers

Carbon nanotubes fibers of the present invention is an elongated fibers formed by being drawn from a carbon nanotube aggregate of the embodiment 1 or embodiment 2, have, a bundle by the carbon nanotubes continuous plural It is those with, and has a continuously continuous structure.

[0065] The carbon nanotube fiber is good even if not at stake twisted it takes even if Yogu twist to Les,. It has a higher intensity, from the viewpoint of easy handling, twisting takes to have fiber (carbon nanotube twisted) are preferred.

[0066] Fiber length may be appropriately determined depending on the application of the final product Nag limited, the fiber length is preferably 25cm or more, more preferably more than 30cm. Fiber diameter is also not limited, it may be suitably determined depending on the application of the final product.

[0067] The carbon nanotube fibers, it may also contain a binder Les,. Thus, it is possible to further increase than the intensity of the car carbon nanotube fibers, it is easy to handle. Vine da one is not limited as long as it binds the between carbon nanotubes can be a known by-Nda. For example, poly Bulle alcohol. After binding method also forms a limiting Nag example carbon nanotubes fibers, a method of immersing the carbon nanotube fibers in a binder, and a method of applying or spraying a binder in the carbon nanotube fibers. Adhesion amount limiting Nag bar Inda one type of binder may be suitably determined depending on the final product applications and the like.

[0068] 4. the carbon nanotube two-dimensional structure

Carbon nanotube dimensional structure of the present invention is the present invention the carbon nanotube fibers are arranged two-dimensionally.

[0069] a two-dimensional structure of carbon nanotubes Yogu example be formed in a planar shape, woven material form, film form, may be in any form of a plate-like shape. In the present invention, Shi particularly preferred that the onset Ming carbon nanotube fiber is a carbon nanotube sheet formed by adjacent plurality of parallel les.

[0070] a two-dimensional structure of carbon nanotubes, contain a binder such as Le, it may also be,. By Sunda one it is not limited as long as it binds the carbon nanotube fibers can be used a known binder described above.

[0071] a two-dimensional structure of carbon nanotubes, carbon nanotube aggregate arranging plural carbon nanotubes fibers obtained by pulling by tying the Yogu carbon nanotube which was pulled out of carbon nanotubes on the surface linearly from (or knitted woven) may also be used.

[0072] Carbon nanotubes dimensional structure of the present invention, be those of carbon nanotubes fibers of the present invention is formed in combination with known fibers other than carbon nanotubes fibers partially comprise long as Yogu present invention Temoyore,.

[0073] 5. carbon nanotubes fine layer body

Carbon nano Chu laminate of the present invention is the present invention the carbon nanotube two-dimensional structures are laminated.

[0074] In particular, the present invention, there is carbon nanotube fibers plurality of parallel adjacent to become carbon nanotube sheet (single layer) are stacked two or more layers, in each monolayer same workers in contact P, the single is not the same direction of the carbon nanotube fibers constituting the layer product Sotai (cross laminate) is preferred. Angle of the carbon nanotube fibers in adjacent unit layers (Nagajikukata direction) may be Yogu oblique be perpendicular.

[0075] The average thickness of the laminate may be selected from a wide range depending on the application of the final product Nag limited.

[0076] 6. method of manufacturing the carbon nanotube fibers

Method of manufacturing the carbon nanotube fibers of the present invention, the present invention is (embodiment 1 or embodiment 2), the carbon nanotube from the end surface of the carbon nanotube aggregate formed by high density and high orientation on a substrate (side) by drawing a portion of the aggregate, to continuously form an elongate carbon nanotube fibers, further comprising a step. By drawing a portion of the carbon nanotube aggregate of the present invention, a force similar to the frictional forces between the aggregate in adjacent drawn carbon nanotube and the carbon nanotube (on the substrate) carbon nanotubes acts it is conceivable that. Other Me, drawn further to follow the carbon nanotubes carbon nanotubes is drawn in the aggregate, than to the process progresses continuously one after another, long carbon nano tube fibers or carbon nanotubes two-dimensional structure the body is formed.

[0077] In this continuous process, it is pulled out of the carbon nanotube linear, i.e., is pulled out by gripping a point of the end face of the force one carbon nanotube aggregate can produce carbon nanotubes fibers.

[0078] On the other hand, when pulling out the carbon nanotube surface, i.e., pull an end surface of the carbon nanotube aggregate while maintaining the width after gripping a certain width can be produced carbon nanotube two-dimensional structure. Further, even cowpea to weave multiple sequence or knitted carbon nanotube fibers can be produced a two-dimensional structure of carbon nanotubes

[0079] The method to draw the limited Nag example, by pulling apart the substrate of the carbon nanotube aggregate was gripped by (1) a known jig part of the aggregate of carbon nanotubes, carbon between the substrate and the jig how to form a nanotube fibers or two-dimensional structure, (2) substrate was bisected aggregate of carbon nanotubes, more pulling apart the substrate, the carbon nanotube fibers or two-dimensional between said two divided substrate a method of forming a structure, and the like.

[0080] If you wish twisted carbon nanotube fibers, (3) In the method of forming the above (1) or (2), a method of drawing out while rotating the jig or the substrate, (4) above (1) or (2 ) forming a carbon nanotube fiber by the method, a method of rotating the ends of the carbon nanotubes textiles in the opposite direction, may be performed, or the like.

[0081] a method for producing a carbon nanotube fiber two-dimensional carbon nanotube structure or carbon nanotube laminate Nag restrictive we are permitted to use known methods. For example, if the two-dimensional structure of carbon nanotubes and woven in plain weave, may be adopted known weave, such as a twill weave.

