WO2015083701A1 - Fil torsadé de nanotubes de carbone et procédé de production et source de filage pour un fil torsadé de nanotubes de carbone - Google Patents

Fil torsadé de nanotubes de carbone et procédé de production et source de filage pour un fil torsadé de nanotubes de carbone Download PDF

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WO2015083701A1
WO2015083701A1 PCT/JP2014/081869 JP2014081869W WO2015083701A1 WO 2015083701 A1 WO2015083701 A1 WO 2015083701A1 JP 2014081869 W JP2014081869 W JP 2014081869W WO 2015083701 A1 WO2015083701 A1 WO 2015083701A1
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carbon nanotube
cnt
twisted yarn
yarn
twisted
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PCT/JP2014/081869
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English (en)
Japanese (ja)
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翼 井上
太宇人 中西
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国立大学法人静岡大学
Jnc株式会社
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Priority to JP2015551519A priority Critical patent/JP6554727B2/ja
Publication of WO2015083701A1 publication Critical patent/WO2015083701A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/16—Yarns or threads made from mineral substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/08—Aligned nanotubes
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D10B2101/122—Nanocarbons

Definitions

  • the present invention relates to a carbon nanotube twisted yarn, a method for producing a carbon nanotube twisted yarn, and a spinning source.
  • a carbon nanotube array (also referred to as “CNT array” in this specification) is a structure formed when a plurality of carbon nanotubes (also referred to as “CNT” in this specification) are synthesized.
  • CNT synthetic structure in which at least a part of a plurality of synthesized CNTs has a predetermined direction (as a specific example, a normal line of a surface included in the substrate) It is an aggregate of CNTs oriented in the direction substantially parallel).
  • the length (height) of the CNT array grown from the substrate in a direction away from the substrate when attached to the substrate is referred to as “growth height”.
  • a plurality of CNTs are continuously drawn from the CNT array by picking a part of the CNTs constituting the CNT array and pulling the CNTs away from the CNT array.
  • a structure having a structure in which a plurality of CNTs are entangled with each other is called a “CNT entangled body”, which is formed by a process similar to the process of manufacturing yarn from fibers according to the prior art.
  • a structure containing CNT such as the above CNT entangled body is referred to as “CNT-containing structure” in this specification.
  • each shape of the CNT contained in the CNT synthetic structure or the CNT-containing structure is referred to as a “primary structure”, and the shape of the CNT synthetic structure or the CNT-containing structure is also referred to as a “secondary structure”. .
  • CNT yarn a structure that is a kind of CNT entangled body and has a length equal to or longer than the length of the CNT in the long axis direction.
  • CNT twisted yarn a structure manufactured including a step of twisting a plurality of CNT yarns.
  • CNT Since CNT has a specific structure of having an outer surface made of graphene, it is expected to be applied in various fields as a functional material and a structural material. Specifically, CNT has high mechanical strength, light weight, good electrical conductivity characteristics, good thermal characteristics such as heat resistance and thermal conductivity, high chemical corrosion resistance, and good field electron emission characteristics. It has excellent characteristics such as. Therefore, CNTs can be used as lightweight high-strength wires, scanning probe microscope (SPM) probes, field emission display (FED) cold cathodes, conductive resins, high-strength resins, corrosion-resistant resins, wear-resistant resins, Highly lubricious resins, secondary battery and fuel cell electrodes, LSI interlayer wiring materials, biosensors, and the like are considered.
  • SPM scanning probe microscope
  • FED field emission display
  • CNT-containing structures are formed to improve handling.
  • Specific examples of the CNT-containing structure include CNT yarn and CNT twisted yarn.
  • Patent Document 1 discloses a CNT twisted yarn.
  • a CNT twisted yarn is essentially different from a filamentous body obtained by twisting a conventional fibrous member (also referred to as “conventional filamentous body” in this specification) in terms of mechanical strength generation mechanism.
  • a conventional fibrous member also referred to as “conventional filamentous body” in this specification
  • an external force is applied to the nearest CNTs in the direction in which the short axis direction distance decreases, and these fibrous members are predetermined. It is premised that the contact state is achieved by the applied pressure. In this state, the tensile force in the major axis direction of the conventional filamentous body is caused by the frictional force generated between the fibrous members.
  • CNT twisted yarn adjacent CNTs are aggregated due to van der Waals force acting between the outermost graphenes of the CNTs located in the nearest position among the CNTs constituting the CNT twisted yarn.
  • An axial tensile stress is provided. Accordingly, the structure of CNT twisted yarn (secondary structure) and the relationship between the primary structure or secondary structure of a plurality of CNTs constituting the CNT twisted yarn and the mechanical properties of the CNT twisted yarn have not necessarily been clarified.
  • the present invention relates to a CNT twisted yarn that is a material that is essentially different from conventional filaments, and an object of the present invention is to provide a CNT twisted yarn having excellent mechanical properties. Another object of the present invention is to provide a method for producing such a CNT twisted yarn excellent in mechanical properties and a spinning source suitable for production.
  • the average tensile strength T (unit: MPa) of the carbon nanotube twisted yarn is an arithmetic average value of measured values of the tensile strength measured by measuring three or more of the carbon nanotube twisted yarns manufactured under the same conditions.
  • the average diameter ⁇ (unit: ⁇ m) of the carbon nanotube twisted yarn is the three or more carbon nanotube twisted yarns used for measurement of tensile strength or three or more CNT twisted yarns manufactured under the same conditions as the CNT twisted yarns.
  • the average diameter d is an arithmetic average value, and the average diameter d (unit: nm) of the carbon nanotubes was manufactured under the same conditions as the three or more carbon nanotube twisted yarns or the CNT twisted yarns used for measurement of tensile strength. It is an arithmetic average value of average diameters of three or more carbon nanotubes constituting the CNT twisted yarn.
  • the carbon nanotube twisted yarn is manufactured from a spinning source including the carbon nanotube array, and the carbon nanotube array of the spinning source includes a substrate in an atmosphere including a gas phase catalyst. And a second step of obtaining a carbon nanotube array composed of a plurality of carbon nanotubes on the substrate by causing at least a raw material gas to exist in an atmosphere containing the gas phase catalyst.
  • the carbon nanotube twisted yarn described in any one of [1] to [9] above.
  • a carbon nanotube twisted yarn comprising: a spinning step of forming a carbon nanotube yarn having a length equal to or longer than the length of the carbon nanotube yarn; and a twisting step of twisting a plurality of the carbon nanotube yarns to obtain the carbon nanotube twisted yarn.
  • the carbon nanotube array of the spinning source includes a first step in which a substrate is present in an atmosphere including a gas phase catalyst, and at least a source gas is present in the atmosphere including the gas phase catalyst.
  • the manufacturing method according to any one of [11] to [14], wherein the manufacturing method includes a second step of obtaining a carbon nanotube array including a plurality of carbon nanotubes.
  • a spinning source comprising a carbon nanotube array, which is used in the method for producing a twisted carbon nanotube according to any one of [11] to [15].
  • a CNT twisted yarn excellent in mechanical properties is provided.
  • a method for producing such a CNT twisted yarn excellent in mechanical properties and a spinning source suitable for the production are also provided by the present invention.
