WO2023026950A1 - カーボンナノチューブ集合線の製造方法及びカーボンナノチューブ集合線製造装置 - Google Patents
カーボンナノチューブ集合線の製造方法及びカーボンナノチューブ集合線製造装置 Download PDFInfo
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
Definitions
- the present disclosure relates to a carbon nanotube stranded wire manufacturing method and a carbon nanotube stranded wire manufacturing apparatus.
- Carbon nanotubes (hereinafter also referred to as "CNTs"), which have a cylindrical structure of graphene sheets in which carbon atoms are hexagonally bonded, have 1/5 the mass of copper, 20 times the strength of steel, and excellent conductivity. It is a material with Therefore, electric wires using carbon nanotubes are expected as a material that contributes to weight reduction, downsizing, and improvement of corrosion resistance of motors for automobiles.
- Carbon nanotubes currently produced have a diameter of about 0.4 nm to 20 nm and a maximum length of about 55 cm.
- it is necessary to make the wire rod longer, and techniques for obtaining an elongated wire rod using the carbon nanotube are being studied.
- Patent Document 1 a carbon-containing gas is supplied to catalyst particles in a floating state in a carbon nanotube synthesis furnace to grow a plurality of carbon nanotubes from the catalyst particles.
- a method for obtaining an elongated carbon nanotube assemble line by aligning and assembling carbon nanotubes in their longitudinal direction is disclosed.
- the method for producing the carbon nanotube stranded wire of the present disclosure includes: A carbon-containing gas is supplied from one first end of a tubular carbon nanotube synthesis furnace to grow carbon nanotubes from each of the plurality of catalyst particles suspended in the carbon nanotube synthesis furnace, thereby producing a plurality of carbon nanotubes.
- a method for manufacturing a carbon nanotube stranded wire comprising:
- the carbon nanotube bundled wire manufacturing apparatus of the present disclosure includes: a tubular carbon nanotube synthesis furnace; a carbon-containing gas supply port provided at one first end of the carbon nanotube synthesis furnace; a first flow path provided in the carbon nanotube synthesis furnace; and a recovery gas flow generator provided at a second end opposite to the first end of the carbon nanotube synthesis furnace.
- FIG. 1 is a diagram illustrating a typical configuration example of a carbon nanotube stranded wire manufacturing apparatus according to a second embodiment.
- FIG. 2 is a perspective view showing an example of a recovery gas flow generator.
- 3 is a perspective view of the recovery gas flow generator shown in FIG. 2 as viewed from the direction of arrow A1 (the right side in FIG. 2).
- FIG. 4 is a view of the recovery gas flow generator shown in FIG. 2 as viewed from the direction of arrow B1 (left side in FIG. 2).
- 5 is a cross-sectional view taken along line XI-XI of the recovery gas flow generator shown in FIG. 2.
- FIG. FIG. 6 is a perspective view showing another example of the recovery gas flow generator. 7 is a cross-sectional view of the recovery gas flow generator shown in FIG. 6 taken along the line XII-XII.
- the carbon nanotube stranded wire produced in the carbon nanotube synthesis furnace moves to the downstream side of the carbon nanotube synthesis furnace along with the flow of the raw material gas.
- As a method for efficiently recovering the carbon nanotube assembly wires using the same carbon nanotube synthesis furnace it is conceivable to increase the flow rate of the raw material gas and increase the flow velocity of the gas.
- the upper limit of the flow rate of the raw material gas is determined in consideration of the catalytic reaction for synthesizing carbon nanotubes. Therefore, when the same carbon nanotube synthesis furnace is used, in order to improve the recovery efficiency of carbon nanotubes, the flow rate of the raw material gas is increased above the upper limit of the raw material gas flow rate determined in consideration of the catalytic reaction. cannot be employed.
- an object of the present disclosure is to provide a method for producing a carbon nanotube stranded wire that can efficiently recover the carbon nanotube stranded wire produced in a carbon nanotube synthesis furnace.
- Another object of the present disclosure is to provide a carbon nanotube assembly wire manufacturing apparatus capable of efficiently recovering carbon nanotube assembly wires produced in a carbon nanotube synthesis furnace.
- the method for producing a carbon nanotube stranded wire of the present disclosure includes: A carbon-containing gas is supplied from one first end of a tubular carbon nanotube synthesis furnace to grow carbon nanotubes from each of the plurality of catalyst particles suspended in the carbon nanotube synthesis furnace, thereby producing a plurality of carbon nanotubes.
- a method for manufacturing a carbon nanotube stranded wire comprising:
- the flow velocity of the recovery gas flow is 2 to 100 times the flow velocity of the carbon-containing gas. According to this, the collection efficiency of the CNT aggregated wire is further improved.
- the recovery gas flow is generated using an inert gas. According to this, the collection efficiency of the CNT-assembled wire can be improved while maintaining the quality of the carbon nanotube-assembled wire.