[0082] If necessary, carbon nanotube fibers, even also two-dimensional structure of carbon nanotubes is coated and dried the binder or the like at the time of production of carbon nanotubes laminate yo les. It is also possible to employ the above method in combination with known fibers as necessary. Effect of the invention

According [0083] to the carbon nanotube aggregate of the present invention, it is possible to produce a long carbon nanotube fiber 維等 with high probability.

[0084] Carbon nanotubes fibers of the present invention has high strength derived from the carbon nanotubes, high electrical resistance, ballistic 'various fiber products such as protective clothing; member of various electric products such as wire; variety of such it can be used for applications.

[0085] According to the production method of the present invention, it is possible to produce a carbon nanotube fibers long carbon nano tube fibers with high probability. Further, it is possible to produce a two-dimensional structures or laminates carbon nanotubes having a large area.

BEST MODE FOR CARRYING OUT THE INVENTION

[0086] Examples and Comparative Examples illustrate the present invention in detail. The present invention is not limited to the embodiments below.

[0087] 沏 I

Measurements of G / D ratio and O / C ratio of the carbon nanotube aggregate of the examples and comparative examples was conducted in the following manner.

[0088] (1) G / D ratio

Using microscopic Raman spectrophotometer to measure the Raman spectra. The measurement conditions were as follows.

[0089] device name: RENISHAW RAMASCOPE1000

Incident probe: Laser

Detection signal: the scattered light

Use Laser: He- Ne laser

Output: 10mW

Irradiation beam diameter: φ Ι Α μ πι

The objective lens magnification: 20 times

Measuring the wave number range: 150~4000cm- 1

Cumulative number of times: 3 times

[0090] In the wave number region of 800~2000cm _ 1 of the measured Raman spectrum, the scan both ends of the pair Kutonore a baseline with straight lines, the absorption peak D bands appearing near 1350cm _ 1, 1590cm _ 1 near the absorption peak appearing in the G band was determined and the area of ​​each band by performing waveform separation by these two absorption peak curve fitting using Lorentz function. The absorption peak area of ​​G band obtained by dividing the absorption peak area of ​​D band was calculated G / D ratio. The area of ​​the G-band and D-band were calculated using 巿 sales software (Microcal Software. Inc made origin Ver6).

[0091] (2) an oxygen / atomic ratio of carbon (〇 / C ratio)

O / C ratio, using X-ray photoelectron spectrometer was boss measured by photoelectron spectroscopy (ESCA). The measurement conditions were as follows.

[0092] measurement device name: ESCA-5801MC (ULVAC 'Huai Co., Ltd.)

X-ray source: Al K shed

1, 2

Output: 14kV, 25mA

Detector of the path energy: 11.75eV

Of photoelectron escape angle: 45 degrees

Measurements pitch: 0. leV pitch

Measurement Time: 100ms per pitch

Cumulative number of times: 50 times

The degree of vacuum in the chamber one: 1 X 10- 7 Pa~l X 10- 8 Pa

[0093] In addition, as a correction of the peak due to the measurement time of the charging, the combined binding energy Noregi value of the main peak of carbon (Cls) to 284. 8 eV.

[0094] In the obtained spectrum, Cls peak area determined by drawing a linear base line in a range of binding energy 282~298EV, oxygen (Ols) peak area, back Shirley method in the range of 526-5 40 eV It was determined by subtracting the ground. 2 endpoints strength when pulling the background had use a value obtained by numerical average strength of 10 points in the vicinity of each end point.

[0095] O / C ratio is the ratio of the Cls peak area for Ols peak area obtained above, was calculated by dividing the sensitivity correction value of the device-specific. Incidentally, specific sensitivity correction value used in the present invention "ESCA_ 58 01MC" (manufactured by ULVAC 'Huai Inc.) is 2. was 40.

[0096] Example 1

Silicon substrate (commercially available, 1 cm 2) by sputtering iron was prepared a silicon substrate steel shell films are laminated in a thickness of 4 nm.

[0097] This substrate was placed in a thermal CVD apparatus to form a carbon nanotube aggregate in a substrate shape by thermal CVD method. Gas supplied into the thermal CVD was a mixed gas of acetylene gas and helium gas (acetylene gas 5 · 77vt%). The thermal CVD conditions, temperature: 700 ° C, pressure: atmospheric pressure, rate of increase of the acetylene gas concentration in the initial stages: 0. 10 vol% / sec, reaction time was 10 minutes.

[0098] In the carbon nanotube aggregate of Example 1, the coverage of the amorphous carbon 57%, the average thickness of the amorphous carbon was 1. lnm. Carbon nanotube aggregate of the G / D ratio is 0.66 in Example 1, the oxygen Z carbon atomic ratio (〇 / C ratio) is 0.008, a bulk density of 40 mg / cm 3, the order parameter (OP) 0 . it was 94. The average length of the carbon nanotube was 190 mu m. A scanning electron microscope (SEM) photograph of a cross section of the obtained carbon nanotube assembly shown in FIG.

[0099] Example 2

Except that the reaction time was 30 minutes in the same manner as in Example 1 to produce a carbon nanotube aggregate of Example 2.

[0100] In the carbon nanotube aggregate of Example 2, the coverage power of the amorphous carbon S100%, the average thickness of the amorphous carbon was 1 · 7 nm. 2 car carbon nanotube G / D ratio is 0.60 in the embodiment, 〇 / C ratio 0 - 002, the bulk density 20 mg / cm 3, OP was 0.92. The average length of the carbon nanotube was 220 / im.

[0101] Comparative Example 1

The reaction time to minutes 5, except that the rate of rise of the acetylene gas concentration at the initial stage and 0. 25 vol% / sec in the same manner as in Example 1 was manufacture of carbon nanotubes of Comparative Example 1.