  • the measurement results of four different CNT twisted yarns manufactured under the same conditions are shown (solid line, broken line, long broken line, and alternate long and short dash line). It is a stress strain diagram of the CNT twisted yarn whose average diameter is 12.5 micrometers based on the Example of this invention.
  • the measurement results of five different CNT twisted yarns manufactured under the same conditions are shown (solid line, broken line, long broken line, one-dot chain line and two-dot chain line). It is a stress strain diagram of the CNT twisted yarn whose average diameter is 15.8 micrometers based on the Example of this invention.
  • the measurement results of five different CNT twisted yarns manufactured under the same conditions are shown (solid line, broken line, long broken line, one-dot chain line and two-dot chain line). It is a stress strain diagram of the CNT twisted yarn whose average diameter is 17.1 micrometers based on the Example of this invention.
  • the measurement results of four different CNT twisted yarns manufactured under the same conditions are shown (solid line, broken line, long broken line, and alternate long and short dash line). It is a stress strain diagram of the CNT twisted yarn whose average diameter is 22.0 micrometers based on the Example of this invention.
  • the measurement results of four different CNT twisted yarns manufactured under the same conditions are shown (solid line, broken line, long broken line, and alternate long and short dash line).
  • Carbon nanotube twisted yarn (CNT twisted yarn)
  • the CNT twisted yarn according to an embodiment of the present invention may have a breaking load index F represented by the following formula (1) of 150 nN or more in a state where only the CNT yarn is twisted.
  • the breaking load index F is positioned as one of the scales for evaluating the tensile strength per CNT constituting the CNT twisted yarn.
  • F T ⁇ 2 / ( ⁇ / d) 2 (1)
  • the average tensile strength T (unit: MPa) of the CNT twisted yarn is an arithmetic average value of measured values of the tensile strength measured using three or more CNT twisted yarns manufactured under the same conditions as the measurement target.
  • the average diameter ⁇ (unit: ⁇ m) of the CNT twisted yarn is an average of three or more CNT twisted yarns used for measurement of tensile strength or three or more CNT twisted yarns manufactured under the same conditions as those CNT twisted yarns. Arithmetic mean value of diameter.
  • the average diameter d (unit: nm) of the CNT is the above three or more CNT twisted yarns used for measuring the tensile strength or the three or more CNT twisted yarns that are produced under the same conditions as those CNT twisted yarns. It is the arithmetic average value of the average diameter of CNT.
  • the CNT twisted yarn according to an embodiment of the present invention having a breaking load index F of 150 nN or more can be obtained only by a twisting step without performing a CNT converging step using a cohesive force of a readily volatile organic material such as acetone.
  • a CNT twisted yarn having excellent mechanical properties is expected to have excellent secondary processability.
  • the secondary processing here means processing for obtaining a structure by integrating a plurality of thread-like CNT-containing structures such as weaving and knitting.
  • the breaking load index F of the CNT twisted yarn in a state where only the CNT yarn is twisted is: It is preferably 200 nN or more, more preferably 250 nN or more, and particularly preferably 300 nN or more.
  • a specific method for measuring the average tensile strength of the CNT twisted yarn according to an embodiment of the present invention is as follows.
  • the CNT twisted yarn to be measured is held so that the gauge distance is 10 mm.
  • a tensile test is performed in which the held CNT twisted yarn is pulled at a tensile rate of 1 mm / min in an environment of 23 ° C. and a relative humidity of 50%, and the tensile load is measured and the amount of elongation is determined in a non-contact manner (that is, by image observation). Measure.
  • the tensile strength is obtained by dividing the breaking load, which is the tensile load when the CNT twisted yarn is broken, by the sectional area of the CNT twisted yarn calculated from the measured value of the diameter of the CNT twisted yarn described below.
  • the measurement of the tensile strength is performed on three or more CNT twisted yarns manufactured under the same conditions, and the arithmetic average of the obtained measured values is defined as the average tensile strength of the CNT twisted yarn.
  • a specific method for measuring the average diameter of the CNT twisted yarn according to an embodiment of the present invention is as follows.
  • the CNT twisted yarn subjected to the above tensile test or the CNT twisted yarn manufactured under the same conditions as the CNT twisted yarn is fixed in a stretched state in an electron microscope, and the fixed CNT twisted yarn is stretched in the long axis direction (tensile Observe from the direction perpendicular to (direction). From the observation image, two line segments that are parallel to the major axis direction and that are in contact with the respective ends of the CNT twisted yarn most are defined, and the separation distance between these line segments is defined as the diameter of the observed CNT twisted yarn. To do.
  • the diameter of the same CNT twisted yarn may be measured using a plurality of positions as an observation field, and the arithmetic average value of the measurement results may be the diameter of the observed CNT twisted yarn.
  • the measurement of the diameter of the above CNT twisted yarn was carried out for three or more CNT twisted yarns subjected to the above-mentioned tensile test, or three or more CNT twisted yarns manufactured under the same conditions as the CNT twisted yarn, and obtained.
  • the arithmetic average of the measured values is taken as the average diameter of the CNT twisted yarn.
  • a specific method for measuring the average diameter of the CNTs constituting the CNT twisted yarn according to one embodiment of the present invention is as follows. A plurality of CNTs that give CNT twisted yarns to be evaluated, or a plurality of CNTs manufactured under the same manufacturing conditions as the CNTs are prepared separately, and these CNTs are observed from a direction orthogonal to the major axis direction. Three or more CNT diameters are measured from the observed image, and the arithmetic average value of the measurement results is taken as the average diameter of the plurality of CNTs. A plurality of points may be measured for one CNT.
  • the number of CNT twisted yarns used for measurement of tensile strength is not particularly limited as long as it is 3 or more. If there are three or more, the measurement value of the mechanical properties of the CNT can be evaluated without being affected by variations. Furthermore, the number of CNT twisted yarns used for measurement of tensile strength is preferably 4 or more, and more preferably 5 or more. The upper limit of the number of CNT twisted yarns used for measurement of tensile strength is not particularly limited.
  • the rupture load index F (unit: nN) is below the average diameter d (unit: nm) of the CNT when only the CNT yarn is twisted.
  • Expression (2) may be satisfied.
  • the CNT twisted yarn according to an embodiment of the present invention satisfies at least one of F ⁇ 150 nN and the following formula (2).
  • F (unit: nN) and d (unit: nm) are as defined above.
  • the CNT twisted yarn according to an embodiment of the present invention preferably satisfies the following formula (3) in a state where only the CNT yarn is twisted.
  • E ⁇ 400 / ⁇ (3) ⁇ (unit: ⁇ m) is as defined above.
  • the average Young's modulus E (unit: GPa) of the CNT twisted yarn is the Young's modulus obtained as the initial slope of the stress strain line obtained from the measurement result of the tensile test performed to determine the average tensile strength of the CNT twisted yarn. Arithmetic mean value.
  • a CNT twisted yarn according to an embodiment of the present invention is obtained by the following formula ( 3-1) is preferably satisfied, the following formula (3-2) is more preferably satisfied, the following formula (3-3) is more preferably satisfied, and the following formula (3-4) is particularly preferably satisfied. preferable.
  • E ⁇ 450 / ⁇ (3-1) E ⁇ 500 / ⁇ (3-2)
  • E ⁇ 550 / ⁇ (3-3) E ⁇ 600 / ⁇ (3-4)
  • the CNT twisted yarn according to an embodiment of the present invention preferably satisfies the following formula (4) in a state where only the CNT yarn is twisted.