[0102] In the carbon nanotube aggregate of the Comparative Example 1, the coverage force 7% amorphous carbon, the average thickness of the amorphous carbon was 0. 2 nm. GZD ratio of aggregate of carbon nanotubes 0. 69, OZC ratio 0.01, bulk density 60mgZcm 3, OP was 0.95. The average length of the carbon nanotube was 160 mu m.

[0103] Comparative Example 2

The reaction time 2 min and, except that the rate of rise of the acetylene gas concentration in the initial stages and 0. 35 vol% / sec in the same manner as in Example 1 to prepare a carbon nanotube aggregate of Comparative Example 2. [0104] In the carbon nanotube aggregate of the Comparative Example 2, the coverage power of the amorphous carbon ¾%, the average thickness of the amorphous carbon was 0 · lnm. G / D ratio of aggregate of carbon nanotubes 1. 60, O / C ratio is 0.00, bulk density 15 mg / cm 3, OP was 0.75. The average length of the carbon nanotube was 160 mu m.

[0105] Example 3

The carbon nanotube aggregate produced in Comparative Example 1, low-temperature plasma surface treatment apparatus (Hirano Hikarion Ltd., low-temperature plasma surface treatment apparatus) using, by performing plasma treatment, the carbon nanotubes of Example 3 to produce an aggregate. The plasma treatment, puts the carbon nanotube aggregate substrate parallel plate electrode having a diameter of 30 cm, was initiated at room temperature while flowing cooling water to the electrodes of this (room temperature). Radiation output was 300 W, an oxygen gas flow 45. 9ccm, the pressure in the chamber one 0. 221Torr, the processing time was 10 minutes.

[0106] In the carbon nanotube aggregate of Example 3, the coverage power of the amorphous carbon ¾7%, the average thickness of the amorphous carbon was 0. 7 nm. Carbon nanotube aggregate of the G / D ratio is 0.56 in Example 3, 〇 / C ratio 0.14, bulk density 60 mg / cm 3, OP was 0.91.

[0107] Example 4

The conditions of the plasma treatment, irradiation power: 500 W, treatment time except for using 5 minutes in the same manner as in Example 3, were produced aggregate of carbon nanotubes of Example 4.

[0108] Example G / D ratio of aggregate of carbon nanotubes 4 0. 55, O / C ratio is 0.10, bulk density 60 mg / cm ", OP was 0.95.

[0109] Example 5

The conditions of the plasma treatment, irradiation power: 500 W, treatment time except for using 20 minutes in the same manner as in Example 3, were produced aggregate of carbon nanotubes of Example 5.

[0110] Example 0.53 is GZD ratio of aggregate of carbon nanotubes 5, O / C ratio is 0.27, bulk density 60 mg / cm 3, 〇_P was 0.92.

[0111] Example 6

The aggregate of carbon nanotubes produced in Example 2, low-temperature plasma surface treatment apparatus (Hirano Hikarion Ltd., low-temperature plasma surface treatment apparatus) using, by performing plasma treatment, the carbon nanotube aggregate of Example 6 It was prepared. The plasma treatment, puts the carbon nanotube aggregate substrate parallel plate electrode having a diameter of 30 cm, was initiated at room temperature while flowing this electrode to the cooling water (room temperature). Irradiation output 500 W, an argon gas flow amount 45. 9ccm, pressure in the chamber one can 0. 221Torr, the processing time was 10 minutes.

[0112] Example GZD ratio of aggregate of carbon nanotubes 6 0. 50, O / C ratio is 0.09, bulk density 20 mg / cm 3, 〇_P was 0.91.

[0113] Example 7

The conditions of the plasma treatment, irradiation power: 100W, treatment time except for using 50 minutes in the same manner as in Example 3, were produced aggregate of carbon nanotubes of Example 7.

[0114] GZD ratio 0. 57, O / C ratio is 0.20 in the aggregate of carbon nanotubes of Example 7, the bulk density 55 mg / cm 3, 〇_P was 0.88.

[0115] Comparative Example 3

The conditions of the plasma treatment, irradiation power: 500 W, treatment time except for using 40 minutes in the same manner as in Example 3, were produced aggregate of carbon nanotubes of Comparative Example 3.

[0116] Comparative Example G / D ratio of aggregate of carbon nanotubes of 3 0. 45, O / C ratio is 0.40, bulk density 58 mg / cm 3, OP was 0.75.

[0117] Comparative Example 4

The conditions of the plasma treatment, irradiation power: 500 W, treatment time except for using inter 35 minutes in the same manner as in Example 3, were produced aggregate of carbon nanotubes of Comparative Example 4.

[0118] G / D ratio of aggregate of carbon nanotubes of Comparative Example 4 0. 55, O / C ratio is 0.45, bulk density 57 mg / cm 3, OP was 0.70.

[0119] drawer Tokuken test of the carbon nanotube aggregate

(1) Measurement of the drawer probability

The end surface of the carbon nanotube aggregate produced, X-type forceps (FONTAX Ltd., product type number "4X_S") a plurality of knobs of carbon nanotubes tip of piercing 0.. 5 to lmm, withdrawal speed 0. 5~2CmZ sec It pulled in the direction parallel to in the substrate. A case in which pulled out a length 2. 0cm or more of the carbon nanotube fiber was "〇". 2. when the fiber is cut in less than 0c m as "X". This measurement, Example:! ~ 7 and Comparative Example: For each carbon nanotube aggregate of 1-4, carried out 10 times, respectively, to determine the number of "〇". This is shown in Table 1.

[0120] (2) Measurement of the maximum twisting length

The end surface of the carbon nanotube aggregate produced, X-type forceps (FONTAX Ltd., product type number "4X_S") after pinched plurality of carbon nanotubes tip of piercing 0.. 5 to lmm, a carbon nanotube pinched XYZ inspection twist machine on the stage by Do not multiplied by the twist in the spinning speed lcm / minute is fixed to (Daiei science equipment Mfg. Co., Ltd., product type number "M_ 1") draws et al., carbon nanotube fibers (carbon nanotube twisted yarn) It was manufacturing. This measurement is performed 10 times, of which, of twine that was pulled out longest length and the maximum twisting length. This is shown in Table 1.

[0121] Because the circumference of 卷取 up roll of test 燃機 is 20 cm, was 25cm in length to give sufficient plated one rotation with reference twisting length. That is, when the maximum twisting length is more than 25cm and The symbol "", and the case was less than 25cm was evaluated as "X".

Note that the SEM photograph of the carbon nanotube twisted yarn obtained by using the aggregate of carbon nanotubes of Example 3 in FIG. 3, SEM photographs of the resulting carbon nanotubes twisted with aggregate of carbon nanotubes of Example 4 It is shown in Figure 4.

[0122] [Table 1]

Drawer probability maximum retardant yarns length

(10 times) length [m] evaluation

Example 1 6 1.2 〇

Example 2 5 0.3 〇

Example 3 8 2.0 〇

Example 4 7 1.5 〇

Example 5 7 1.6 〇

Example 6 7 1.4 〇

Example off 8 1.8 〇

Comparative Example 1 6 o 0. 2 X

Comparative Example 2 1 0. o 0 X

Comparative Example 3 3 X

Comparative Example 4 2 0. 04 X

[0123] Example 8

Flat metal plate (width 5 mm, length 5 cm) were fixed on the XYZ stage Poribyuruaru call 5 wt% aqueous solution at the tip of the (Nacalai tester manufactured, product name "Poly Bulle alcohol (Code 28 310- 35)") was applied. Then, the distal end portion of the flat metal plate, insert the end face of the force one carbon nanotube aggregate prepared in Example 2, by moving the XYZ stage 1 cm / min, the carbon nanotube sheet (width 5 mm, length is 15mm) was prepared. The optical micrograph of the carbon nanotube sheet was produced (taken with a Nikon system stereoscopic microscope SMZ- 1500) shown in FIG.

[0124] Example 9

But using aggregate of carbon nanotubes produced in Example 1 in the same manner as in Example 8, it was prepared three carbon nanotube sheet (width 5 mm, length 10 mm) a. Then in these four carbon nanotube sheet fiber axis direction respectively 0 ° of each sheet, 30 °, by superimposing each at an angle of 90 ° and 0.99 °, the car carbon nanotubes cross laminate It was produced. It shows a photograph of the fabricated cross laminate 6

[0125] to the end surface of the aggregate of carbon nanotubes produced in Example 10 Example 5, 0.5 the tip of the X-type forceps 5: After pinched plurality of carbon nanotubes piercing 1 mm, the car carbon nanotubes pinched XYZ inspection twist machine on the stage by pulling out while applying a twist is fixed to (Daiei scientific instruments Mfg. Co., Ltd., product type number "M _ 1") in the spinning speed 1 cmZ minute, to prepare a carbon nanotube twisted yarn. The carbon nanotube twisted yarn obtained taking Ri cut to a length of 6 cm, poly Bulle alcohol 0. 01wt% aqueous solution (manufacturer name "Nacalai Tester Co.," product name "Poly Bulle alcohol (Code 28310- 35)") to after soaking for 30 minutes, by a child air drying, to prepare a binder containing carbon nanotubes twisted example 10.

[0126] Therefore resulting also shatter touch a carbon nanotube twisted yarn retained the shape of the twisted yarn Nag, it has been force component having a practical strength.

[0127] Example 11

After soaking for 45 minutes the carbon nanotube sheet poly Bulle alcohol 0. 01wt% aqueous solution prepared in Example 8, by air drying, to prepare a binder containing carbon nanotubes sheet of Example 11.

[0128] For obtained not become shattered even touch the carbon nanotube sheet which retained the shape of the Nag sheet was found to have practical strength.

BRIEF DESCRIPTION OF THE DRAWINGS

Garden 1 shows the scan Bae Kutonore obtained by Raman spectroscopy.

FIG. 2 is mosquito Example 1 - Bon'nanochu - shows an SEM photograph of the probe assembly.

FIG. 3 is mosquito Example 3 - Bon'nanochu - shows an SEM photograph of the probe fiber.

FIG. 4 is mosquito Example 4 - Bon'nanochu - shows an SEM photograph of the probe fiber.

FIG. 5 is mosquito Example 8 - Bon'nanochu - shows the SEM photograph of Bushito.