  • E (unit: GPa) and d (unit: nm) are as defined above.
  • a CNT twisted yarn according to an embodiment of the present invention is obtained by the following formula ( 4-1) is preferably satisfied, the following formula (4-2) is more preferably satisfied, the following formula (4-3) is more preferably satisfied, and the following formula (4-4) is particularly satisfied. preferable.
  • E ⁇ 450 / d (4-1) E ⁇ 500 / d (4-2)
  • E ⁇ 550 / d (4-3) E ⁇ 600 / d (4-4)
  • the CNT twisted yarn according to an embodiment of the present invention preferably satisfies the following formula (5) in a state where only the CNT yarn is twisted.
  • T (unit: MPa) and ⁇ (unit: ⁇ m) are as defined above.
  • a CNT twisted yarn according to an embodiment of the present invention is obtained by the following formula ( 5-1) is preferably satisfied, more preferably the following formula (5-2) is satisfied, and it is particularly preferable that the following formula (5-3) is satisfied.
  • T ⁇ ⁇ 10 ⁇ ⁇ + 850 (5-1) T ⁇ ⁇ 10 ⁇ ⁇ + 900 (5-2) T ⁇ ⁇ 10 ⁇ ⁇ + 950 (5-3)
  • the CNT twisted yarn according to an embodiment of the present invention preferably satisfies the following formula (6) in a state where only the CNT yarn is twisted.
  • T (unit: MPa) and d (unit: nm) are as defined above.
  • the CNT twisted yarn satisfying the above formula (6) has excellent mechanical properties for each of the CNTs constituting the CNT twisted yarn. Therefore, by satisfying the above formula (6), it is easy to obtain a CNT twisted yarn having excellent mechanical properties.
  • the CNT twisted yarn according to an embodiment of the present invention preferably has a weight density of 0.6 g / cm 3 or more when only the CNT yarn is twisted.
  • a weight density is high, the breaking load in the major axis direction of the CNT twisted yarn tends to increase, and a CNT twisted yarn excellent in mechanical properties is easily obtained.
  • the weight density is more preferably 0.8 g / cm 3 or more, and particularly preferably 1.0 g / cm 3 or more.
  • the upper limit of said weight density is not specifically limited. In principle, the density of graphite (2.2260 g / cm 3 ) is the upper limit.
  • the above-mentioned weight density is usually 1.8 g / cm 3 or less, preferably 1.5 g / cm 3 or less, and 1.3 g / cm 3 or less. More preferably.
  • the twist angle of the CNT twisted yarn according to one embodiment of the present invention is not particularly limited.
  • the twist angle is preferably 5 ° or more and 60 ° or less, more preferably 20 ° to 45 °, and 15 ° to 30 °. Particularly preferred.
  • the CNTs contained in the CNT twisted yarn according to an embodiment of the present invention preferably include those having a length in the major axis direction (also referred to as “CNT length” in the present specification) of 0.6 mm or more. .
  • the longer the CNT length the greater the number of rotations of the CNT located on the outermost side of the CNT twisted yarn around the long axis of the CNT twisted yarn, and the mechanical properties of the CNT twisted yarn are likely to increase.
  • the CNT length is preferably 0.8 mm or more, and more preferably 1.0 mm or more.
  • the upper limit of the CNT length is not particularly limited.
  • the CNT length is excessively long, it may be difficult to form the CNT yarn depending on the method of manufacturing the CNT yarn.
  • a spinning source comprising a CNT array, which will be described later, it is difficult to spin the CNT yarns when the growth height of the CNT array is 3 mm or more.
  • the aspect ratio (length / diameter in the major axis direction) of the CNT constituting the CNT twisted yarn according to an embodiment of the present invention is 1,000 or more from the viewpoint of easily obtaining a CNT twisted yarn excellent in mechanical properties. Preferably, it is 5,000 or more, more preferably 10,000 or more, and particularly preferably 30,000 or more.
  • the upper limit of the aspect ratio is not particularly limited from the viewpoint of easily obtaining a CNT twisted yarn excellent in mechanical properties.
  • the aspect ratio of the CNT constituting the CNT twisted yarn is exemplified by 1,000,000 or less, preferably 100,000 or less, and more preferably 70,000 or less.
  • the CNT twisted yarn according to an embodiment of the present invention can change its mechanical properties by changing the primary structure of the CNT contained in the CNT twisted yarn, even if the diameter of the CNT twisted yarn is almost the same. . That is, it is possible to improve the mechanical properties of the CNT twisted yarn by increasing the CNT length. Moreover, it is possible to improve the mechanical properties of the CNT twisted yarn by reducing the diameter of the CNT or increasing the aspect ratio. In addition, when controlling the physical properties of the CNT twisted yarn by the primary structure of such CNTs, it is preferable that the CNTs are appropriately manufactured. From this point of view, the spinning composed of the CNT array manufactured by the gas phase catalytic method described later It is preferably a CNT twisted yarn manufactured using a source.
  • the basic tendency of the CNT twisted yarn according to an embodiment of the present invention is that the resistivity (unit: ⁇ cm) is almost uncorrelated with the diameter of the CNT twisted yarn (that is, the correlation coefficient is close to 0). It has a positive correlation with the average diameter of CNT contained in the CNT twisted yarn. That is, even if the diameter of the CNT twisted yarn varies, the resistivity tends not to fluctuate, and when the average diameter of the CNT contained in the CNT twisted yarn is changed, the resistivity of the CNT twisted yarn decreases as the diameter decreases. Has a tendency to decline. Therefore, by reducing the diameter of the CNT contained in the CNT twisted yarn, it is possible to obtain a CNT twisted yarn excellent in mechanical properties and electrical properties only by the CNT yarn twisting step.
  • the production method of the CNT twisted yarn according to one embodiment of the present invention is not particularly limited as long as it has the above-described mechanical properties.
  • the CNT twisted yarn which concerns on one Embodiment of this invention can be efficiently manufactured by manufacturing with the following manufacturing method.
  • the method for producing a CNT twisted yarn according to an embodiment of the present invention includes a CNT yarn having a length equal to or greater than the length of the CNT in the major axis direction from a plurality of CNTs constituting a spinning source including a CNT array.
  • a specific example of the spinning process is as follows. When the CNTs constituting the CNT array are pulled out in a direction perpendicular to the CNT growth direction of the CNT array that constitutes the spinning source, a plurality of CNTs are connected to other CNTs by van der Waals force at the end (confounded) ), A CNT yarn is formed.
  • FIG. 1 is an image showing a state where a CNT array (right side in the figure) is manufactured by spinning a CNT array (left side in the figure).
  • FIG. 2 is an image showing a state in which CNT yarn is manufactured by spinning a CNT array having a width of about 5 mm.
  • a plurality of CNTs are arranged so that their major axes are aligned in a direction parallel to the major axis direction of the CNT yarn.
  • the tension applied to the CNT yarn is low, all the CNTs located in the observation field of view are arranged in a state where their major axis directions are not aligned. .
  • the manufacturing method of the CNT twisted yarn which concerns on one Embodiment of this invention is equipped with the twisting process which twists several of the CNT yarn which passed through said spinning process, and obtains a CNT twisted yarn.