FIG. 6 is mosquito Example 9 - shows an optical micrograph of the probe cross laminate - Bon'nanochu

Claims

Claims [1] carbon nanotubes on the substrate is a plurality of formed les, a carbon nanotube aggregate Ru,
(1) the surface amorphous carbon of the carbon nanotubes are laminated in 55-100% coverage,
(2) the average thickness of the amorphous carbon 0. 3-5 nm,
(3) the order parameter of the aggregate of carbon nanotubes is 0. 85: 1. 0,
(4) the bulk density of the carbon nanotube aggregate is:! A ~ 1000mg / cm 3,
(5) atomic ratio of oxygen / carbon of the carbon nanotube aggregate 0. 002-0. Is 350,
(6) in the Raman spectrum of the carbon nanotube aggregate, the area ratio of the G band and 1350 cm _ 1 appears in the vicinity of D band appearing in the vicinity of 1590 cm _ 1 (G / D ratio) is from 0.45 to 0 · 75 ,
Carbon nanotube aggregate, characterized in that.
[2] Carbon nanotubes fibers obtained by although aggregate of carbon nanotubes of claim 1 is a plurality of contiguous from the substrate drawn et.
[3] twisted by being formed, the carbon nanotube fibers of claim 2.
[4] further comprises a binder, a carbon nanotube fiber according to claim 2 or 3.
[5] Carbon nanotubes cross laminate of a carbon nanotube fiber of claim 2.
[6] further comprises a binder, carbon nanotubes cross laminate according to claim 5.
[7] the carbon nanotubes on the substrate is a plurality of formed a carbon nanotube aggregate les, Ru,
(A) polar processing has been performed,
(B) the order parameter is 0. 85-1 aggregate of carbon nanotubes. 0,
(c) the bulk density of the carbon nanotube aggregate: a ~ 1 OOOmg / cm 3,
(d) the atomic ratio of oxygen / carbon of a carbon nanotube aggregate 0. 05-0. 35 der is, in the Raman spectrum of (e) the aggregate of carbon nanotubes, G band and LSSOcnT 1 appearing near 1590cm area ratio of the D band appearing in the vicinity (G / D ratio) is from 0.45 to 0 · 60,
Carbon nanotube aggregate, characterized in that.
[8] polarization treatment is oxidized, the carbon nanotube assembly according to claim 7.
[9] oxidation treatment is a plasma treatment, a carbon nanotube assembly according to claim 8.
[10] A method of manufacturing a long carbon nanotube fibers,
By drawing a plurality of the carbon nanotube aggregate from the end surface of the carbon nanotube aggregate according to any one of claims 1 and 7-9, the step of continuously forming the elongated carbon nanotubes fibers,
Method of manufacturing the carbon nanotube fibers having a.
PCT/JP2007/053693 2006-02-28 2007-02-27 Carbon nanotube assembly, carbon nanotube fiber and process for producing carbon nanotube fiber WO2007099975A1 (en)

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KR101210701B1 (en) 2007-10-23 2012-12-18 혼하이 프리시젼 인더스트리 컴퍼니 리미티드 The electronic device using a touch panel and a manufacturing method thereof, and a touch panel
US8363017B2 (en) 2007-12-12 2013-01-29 Beijing Funate Innovation Technology Co., Ltd. Touch panel and display device using the same
US8390580B2 (en) 2008-07-09 2013-03-05 Tsinghua University Touch panel, liquid crystal display screen using the same, and methods for making the touch panel and the liquid crystal display screen
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US8457331B2 (en) 2009-11-10 2013-06-04 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
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US8537640B2 (en) 2009-09-11 2013-09-17 Tsinghua University Active sonar system
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US8603585B2 (en) 2007-12-14 2013-12-10 Tsinghua University Method for making carbon nanotube composite
KR101376139B1 (en) 2012-08-07 2014-03-19 포항공과대학교 산학협력단 Method of manufacturing carbon nanotube yarn and apparatus for the same
WO2014055699A1 (en) * 2012-10-04 2014-04-10 Applied Nanostructured Solutions, Llc Methods for making carbon nanostructure layers
US8811631B2 (en) 2009-11-16 2014-08-19 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8905320B2 (en) 2009-06-09 2014-12-09 Tsinghua University Room heating device capable of simultaneously producing sound waves
US8906338B2 (en) 2009-04-22 2014-12-09 Tsinghua University Method for making carbon nanotube film
JP2015510034A (en) * 2012-01-12 2015-04-02 センター ナショナル デ ラ レシェルシェ サイエンティフィック(シーエヌアールエス)Centre National De La Recherche Scientifique(Cnrs) Improvement of adhesion or attachment through a carbon layer of carbon nanotubes on the surface of the material
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US9040159B2 (en) 2007-12-12 2015-05-26 Tsinghua University Electronic element having carbon nanotubes
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US9447259B2 (en) 2012-09-28 2016-09-20 Applied Nanostructured Solutions, Llc Composite materials formed by shear mixing of carbon nanostructures and related methods
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US9836133B2 (en) 2010-12-27 2017-12-05 Tsinghua University Touch pen

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101437663B (en) 2004-11-09 2013-06-19 得克萨斯大学体系董事会 Fabrication and application of nanofiber ribbons and sheets and twisted and non-twisted nanofiber yarns
CN105003405A (en) 2012-08-01 2015-10-28 德克萨斯州大学系统董事会 Coiled and non-coiled twisted nanofiber yarn and polymer fiber torsional and tensile actuators

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006049435A (en) * 2004-08-02 2006-02-16 Sony Corp Carbon nanotube and its arrangement method, field effect transistor using the same and its manufacturing method, and semiconductor device
JP2006062924A (en) * 2004-08-30 2006-03-09 Hitachi Zosen Corp Method for controlling density in formation of carbon nanotube

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006049435A (en) * 2004-08-02 2006-02-16 Sony Corp Carbon nanotube and its arrangement method, field effect transistor using the same and its manufacturing method, and semiconductor device
JP2006062924A (en) * 2004-08-30 2006-03-09 Hitachi Zosen Corp Method for controlling density in formation of carbon nanotube

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIANG K. ET AL.: "Spinning continuous carbon nanotube yarns", NATURE, vol. 419, 2002, pages 801, XP002298429 *
SUEKANE O. ET AL.: "Netsu CVD-ho o Mochiita Brush-jo Taso Carbon Nanotube no Kosoku Seicho", OYO BUTSURI, vol. 73, no. 5, 2004, pages 615 - 619, XP003017367 *
ZHANG M. ET AL.: "Multifunctional carbon nanotube yarns by downsizing an ancient technology", SCIENCE, vol. 306, 2004, pages 1358 - 1361, XP003017368 *

Cited By (158)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2008102813A1 (en) * 2007-02-20 2010-05-27 独立行政法人産業技術総合研究所 Beam-like body and a manufacturing method thereof made of carbon nanotubes
WO2008102813A1 (en) * 2007-02-20 2008-08-28 National Institute Of Advanced Industrial Science And Technology Beam-like material comprising carbon nanotube, and method for production thereof
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US8248377B2 (en) 2007-10-23 2012-08-21 Tsinghua University Touch panel
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US8502786B2 (en) 2007-10-23 2013-08-06 Tsinghua University Touch panel
KR101210701B1 (en) 2007-10-23 2012-12-18 혼하이 프리시젼 인더스트리 컴퍼니 리미티드 The electronic device using a touch panel and a manufacturing method thereof, and a touch panel
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US8248381B2 (en) 2007-12-12 2012-08-21 Tsinghua University Touch panel and display device using the same
US8199119B2 (en) 2007-12-12 2012-06-12 Beijing Funate Innovation Technology Co., Ltd. Touch panel and display device using the same
JP2009146412A (en) * 2007-12-12 2009-07-02 Hon Hai Precision Industry Co Ltd Touch panel and display device using the same
US8237671B2 (en) 2007-12-12 2012-08-07 Tsinghua University Touch panel and display device using the same
US9040159B2 (en) 2007-12-12 2015-05-26 Tsinghua University Electronic element having carbon nanotubes
JP2009146413A (en) * 2007-12-12 2009-07-02 Hon Hai Precision Industry Co Ltd Touch panel and display device using the same
US8237674B2 (en) 2007-12-12 2012-08-07 Tsinghua University Touch panel and display device using the same
US8363017B2 (en) 2007-12-12 2013-01-29 Beijing Funate Innovation Technology Co., Ltd. Touch panel and display device using the same
US8248380B2 (en) 2007-12-14 2012-08-21 Tsinghua University Touch panel and display device using the same
US8237673B2 (en) 2007-12-14 2012-08-07 Tsinghua University Touch panel and display device using the same
US8237672B2 (en) 2007-12-14 2012-08-07 Tsinghua University Touch panel and display device using the same
US8603585B2 (en) 2007-12-14 2013-12-10 Tsinghua University Method for making carbon nanotube composite
KR101212372B1 (en) 2007-12-14 2012-12-13 혼하이 프리시젼 인더스트리 컴퍼니 리미티드 A display device using a touch panel and a touch panel
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JP2009146422A (en) * 2007-12-14 2009-07-02 Hon Hai Precision Industry Co Ltd Touch panel and display device using the same
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US8411044B2 (en) 2007-12-14 2013-04-02 Tsinghua University Touch panel, method for making the same, and display device adopting the same
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US8574393B2 (en) 2007-12-21 2013-11-05 Tsinghua University Method for making touch panel
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US8125878B2 (en) 2007-12-27 2012-02-28 Tsinghua University Touch panel and display device using the same
US8237668B2 (en) 2007-12-27 2012-08-07 Tsinghua University Touch control device
US8325145B2 (en) 2007-12-27 2012-12-04 Tsinghua University Touch panel and display device using the same
US8237669B2 (en) 2007-12-27 2012-08-07 Tsinghua University Touch panel and display device using the same
JP2009157926A (en) * 2007-12-27 2009-07-16 Hon Hai Precision Industry Co Ltd Touch panel and display using the same
JP2009174093A (en) * 2008-01-25 2009-08-06 Sonac Kk Method for producing carbon fiber
JP2009184906A (en) * 2008-02-01 2009-08-20 Hon Hai Precision Industry Co Ltd Carbon nanotube structure and manufacturing method thereof
JP2011098885A (en) * 2008-02-29 2011-05-19 National Institute Of Advanced Industrial Science & Technology Carbon nanotube film structure and carbon nanotube microstructure
JP2009215120A (en) * 2008-03-11 2009-09-24 National Institute For Materials Science Nanocarbon material composite, method for producing the same, and electron emission element using nanocarbon material composite
US8263698B2 (en) 2008-04-16 2012-09-11 Nissin Kogyo Co., Ltd. Carbon nanofiber, method for production thereof, method for production of carbon fiber composite material using carbon nanofiber, and carbon fiber composite material
WO2009128374A1 (en) * 2008-04-16 2009-10-22 日信工業株式会社 Carbon nanofiber, method for production thereof, method for production of carbon fiber composite material using carbon nanofiber, and carbon fiber composite material
CN102007236B (en) 2008-04-16 2013-08-07 日信工业株式会社 Carbon nanofiber, method for production thereof, method for production of carbon fiber composite material using carbon nanofiber, and carbon fiber composite material
US8415420B2 (en) 2008-04-16 2013-04-09 Nissin Kogyo Co., Ltd. Carbon nanofiber, method for production thereof, method for production of carbon fiber composite material using carbon nanofiber, and carbon fiber composite material
JP2009275337A (en) * 2008-04-16 2009-11-26 Mefs Kk Carbon nanofiber, method for production thereof, method for production of carbon fiber composite material using carbon nanofiber, and carbon fiber composite material
JP2009265667A (en) * 2008-04-23 2009-11-12 Hon Hai Precision Industry Co Ltd Method for making liquid crystal display panel