  • the twisting step a plurality of CNT yarns are arranged so that the major axis directions thereof are substantially parallel, and the CNTs are twisted so that the major axis direction is the center of rotation.
  • tension is applied to each CNT yarn in the major axis direction. The higher the tension, the easier it is to obtain a CNT twisted yarn with a higher weight density.
  • the maximum value of tension that can be applied to the CNT yarn depends on the magnitude of interaction between the CNTs constituting the CNT yarn (the magnitude of Van der Waals force), the defect density of the CNT constituting the CNT yarn, and the like. .
  • the twisting operation may be performed a plurality of times.
  • the tension applied to the CNT yarn is set lower in the first twisting operation, and the tension applied to the CNT twisted yarn is set higher than the tension in the first operation in the second twisting operation.
  • the characteristics of the CNT twisted yarn can be improved. That is, the main purpose of the initial twisting operation is to arrange a plurality of CNT yarns so as to be proximal to each other. As a result, in the first twisting operation, a CNT twisted yarn having a low degree of interaction and a low weight density is obtained. Subsequently, the tension applied to the CNT twisted yarn is made higher than the tension applied in the initial twisting operation, and the twisting operation is performed.
  • FIG. 4 is a diagram showing the observation results of the CNT twisted yarn obtained by performing the twisting operation twice.
  • FIG. 5 is a diagram showing an observation result of the appearance of a wound body obtained by winding a CNT twisted yarn.
  • the manufacturing method includes a converging step of performing converging to reduce the separation distance of CNTs arranged proximally in the CNT twisted yarn by a method other than twisting. Also good.
  • the specific operation for configuring the focusing process is not limited. As an example of such an operation, a volatile organic compound such as acetone is attached to the CNT in the CNT twisted yarn, and the CNTs that are arranged close to each other in the NT twisted yarn due to the cohesive force when the volatile organic compound volatilizes.
  • a focusing method is also referred to as an aggregating and focusing operation.
  • the temporal relationship between the converging process and the twisting process is not limited.
  • the converging step by the aggregation converging method may be performed before the twisting step, may be performed during the twisting step, or may be performed after the twisting step.
  • facilities including abatement facilities for safely handling easily volatile organic compounds are required.
  • the tension applied to a plurality of CNT yarns to be subjected to the twisting step is increased over time, and the long axis direction of the CNTs in the CNT yarns and the long axis of the CNT yarns Alignment work to align the direction may be performed.
  • Alignment work to align the direction may be performed.
  • the manufacturing method of the CNT twisted yarn which concerns on one Embodiment of this invention may be provided with the coating process which coat
  • the temporal relationship between the coating process and the twisting process is not limited.
  • the coating process may be performed before the twisting process, may be performed during the twisting process, or may be performed after the twisting process.
  • the material used in the coating process may form a chemical bond with CNTs constituting the CNT twisted yarn or may not form such a bond.
  • a plurality of CNT twisted yarns obtained through the twisting step may be further twisted.
  • Such twisting can further improve the mechanical properties of the CNT twisted yarn. From the viewpoint of efficiently improving mechanical properties, it is preferable that two CNT twisted yarns are used for this twisting.
  • Control of physical properties of CNT twisted yarn by setting CNT twisted As described above, it is possible to control mechanical properties and electrical properties of CNT twisted yarn by changing the primary structure of CNT constituting the CNT twisted yarn. . Therefore, in one specific example of the manufacturing method according to an embodiment of the present invention, by adjusting the average diameter of the CNTs constituting the CNT twisted yarn, the tensile strength and / or the resistivity is reduced while the diameter of the CNT twisted yarn is the same. Different CNT twisted yarns can be obtained.
  • Spinning Source A CNT twisted yarn according to an embodiment of the present invention is manufactured from a spinning source including a CNT array in a specific example.
  • the method for producing the CNT array is not particularly limited. Since the CNT array manufactured by the vapor phase catalyst method described below has excellent spinnability, a CNT array having a growth height of 0.6 mm or more can be easily manufactured. A CNT yarn having a long CNT length can be easily produced from a spinning source composed of a CNT array having a high growth height. From CNT yarns having CNTs having a long CNT length as constituent elements, CNT twisted yarns having excellent mechanical properties and electrical properties can be easily obtained.
  • the growth height of the CNT array is preferably 0.6 mm or more, more preferably 0.8 mm or more, and particularly preferably 1.0 mm or more.
  • the upper limit of the growth height of the CNT array is not particularly limited, but if the growth height of the CNT array is excessively high, the spinning property may tend to be lowered, and the production efficiency is lowered depending on the manufacturing method.
  • the growth height of the CNT array is preferably about 3 mm, more preferably about 2.5 mm, and particularly preferably about 2.0 mm.
  • the CNT constituting the CNT array produced by the gas phase catalytic method has an aspect ratio higher than that of the CNT constituting the CNT array produced by the production method according to the prior art (specific example is the solid phase catalyst method). It is easy to increase. As described above, a CNT having a high aspect ratio has a good effect on the electrical characteristics and the like including the mechanical characteristics of the finally obtained CNT twisted yarn, and thus is composed of a CNT array manufactured by a gas phase catalytic method. A CNT twisted yarn using a spinning source as a production raw material tends to be excellent in mechanical properties and electrical properties.
  • the CNT array shown in FIG. 1 is manufactured by a gas phase catalytic method. Further, according to the gas phase catalyst method, the growth rate of the CNT array can be easily increased.
  • a method of manufacturing a CNT array by a gas phase catalyst method includes a first step of causing a substrate to exist in an atmosphere including a gas phase catalyst, and causing at least a source gas to exist in the atmosphere including the gas phase catalyst. And a second step of obtaining a CNT array composed of a plurality of CNTs.
  • FIG. 6 is a diagram schematically showing a configuration of an example of a manufacturing apparatus for manufacturing a CNT array by a gas phase catalytic method.
  • the CNT array manufacturing apparatus 10 includes an electric furnace 12.
  • the electric furnace 12 has a substantially cylindrical shape extending along a predetermined direction A (the direction in which the source gas flows).
  • a reaction vessel tube 14 which is a first chamber having a growth region which is a region where CNTs are formed is passed.
  • the reaction vessel tube 14 is a substantially cylindrical member made of a heat-resistant material such as quartz, has an outer diameter smaller than that of the electric furnace 12, and extends along a predetermined direction A.
  • a substrate 28 having a surface on which a CNT array grows is disposed in the growth region of the reaction vessel tube 14. That is, the growth region in the CNT array manufacturing apparatus 10 includes a region in the reaction vessel tube 14 where the substrate 28 is disposed.
  • the electric furnace 12 includes a heater 16 and a thermocouple 18.
  • the first temperature adjusting device includes a heater 16 and a thermocouple 18.
  • the heater 16 is a certain region in the predetermined direction A of the reaction vessel tube 14 (in other words, a certain region in the axial direction of the substantially cylindrical reaction vessel tube 14, hereinafter also referred to as “heating region”). Heat is generated to increase the temperature of the atmosphere in the tube in the heating region of the reaction vessel tube 14.
  • the thermocouple 18 is disposed in the vicinity of the heating region of the reaction vessel tube 14 inside the electric furnace 12, and can output an electric signal representing a temperature related to the temperature of the atmosphere in the tube in the heating region of the reaction vessel tube 14.
  • the heater 16 and the thermocouple 18 are electrically connected to the control device 20.