US8068624B2 (en) 2008-04-28 2011-11-29 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8059841B2 (en) 2008-04-28 2011-11-15 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8050430B2 (en) 2008-04-28 2011-11-01 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8068625B2 (en) 2008-04-28 2011-11-29 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8259967B2 (en) 2008-04-28 2012-09-04 Tsinghua University Thermoacoustic device
US8050431B2 (en) 2008-04-28 2011-11-01 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8199938B2 (en) 2008-04-28 2012-06-12 Beijing Funate Innovation Technology Co., Ltd. Method of causing the thermoacoustic effect
US8259966B2 (en) 2008-04-28 2012-09-04 Beijing Funate Innovation Technology Co., Ltd. Acoustic system
US8259968B2 (en) 2008-04-28 2012-09-04 Tsinghua University Thermoacoustic device
US8019097B2 (en) 2008-04-28 2011-09-13 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8270639B2 (en) 2008-04-28 2012-09-18 Tsinghua University Thermoacoustic device
US8019100B2 (en) 2008-04-28 2011-09-13 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8249279B2 (en) 2008-04-28 2012-08-21 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8073164B2 (en) 2008-04-28 2011-12-06 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8452031B2 (en) 2008-04-28 2013-05-28 Tsinghua University Ultrasonic thermoacoustic device
US8073165B2 (en) 2008-04-28 2011-12-06 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8073163B2 (en) 2008-04-28 2011-12-06 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
JP2009268108A (en) * 2008-04-28 2009-11-12 Hon Hai Precision Industry Co Ltd Thermoacoustic device
US8068626B2 (en) 2008-04-28 2011-11-29 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8019098B2 (en) 2008-04-28 2011-09-13 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8019099B2 (en) 2008-04-28 2011-09-13 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
EP2120274A2 (en) 2008-05-14 2009-11-18 Tsing Hua University Carbon Nanotube Thin Film Transistor
EP2120274B1 (en) * 2008-05-14 2018-01-03 Tsing Hua University Carbon Nanotube Thin Film Transistor
JP2009278110A (en) * 2008-05-14 2009-11-26 Hon Hai Precision Industry Co Ltd Thin film transistor
JP2009278106A (en) * 2008-05-14 2009-11-26 Hon Hai Precision Industry Co Ltd Thin film transistor
JP2009278111A (en) * 2008-05-14 2009-11-26 Hon Hai Precision Industry Co Ltd Thin film transistor
JP2009278105A (en) * 2008-05-14 2009-11-26 Hon Hai Precision Industry Co Ltd Method of manufacturing thin film transistor
JP2009278104A (en) * 2008-05-16 2009-11-26 Hon Hai Precision Industry Co Ltd Thin film transistor
JP2009278109A (en) * 2008-05-16 2009-11-26 Hon Hai Precision Industry Co Ltd Thin film transistor
JP2009296593A (en) * 2008-06-04 2009-12-17 Hon Hai Precision Industry Co Ltd Thermoacoustic device
JP2009296594A (en) * 2008-06-04 2009-12-17 Hon Hai Precision Industry Co Ltd Thermoacoustic device
JP2009303217A (en) * 2008-06-13 2009-12-24 Hon Hai Precision Industry Co Ltd Thermoacoustic device
JP2010004537A (en) * 2008-06-18 2010-01-07 Hon Hai Precision Industry Co Ltd Thermoacoustic device
JP2010004535A (en) * 2008-06-18 2010-01-07 Hon Hai Precision Industry Co Ltd Thermoacoustic device
JP2010004536A (en) * 2008-06-18 2010-01-07 Hon Hai Precision Industry Co Ltd Thermoacoustic device
US8237679B2 (en) 2008-07-04 2012-08-07 Tsinghua University Liquid crystal display screen
US8228308B2 (en) 2008-07-04 2012-07-24 Tsinghua University Method for making liquid crystal display adopting touch panel
US8199123B2 (en) 2008-07-04 2012-06-12 Tsinghua University Method for making liquid crystal display screen
US8237677B2 (en) 2008-07-04 2012-08-07 Tsinghua University Liquid crystal display screen
US8105126B2 (en) 2008-07-04 2012-01-31 Tsinghua University Method for fabricating touch panel
US8237680B2 (en) 2008-07-04 2012-08-07 Tsinghua University Touch panel
JP2010015576A (en) * 2008-07-04 2010-01-21 Hon Hai Precision Industry Co Ltd Touch panel
US8411052B2 (en) 2008-07-09 2013-04-02 Tsinghua University Touch panel, liquid crystal display screen using the same, and methods for making the touch panel and the liquid crystal display screen
US8390580B2 (en) 2008-07-09 2013-03-05 Tsinghua University Touch panel, liquid crystal display screen using the same, and methods for making the touch panel and the liquid crystal display screen
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US8030623B2 (en) 2008-07-25 2011-10-04 Tsinghua University Method and device for measuring electromagnetic signal
US8208675B2 (en) 2008-08-22 2012-06-26 Tsinghua University Loudspeaker
US8346316B2 (en) 2008-08-22 2013-01-01 Tsinghua University Personal digital assistant
US8260378B2 (en) 2008-08-22 2012-09-04 Tsinghua University Mobile phone
JP2010049691A (en) * 2008-08-22 2010-03-04 Hon Hai Precision Industry Co Ltd Personal digital assistant
US8300854B2 (en) 2008-10-08 2012-10-30 Tsinghua University Flexible thermoacoustic device
US8208661B2 (en) 2008-10-08 2012-06-26 Tsinghua University Headphone
JP2010116632A (en) * 2008-11-11 2010-05-27 Kansai Electric Power Co Inc:The Apparatus and method for producing fine carbon fiber twisted yarn
JP2010136369A (en) * 2008-12-05 2010-06-17 Hon Hai Precision Industry Co Ltd Thermoacoustic device
US8325949B2 (en) 2008-12-30 2012-12-04 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8311245B2 (en) 2008-12-30 2012-11-13 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic module, thermoacoustic device, and method for making the same