  • a supply device 22 is connected to the upstream side of the reaction vessel tube 14 in the predetermined direction A (one end on the left side in FIG. 6).
  • the supply device 22 includes a raw material gas supply device 30, a gas phase catalyst supply device 31, a gas phase promoter supply device 32, and an auxiliary gas supply device 33.
  • the supply device 22 is electrically connected to the control device 20 and is also electrically connected to each supply device included in the supply device 22.
  • the source gas supply device 30 (first supply device) supplies a carbon compound (for example, a hydrocarbon such as acetylene) that is a source of CNT constituting the CNT array, that is, a source gas containing a carbon source into the reaction vessel pipe 14 ( In particular, it can be supplied to the growth region).
  • a carbon compound for example, a hydrocarbon such as acetylene
  • the supply flow rate of the source gas from the source gas supply device 30 can be adjusted using a known flow rate adjusting device such as a mass flow.
  • the gas phase catalyst supply device 31 can supply the gas phase catalyst to the inside (particularly the growth region) of the reaction vessel tube 14.
  • gas phase catalyst is a halogen-containing catalyst precursor, which is formed on the basis of a substance that can be in a gas phase in the growth region of the reaction vessel 14 and the halogen-containing catalyst precursor. It is used as a general term for suspended substances. At least a part of the substance constituting the gas phase catalyst adheres to the substrate 28, and at least a part of the catalyst contributing to the formation of the CNT array is formed based on the attached substance.
  • vapor phase catalysts include iron group element halides (also referred to herein as “iron group element halides”).
  • iron group element halides include iron fluoride, cobalt fluoride, nickel fluoride, iron chloride, cobalt chloride, nickel chloride, iron bromide, cobalt bromide, nickel bromide, and iodide. Iron, cobalt iodide, nickel iodide and the like can be mentioned.
  • different compounds such as iron chloride (II) and iron chloride (III) may exist depending on the valence of ions of the iron group element.
  • the gas phase catalyst may be composed of one type of material or may be composed of a plurality of types of materials.
  • the vapor phase promoter supply device 32 can supply the vapor phase promoter to the inside of the reaction vessel pipe 14 (particularly, the growth region).
  • the supply flow rate of the gas phase promoter from the gas phase promoter supply device 32 can be adjusted using a known flow rate adjusting device such as mass flow.
  • gas phase co-catalyst means a function of changing the growth rate of a CNT array manufactured by a gas phase catalytic method (hereinafter also referred to as “growth rate adjustment function”), A function for changing the spinnability (hereinafter also referred to as “spinnability adjusting function”) and a function for changing the characteristics of the CNT twisted yarn produced from the CNT obtained from the spinning source comprising the CNT array (hereinafter referred to as “twisted yarn characteristic adjusting function”).
  • growth rate adjustment function A function for changing the spinnability
  • spinnability adjusting function a function for changing the characteristics of the CNT twisted yarn produced from the CNT obtained from the spinning source comprising the CNT array
  • twisted yarn characteristic adjusting function hereinafter referred to as “twisted yarn characteristic adjusting function”.
  • varying the spinning length of the CNT yarn obtained from the CNT array can be mentioned.
  • the details of the twist characteristic adjustment function are not particularly limited. Specific examples include changing the tensile strength and resistivity of the CNT twisted yarn.
  • the material that serves as the gas phase promoter There are no particular limitations on the material that serves as the gas phase promoter. It should be set as appropriate based on the type of gas phase catalyst, the function required for the gas phase cocatalyst, and the like.
  • Specific examples of the gas phase promoter include organic compounds such as acetone; halogen compounds such as chlorine molecules and hydrogen chloride.
  • the auxiliary gas supply device 33 is a reaction vessel for gases other than the raw material gas, the gas phase catalyst and the gas phase cocatalyst, for example, an inert gas such as argon (this gas is generically referred to as “auxiliary gas” in this specification).
  • an inert gas such as argon
  • the inside of the tube 14 (particularly the growth region) can be supplied.
  • the supply flow rate of the auxiliary gas from the auxiliary gas supply device 33 can be adjusted using a known flow rate adjusting device such as a mass flow.
  • a pressure regulating valve 23 (a part of the pressure regulating device) and an exhaust device 24 (same as above) are connected to the other end on the downstream side (right side in FIG. 6) of the reaction vessel pipe 14 in the predetermined direction A.
  • the pressure adjusting valve 23 can adjust the pressure in the reaction vessel pipe 14 by changing the degree of opening and closing of the valve.
  • the exhaust device 24 evacuates the inside of the reaction vessel tube 14.
  • the specific type of the exhaust device 24 is not particularly limited, and a rotary pump, an oil diffusion pump, a mechanical booster, a turbo molecular pump, a cryopump, or the like can be used alone or in combination.
  • the pressure adjustment valve 23 and the exhaust device 24 are electrically connected to the control device 20.
  • a pressure gauge 13 for measuring the internal pressure is provided inside the reaction vessel tube 14.
  • the pressure gauge 13 is electrically connected to the control device 20 and can output an electric signal representing the pressure inside the reaction vessel pipe 14 to the control device 20.
  • control device 20 is electrically connected to the heater 16, the thermocouple 18, the supply device 22, the pressure gauge 13, the pressure adjustment valve 23, and the exhaust device 24, and outputs electrical signals output from these devices and the like. It inputs or controls the operation of these devices and the like based on the inputted electric signal.
  • control device 20 a specific operation of the control device 20 will be exemplified.
  • the control device 20 inputs an electrical signal regarding the internal temperature of the reaction vessel tube 14 output from the thermocouple 18 and outputs a control signal related to the operation of the heater 16 determined based on the electrical signal to the heater 16. can do.
  • the heater 16 receiving the control signal from the control device performs an operation of increasing or decreasing the amount of generated heat based on the control signal, and changes the internal temperature of the heating region of the reaction vessel pipe 14.
  • the control device 20 inputs an electric signal regarding the internal pressure of the heating region of the reaction vessel tube 14 output from the pressure gauge 13 and relates to the operation of the pressure adjusting valve 23 and the exhaust device 24 determined based on the electric signal.
  • a control signal can be output to the pressure regulating valve 23 and the exhaust device 24.
  • the pressure adjustment valve 23 and the exhaust device 24 that have received the control signal from the control device 20 change the opening degree of the pressure adjustment valve 23 or change the exhaust capability of the exhaust device 24 based on the control signal. Perform operations such as.
  • the control device 20 can output a control signal for controlling the operation of each device or the like to each device according to a preset time table.
  • the control signal for determining the start and stop of substance supply and the supply flow rate from each of the raw material gas supply device 30, the gas phase catalyst supply device 31, the gas phase promoter supply device 32 and the auxiliary gas supply device 33 provided in the supply device 22 Can be output to the supply device 22.
  • the supply device 22 to which the control signal is input operates each supply device in accordance with the control signal, and starts or stops the supply of each material such as the source gas into the reaction vessel tube 14.
  • the substrate 28 is present in an atmosphere containing a gas phase catalyst.
  • the specific structure (composition, shape) of the substrate 28 is not limited as long as the CNT array can be grown on at least a part of the surface of the substrate 28.
  • Specific examples of the substrate 28 include a quartz substrate and a silicon substrate having a thermal oxide film.
  • the method for supplying the gas phase catalyst into the reaction vessel tube 14 is not limited. As in the above-described manufacturing apparatus 10, it may be supplied from the supply device 22, or a physical state other than the gas phase (typically a solid phase state) that gives a gas phase catalyst to the inside of the heating region of the reaction vessel tube 14.
  • the material also referred to as “catalyst source” in this specification
  • the gas phase catalyst may be present inside the heating region of the reaction vessel tube 14.
  • the iron (II) chloride anhydride will be arrange
  • a gas phase catalyst composed of iron (II) chloride vapor can be present in the reaction vessel tube 14.
  • the atmosphere in the reaction vessel tube 14 in the first step specifically, the pressure in the growth region where the substrate 28 is disposed is not particularly limited. It may be atmospheric pressure (about 1.0 ⁇ 10 5 Pa), negative pressure, or positive pressure.
  • the inside of the reaction vessel tube 14 is set to a negative pressure atmosphere in the second step, it is preferable to reduce the transition time between steps by setting the atmosphere to a negative pressure also in the first step.
  • the specific total pressure of the atmosphere is not particularly limited.
  • the pressure may be 10 ⁇ 2 Pa or more and 10 4 Pa or less.
  • the temperature of the atmosphere in the reaction vessel pipe 14 in the first step is not particularly limited. It may be normal temperature (about 25 ° C.), may be heated, or may be cooled.
  • the growth region of the reaction vessel tube 14 is preferably heated in the second step, the growth region is also heated in the first step to shorten the transition time between steps. May be preferred.
  • the anhydride of iron (II) chloride was heated to sublimate iron (II), and the generated iron (II) chloride
  • the sublimation temperature of iron (II) chloride is about 950 K at atmospheric pressure (about 1.0 ⁇ 10 5 Pa).
  • a CNT array composed of a plurality of CNTs is obtained on a substrate by causing at least a source gas to exist in an atmosphere containing a gas phase catalyst.
  • the kind of source gas is not specifically limited, Usually, a hydrocarbon-type material is used and acetylene is mentioned as a specific example.
  • the method for causing the source gas to exist in the reaction vessel pipe 14 (particularly the growth region) is not particularly limited.
  • the material gas may be present by supplying the source gas from the source gas supply apparatus 30, and the material capable of generating the source gas is placed in the reaction vessel pipe 14.
  • the second step may be started by preliminarily existing, generating a raw material gas from the material, and diffusing it inside the reaction vessel tube 14.
  • the source gas is supplied from the source gas supply device 30, it is preferable to control the supply flow rate of the source gas into the reaction vessel pipe 14 using a flow rate adjusting device.
  • the supply flow rate is expressed in units of sccm, and 1 sccm means a flow rate of 1 ml per minute for a gas converted into an environment of 273 K and 1.01 ⁇ 10 5 Pa.
  • the flow rate of the gas supplied into the reaction vessel tube 14 is the inner diameter of the reaction vessel tube 14, the pressure measured by the pressure gauge 13, etc. in the case of a production apparatus configured as in the production apparatus 10 shown in FIG. 6.
  • a preferable supply flow rate of the source gas containing acetylene is 10 sccm or more and 1000 sccm or less when the pressure of the pressure gauge 13 is 1 ⁇ 10 2 Pa or more and 1 ⁇ 10 3 Pa or less, and in this case, 20 sccm or more and 500 sccm or less. More preferably, it is 50 sccm or more and 300 sccm or less.
  • a gas phase promoter may be further present in the atmosphere containing the gas phase catalyst.
  • the method is not particularly limited.
  • the gas phase promoter may be present by supplying the gas phase promoter from the gas phase promoter supply apparatus 32.
  • the gas phase promoter is supplied from the gas phase promoter supplying device 32, it is preferable to control the supply flow rate of the gas phase promoter to the inside of the reaction vessel pipe 14 using a flow rate adjusting device.
  • a material capable of generating a gas phase promoter is present in the reaction vessel tube 14 in advance, and a gas phase promoter is generated from the material by means such as heating and decompression, and the gas phase promoter is converted into the reaction vessel tube 14. It may be diffused in.
  • the gas phase co-catalyst may be supplied into the reaction vessel pipe 14 in the first step depending on its specific action.
  • the total pressure of the atmosphere in the reaction vessel tube 14 in the second step is not particularly limited. It may be atmospheric pressure (about 1.0 ⁇ 10 5 Pa), negative pressure, or positive pressure. What is necessary is just to set suitably considering the composition (partial pressure ratio) of the substance which exists in the reaction container pipe
  • tube 14 is made into a negative pressure, it will be 1 * 10 ⁇ 1 > Pa or more and 1 * 10 ⁇ 4 > Pa or less, 2 * 10 ⁇ 1 > Pa or more and 5 X10 3 Pa or less is preferable, 5 ⁇ 10 1 Pa or more and 2 ⁇ 10 3 Pa or less is more preferable, and 1 ⁇ 10 2 Pa or more and 1 ⁇ 10 3 Pa or less is particularly preferable.
  • the temperature of the growth region of the reaction vessel tube 14 in the second step is such that the gas phase catalyst and the gas phase promoter used as necessary exist on the substrate 28 using the source gas under the condition that an appropriate amount exists in the growth region.
  • setting a lower temperature on the substrate 28 during the first step may contribute to catalyst formation on the substrate 28, and in this case, the growth region of the reaction vessel tube 14 in the second step.
  • the temperature may be changed to increase from the temperature of the growth region during the first step.
  • the temperature of the substrate 28 during the second step may be controlled by adjusting the temperature of the growth region of the reaction vessel tube 14.
  • the temperature of the substrate 28 during the second step is preferably heated to 8 ⁇ 10 2 K or higher.
  • the temperature of the substrate 28 is 8 ⁇ 10 2 K or higher, the interaction between the gas phase catalyst and the gas phase co-catalyst used as necessary and the source gas is likely to occur on the substrate 28, and the CNT is formed on the substrate 28.
  • the array is easy to grow.
  • the temperature of the base surface during the second step is preferably heated to 9 ⁇ 10 2 K or higher, and is heated to 1.0 ⁇ 10 3 K or higher. Is more preferable, and heating to 1.1 ⁇ 10 3 K or more is particularly preferable.
  • the upper limit of the temperature of the substrate 28 during the second step is not particularly limited, but if it is excessively high, the material constituting the substrate 28 and the material constituting the substrate (they may be the same) may be solid. Therefore, the upper limit is preferably set in consideration of the melting point and sublimation temperature of these materials. Considering the load on the reaction vessel, the upper limit temperature of the substrate 28 is preferably about 1.5 ⁇ 10 3 K.
  • Example 1 Using the manufacturing apparatus having the structure shown in FIG. 6, a CNT array was manufactured by the manufacturing method including the first step and the second step.
  • the first step was performed as follows.
  • a quartz plate (20 mm ⁇ 5 mm ⁇ thickness 1 mm) as a substrate was placed on a boat made of quartz in a reaction vessel tube of a manufacturing apparatus having the structure shown in FIG.
  • iron (II) chloride anhydride as a catalyst source was placed on a portion other than the boat in the reaction vessel tube.
  • the inside of the reaction vessel tube (including the substrate) was heated to 1.1 ⁇ 10 3 K using a heater.