US8763234B2 (en) 2008-12-30 2014-07-01 Beijing Funate Innovation Technology Co., Ltd. Method for making thermoacoustic module
US8331587B2 (en) 2008-12-30 2012-12-11 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic module, thermoacoustic device, and method for making the same
US8325947B2 (en) 2008-12-30 2012-12-04 Bejing FUNATE Innovation Technology Co., Ltd. Thermoacoustic device
US8300856B2 (en) 2008-12-30 2012-10-30 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8331586B2 (en) 2008-12-30 2012-12-11 Tsinghua University Thermoacoustic device
US8345896B2 (en) 2008-12-30 2013-01-01 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8300855B2 (en) 2008-12-30 2012-10-30 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic module, thermoacoustic device, and method for making the same
US8315414B2 (en) 2008-12-30 2012-11-20 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
JP2015078120A (en) * 2008-12-30 2015-04-23 独立行政法人産業技術総合研究所 Monolayer oriented carbon nanotube aggregate, bulky monolayer oriented carbon nanotube aggregate, powdery monolayer oriented carbon nanotube aggregate
US8315415B2 (en) 2008-12-30 2012-11-20 Beijing Funate Innovation Technology Co., Ltd. Speaker
US8462965B2 (en) 2008-12-30 2013-06-11 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic module, thermoacoustic device, and method for making the same
US8325948B2 (en) 2008-12-30 2012-12-04 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic module, thermoacoustic device, and method for making the same
US8379885B2 (en) 2008-12-30 2013-02-19 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic module, thermoacoustic device, and method for making the same
US8238586B2 (en) 2008-12-30 2012-08-07 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8306246B2 (en) 2008-12-30 2012-11-06 Beijing FUNATE Innovation Technology Co., Ld. Thermoacoustic device
US8311244B2 (en) 2008-12-30 2012-11-13 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
JP2010248069A (en) * 2009-04-20 2010-11-04 Hon Hai Precision Industry Co Ltd Method for fabricating carbon nanotube film and device for drawing the same
US8906338B2 (en) 2009-04-22 2014-12-09 Tsinghua University Method for making carbon nanotube film
JP2010275178A (en) * 2009-05-29 2010-12-09 Korea Advanced Inst Of Science & Technology Carbon nanotube bulk material and method for producing the same
US8905320B2 (en) 2009-06-09 2014-12-09 Tsinghua University Room heating device capable of simultaneously producing sound waves
US9077793B2 (en) 2009-06-12 2015-07-07 Tsinghua University Carbon nanotube based flexible mobile phone
JP2011026758A (en) * 2009-06-30 2011-02-10 Japan Exlan Co Ltd High-strength carbon fiber
JP2011026750A (en) * 2009-06-30 2011-02-10 Japan Exlan Co Ltd Method for producing high-strength polyacrylonitrile-based carbon fiber
US8292436B2 (en) 2009-07-03 2012-10-23 Tsinghua University Projection screen and image projection system using the same
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US8406450B2 (en) 2009-08-28 2013-03-26 Tsinghua University Thermoacoustic device with heat dissipating structure
US8537640B2 (en) 2009-09-11 2013-09-17 Tsinghua University Active sonar system
US8249280B2 (en) 2009-09-25 2012-08-21 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8494187B2 (en) 2009-11-06 2013-07-23 Tsinghua University Carbon nanotube speaker
US8457331B2 (en) 2009-11-10 2013-06-04 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
US8811631B2 (en) 2009-11-16 2014-08-19 Beijing Funate Innovation Technology Co., Ltd. Thermoacoustic device
JP2011153392A (en) * 2010-01-28 2011-08-11 Osaka Prefecture Carbon nanotube twisted yarn, and method for producing the same
JP2011219343A (en) * 2010-03-26 2011-11-04 Aisin Seiki Co Ltd Carbon nanotube composite and method for producing same
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US9836133B2 (en) 2010-12-27 2017-12-05 Tsinghua University Touch pen
JP2015510034A (en) * 2012-01-12 2015-04-02 センター ナショナル デ ラ レシェルシェ サイエンティフィック(シーエヌアールエス)Centre National De La Recherche Scientifique(Cnrs) Improvement of adhesion or attachment through a carbon layer of carbon nanotubes on the surface of the material
KR101376139B1 (en) 2012-08-07 2014-03-19 포항공과대학교 산학협력단 Method of manufacturing carbon nanotube yarn and apparatus for the same
US9447259B2 (en) 2012-09-28 2016-09-20 Applied Nanostructured Solutions, Llc Composite materials formed by shear mixing of carbon nanostructures and related methods
US9133031B2 (en) 2012-10-04 2015-09-15 Applied Nanostructured Solutions, Llc Carbon nanostructure layers and methods for making the same
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WO2014055699A1 (en) * 2012-10-04 2014-04-10 Applied Nanostructured Solutions, Llc Methods for making carbon nanostructure layers
US9107292B2 (en) 2012-12-04 2015-08-11 Applied Nanostructured Solutions, Llc Carbon nanostructure-coated fibers of low areal weight and methods for producing the same
JP2016516137A (en) * 2013-03-08 2016-06-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Oriented sheet made by the method and it is bound and aligned carbon nanotubes in the nonwoven sheet
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CN106521971A (en) * 2016-08-25 2017-03-22 北京浩运盛跃新材料科技有限公司 Method for improving performance of carbon nanotube fibers

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