  • the anhydride of iron (II) chloride sublimates in the reaction vessel tube, and the inside of the heating region of the reaction vessel tube contains a gas phase catalyst formed from the anhydride of iron (II) chloride as a catalyst source. It became an atmosphere including.
  • the atmospheric pressure is maintained at 5 ⁇ 10 2 Pa using the pressure adjusting valve, and the temperature in the reaction vessel tube (including the substrate) is set to 1.1 ⁇ 10 3 using the heater.
  • acetylene as a source gas is supplied from the source gas supply unit into the reaction vessel tube, and acetone or the like is supplied from the gas phase cocatalyst supply unit as a gas phase cocatalyst into the reaction vessel tube.
  • acetone or the like is supplied from the gas phase cocatalyst supply unit as a gas phase cocatalyst into the reaction vessel tube.
  • a CNT array was grown on the base surface. Ten minutes after the start of acetylene supply, the supply of acetylene and the gas phase promoter was stopped, and the second step was completed.
  • a CNT array having a growth height of 0.8 mm to 1.0 mm and different diameters was obtained.
  • CNTs were spun by picking up and pulling out the CNTs located on the side of the obtained CNT array to obtain CNT yarns.
  • the CNT yarn is attached to a biaxial winding device, and the twisted CNT yarn is wound while the primary twisting operation is performed while pulling with a load of 5 g. Obtained.
  • the CNT twisted yarn is unwound from the wound body of the CNT twisted yarn, the tip is attached to the biaxial winding device again, and the second twisting operation is performed while pulling with a load of 10 g.
  • the twisted yarn was wound up.
  • a wound body of CNT twisted yarns having a weight density of 0.7 g / cm 3 to 1.0 g / cm 3 and different twist yarn diameters was obtained.
  • the twist angle was in the range of 15 ° to 50 ° for any CNT twisted yarn.
  • Test Example 1 Shape Measurement The CNT array created according to the example was observed from the direction perpendicular to the growth direction, and the diameter of the CNT constituting the CNT array was measured. Ten or more CNTs were measured and the number of measurement locations was 50 or more. The arithmetic average value of the obtained measurement results was defined as the average diameter of the CNTs constituting the CNT array.
  • the average diameter of the CNT twisted yarn was determined as follows. Each of 4 to 5 CNT twisted yarns manufactured under the same conditions was fixed in an electron microscope as a stretched state. These fixed CNT twisted yarns were observed from a direction orthogonal to the major axis direction (tensile direction). From the observation image, two line segments that are parallel to the major axis direction and that are in contact with the respective ends of the CNT twisted yarns are defined. The separation distance between these line segments was taken as the diameter of the observed CNT twisted yarn. The arithmetic average of 4 to 5 CNT twisted yarns obtained in this way was defined as the average diameter of the CNT twisted yarns. Examples of observation results of CNT twisted yarns having different average diameters used for measurement are shown in FIGS.
  • Test Example 2 Measurement of stress strain line The stress strain line of the CNT twisted yarn produced in Example 1 was measured by the following method.
  • the CNT twisted yarn to be measured was held so that the gauge distance was 10 mm.
  • a tensile test is performed in which the held CNT twisted yarn is pulled at a tensile rate of 1 mm / min in an environment of 23 ° C. and a relative humidity of 50%, and the tensile load is measured and the amount of elongation is determined in a non-contact manner (that is, by image observation).
  • Stress strain lines were obtained from these measurement results. Examples of the obtained stress strain lines are shown in FIGS.
  • the Young's modulus of the CNT twisted yarn is obtained from the initial slope of the obtained stress strain line, and the breaking load, which is the tensile load when the CNT twisted yarn breaks, is divided by the cross-sectional area of the CNT twisted yarn calculated from the measured value of the diameter of the CNT twisted yarn.
  • the tensile strength was obtained.
  • the measurement of the stress strain line by this tensile test was performed on 4 to 5 CNT twisted yarns manufactured under the same conditions, and the arithmetic averages of the obtained Young's modulus and tensile strength measurement values were averaged for the average CNT twisted yarns, respectively. And the average tensile strength.
  • the breaking load index of the CNT twisted yarn was determined from the average tensile strength of the CNT twisted yarn, the average diameter of the CNT twisted yarn, and the average diameter of the CNT.
  • FIG. 19 shows a graph showing the dependence of the breaking load index on the average diameter of the CNT twisted yarn
  • FIG. 20 shows a graph showing the dependence of the breaking load index on the average diameter of the CNT.
  • FIG. 21 shows a graph showing the average diameter dependence of the average Young's modulus on the CNT twisted yarn
  • FIG. 22 shows a graph showing the average Young's modulus dependence on the CNT average diameter of the CNT twisted yarn.
  • FIG. 23 shows a graph showing the average tensile strength dependency of the average tensile strength of the CNT twisted yarn
  • FIG. 24 shows a graph showing the average tensile strength dependency of the average tensile strength of the CNT on the average diameter.
  • Table 1 summarizes various measurement results of the CNT twisted yarns produced according to the examples.
  • Example 3 For the CNT twisted yarn manufactured in Example 1, using a DC power source (Egilent E3634A) and a multimeter (Agilent 34410A), the average resistivity of the CNT twisted yarn (CNTs manufactured under the same conditions) by a four-terminal method. The average value of 6 twisted yarns) was obtained. The dependency of the measured average resistivity of each CNT twisted yarn on the average diameter of the CNT twisted yarn is shown in FIG. 25, and the dependency on the average diameter of the CNT is shown in FIG. Table 1 shows the measurement results of the average resistivity of the CNT twisted yarns produced according to the examples.
  • the CNT twisted yarn according to the present invention is excellent in mechanical properties, it is expected to be excellent in secondary workability such as weaving and knitting.
  • the cloth-like body manufactured by the secondary processing is suitably used as, for example, an electric wiring, a heating element, a strain sensor, a transparent electrode sheet, or the like.

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Abstract

L'invention concerne un fil torsadé de nanotubes de carbone (NTC) qui présente un indice de charge de rupture (F), tel que défini par la formule (1), de 150 nN ou plus lorsqu'il est dans un état dans lequel les fils de NTC ont été simplement torsadés. L'invention concerne également un procédé de production du fil torsadé de NTC et une source de filage qui convient pour la production du fil torsadé de NTC. (1) F = Tφ2/(φ/d)2, dans laquelle T est la résistance moyenne à la traction (en MPa) du fil torsadé de NTC et est la moyenne arithmétique de valeurs de résistance à la traction mesurées pour trois brins ou plus du fil torsadé de NTC qui sont produits dans les mêmes conditions, φ est le diamètre moyen (en µm) du fil torsadé de NTC et est la moyenne arithmétique des diamètres moyens de trois brins ou plus du fil torsadé de NTC mesuré pour la résistance à la traction ou de trois brins ou plus du fil torsadé de NTC produit dans les mêmes conditions que le fil torsadé de NTC mesuré pour la résistance à la traction et d est le diamètre moyen (en nm) des NTC et est la moyenne arithmétique des diamètres moyens des NTC qui constituent lesdits trois brins ou plus du fil torsadé de NTC mesuré pour la résistance à la traction ou qui constituent trois brins ou plus du fil torsadé de NTC produit dans les mêmes conditions que le fil torsadé de NCT mesuré pour la résistance à la traction.
PCT/JP2014/081869 2013-12-03 2014-12-02 Fil torsadé de nanotubes de carbone et procédé de production et source de filage pour un fil torsadé de nanotubes de carbone WO2015083701A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016208557A1 (fr) * 2015-06-25 2016-12-29 国立大学法人静岡大学 Procédé de fabrication de forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite
WO2016208558A1 (fr) * 2015-06-25 2016-12-29 国立大学法人静岡大学 Procédé de fabrication de nanotubes de carbone, forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite
CN108541279A (zh) * 2016-01-29 2018-09-14 日立造船株式会社 碳纳米管纱线的制造方法
CN109537110A (zh) * 2018-12-19 2019-03-29 苏州大学 一种碳纳米管纤维的制备方法
JP2019179726A (ja) * 2018-03-30 2019-10-17 古河電気工業株式会社 ヒーター
JP2020164382A (ja) * 2019-03-29 2020-10-08 古河電気工業株式会社 カーボンナノチューブ線材
EP3703077A4 (fr) * 2017-10-26 2021-07-28 Furukawa Electric Co., Ltd. Fil composite de nanotubes de carbone, fil électrique revêtu de nanotubes de carbone et faisceau de fils
EP3703079A4 (fr) * 2017-10-26 2021-08-04 Furukawa Electric Co., Ltd. Fil composite de nanotubes de carbone, fil électrique revêtu de nanotubes de carbone, et faisceau électrique, câblage de robot et ligne aérienne
CN114572765A (zh) * 2022-02-23 2022-06-03 武汉市碳翁科技有限公司 一种碳纳米管加捻收集装置及使用方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102630552B1 (ko) * 2022-11-07 2024-01-30 어썸레이 주식회사 이차전지

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007125923A1 (fr) * 2006-04-24 2007-11-08 National Institute Of Advanced Industrial Science And Technology Nanotube de carbone monoparoi, agregat en fibre de carbone contenant le nanotube de carbone monoparoi et procede de production du nanotube de carbone monoparoi ou de l'agregat en fibre de carbone
JP2009196873A (ja) * 2008-02-25 2009-09-03 National Univ Corp Shizuoka Univ カーボンナノチューブの製造方法及び製造装置
JP2010116632A (ja) * 2008-11-11 2010-05-27 Osaka Prefecture 微細炭素繊維撚糸の製造装置及び製造方法
JP2011207646A (ja) * 2010-03-29 2011-10-20 Osaka Prefecture カーボンナノチューブ集合体、その製造方法及びカーボンナノチューブ撚糸
JP2011208296A (ja) * 2010-03-29 2011-10-20 Osaka Prefecture カーボンナノチューブ撚糸およびその製造方法
JP2013047402A (ja) * 2011-08-29 2013-03-07 Denso Corp カーボンナノチューブ糸接続体及びその製造方法
JP2013174038A (ja) * 2004-11-09 2013-09-05 Board Of Regents The Univ Of Texas System ナノファイバーのリボンおよびシートならびにナノファイバーの撚り糸および無撚り糸の製造および適用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100500556C (zh) * 2005-12-16 2009-06-17 清华大学 碳纳米管丝及其制作方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013174038A (ja) * 2004-11-09 2013-09-05 Board Of Regents The Univ Of Texas System ナノファイバーのリボンおよびシートならびにナノファイバーの撚り糸および無撚り糸の製造および適用
WO2007125923A1 (fr) * 2006-04-24 2007-11-08 National Institute Of Advanced Industrial Science And Technology Nanotube de carbone monoparoi, agregat en fibre de carbone contenant le nanotube de carbone monoparoi et procede de production du nanotube de carbone monoparoi ou de l'agregat en fibre de carbone
JP2009196873A (ja) * 2008-02-25 2009-09-03 National Univ Corp Shizuoka Univ カーボンナノチューブの製造方法及び製造装置
JP2010116632A (ja) * 2008-11-11 2010-05-27 Osaka Prefecture 微細炭素繊維撚糸の製造装置及び製造方法
JP2011207646A (ja) * 2010-03-29 2011-10-20 Osaka Prefecture カーボンナノチューブ集合体、その製造方法及びカーボンナノチューブ撚糸
JP2011208296A (ja) * 2010-03-29 2011-10-20 Osaka Prefecture カーボンナノチューブ撚糸およびその製造方法
JP2013047402A (ja) * 2011-08-29 2013-03-07 Denso Corp カーボンナノチューブ糸接続体及びその製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GHEMES, A. ET AL.: "Fabrication and mechanical properties of carbon nanotube yarns spun from ultra-long multi-walled carbon nanotube arrays", CARBON, vol. 50, 26 May 2012 (2012-05-26), pages 4579 - 4587, XP028403923, DOI: doi:10.1016/j.carbon.2012.05.043 *
INOUE, Y. ET AL.: "One-step grown aligned bulk carbon nanotubes by chloride mediated chemical vapor deposition", APPL. PHYS. LETT., vol. 92, 29 May 2008 (2008-05-29), pages 213113 - 1 -213113-3 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016208557A1 (fr) * 2015-06-25 2016-12-29 国立大学法人静岡大学 Procédé de fabrication de forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite
WO2016208558A1 (fr) * 2015-06-25 2016-12-29 国立大学法人静岡大学 Procédé de fabrication de nanotubes de carbone, forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite
JPWO2016208557A1 (ja) * 2015-06-25 2018-05-31 国立大学法人静岡大学 カーボンナノチューブフォレストの製造方法、紡績源部材、構造体および複合構造体
JPWO2016208558A1 (ja) * 2015-06-25 2018-05-31 国立大学法人静岡大学 カーボンナノチューブの製造方法、カーボンナノチューブフォレスト、紡績源部材、構造体および複合構造体
CN108541279A (zh) * 2016-01-29 2018-09-14 日立造船株式会社 碳纳米管纱线的制造方法
US11208740B2 (en) 2016-01-29 2021-12-28 Hitachi Zosen Corporation Method for producing carbon nanotube yarn
EP3703077A4 (fr) * 2017-10-26 2021-07-28 Furukawa Electric Co., Ltd. Fil composite de nanotubes de carbone, fil électrique revêtu de nanotubes de carbone et faisceau de fils
EP3703079A4 (fr) * 2017-10-26 2021-08-04 Furukawa Electric Co., Ltd. Fil composite de nanotubes de carbone, fil électrique revêtu de nanotubes de carbone, et faisceau électrique, câblage de robot et ligne aérienne
JP2019179726A (ja) * 2018-03-30 2019-10-17 古河電気工業株式会社 ヒーター
CN109537110B (zh) * 2018-12-19 2021-03-12 苏州大学 一种碳纳米管纤维的制备方法
CN109537110A (zh) * 2018-12-19 2019-03-29 苏州大学 一种碳纳米管纤维的制备方法
JP2020164382A (ja) * 2019-03-29 2020-10-08 古河電気工業株式会社 カーボンナノチューブ線材
JP7316822B2 (ja) 2019-03-29 2023-07-28 古河電気工業株式会社 カーボンナノチューブ線材
CN114572765A (zh) * 2022-02-23 2022-06-03 武汉市碳翁科技有限公司 一种碳纳米管加捻收集装置及使用方法
CN114572765B (zh) * 2022-02-23 2023-11-21 武汉市碳翁科技有限公司 一种碳纳米管加捻收集装置及使用方法

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