- the carbon nanotube assembly wire manufacturing apparatus of the present disclosure is a tubular carbon nanotube synthesis furnace; a carbon-containing gas supply port provided at one first end of the carbon nanotube synthesis furnace; a first flow path provided in the carbon nanotube synthesis furnace; and a recovery gas flow generator provided at a second end opposite to the first end of the carbon nanotube synthesis furnace.
- the recovery gas flow generator a through hole configured so that the carbon nanotube assembly line flows from a first hole provided on the side of the carbon nanotube synthesis furnace toward a second hole provided on the opposite side of the carbon nanotube synthesis furnace; and an induction gas outlet provided outside the second hole.
- the carbon nanotube aggregated wire is discharged from the second hole to the outside of the recovery gas flow generator.
- the carbon nanotube aggregated wire can be efficiently recovered.
- the shape of the through hole is preferably a truncated cone. According to this, the recovery gas flow flowing through the through hole converges from the first hole toward the second hole. For this reason, the plurality of stranded carbon nanotube wires flowing along the collecting gas stream approach each other and are gathered to form a stranded wire of CNT stranded wires.
- the shape of the through hole is preferably cylindrical. According to this, the carbon nanotube aggregated wire is discharged from the second hole to the outside of the recovery gas flow generator. The carbon nanotube aggregated wire can be efficiently recovered.
- FIG. 1 is a diagram showing an example of a carbon nanotube stranded wire manufacturing apparatus used in the carbon nanotube stranded wire manufacturing method of the present embodiment.
- a carbon-containing gas is supplied from one first end of a tubular carbon nanotube synthesis furnace (hereinafter also referred to as a "CNT synthesis furnace") 60, and the carbon nanotube is a first step of synthesizing a plurality of carbon nanotubes 1 by growing the carbon nanotubes 1 from each of the plurality of catalyst particles 27 in a floating state in the synthesis furnace 60;
- the plurality of carbon nanotubes 1 are aligned and aggregated along the longitudinal direction of the carbon nanotubes 1 in the first channel 41 provided in the carbon nanotube synthesis furnace 60 to form a carbon nanotube assembly line 21.
- a second step of forming The carbon nanotube assembly line 21 is recovered from the second end opposite to the first end of the carbon nanotube synthesis furnace 60 using a recovery gas flow flowing away from the carbon nanotube synthesis furnace 60. and a third step.
- the carbon nanotube assembly wire produced in the carbon nanotube synthesis furnace can be efficiently recovered.
- a carbon-containing gas is supplied from one first end of a tubular carbon nanotube synthesis furnace 60 (the right end where the carbon-containing gas supply port 62 is provided in FIG. 1), and the carbon nanotube
- the carbon nanotubes 1 are grown from each of the plurality of catalyst particles 27 in a floating state in the synthesis furnace 60 to synthesize a plurality of carbon nanotubes 1 .
- the first step is preferably performed under temperature conditions of, for example, 800°C or higher and 1200°C or lower. Under a temperature condition of 800° C. or higher and 1200° C. or lower, the carbon-containing gas is thermally decomposed, and carbon crystals grow on the catalyst particles in a suspended state to form carbon nanotubes. It is also possible to grow CNTs between the plurality of catalyst particles by separating the plurality of catalyst particles in close contact with each other in the flow of the carbon-containing gas.
- the temperature condition of the first step is more preferably 900° C. or higher and 1150° C. or lower, and still more preferably 950° C. or higher and 1050° C. or lower.
- catalyst particles 27 are floating near the carbon-containing gas supply port 62 of the CNT synthesis furnace 60 .
- the catalyst particles 27 are particles obtained by heating a catalyst (not shown) placed near the carbon-containing gas supply port 62 in the CNT synthesis furnace 60 and collapsing due to the wind pressure of the carbon-containing gas.
- the catalyst examples include ferrocene (Fe(C 5 H 5 ) 2 ), nickelocene (Ni(C 5 H 5 ) 2 ), cobaltocene (Co(C 5 H 5 ) 2 etc.) and the like.
- ferrocene is preferable from the viewpoint of being excellent in disintegration property and catalytic action and being able to obtain long CNTs.
- ferrocene is heated to a high temperature and exposed to a carbon-containing gas, it carburizes to form iron carbide (Fe 3 C) on the surface, which easily collapses from the surface, thereby sequentially releasing the catalyst particles 27 . It is possible.
- the main component of the formed catalyst particles 27 is iron carbide or iron.
- catalyst particles 27 other than the above for example, nickel, cobalt, molybdenum, gold, silver, copper, palladium, and platinum can be used.
- the lower limit of the average diameter of the catalyst particles 27 is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more.
- the upper limit of the average diameter of the catalyst particles 27 is preferably 1000 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 10 ⁇ m or less.
- the average diameter of the catalyst particles 27 is 30 nm or more, the diameter of the carbon nanotubes formed by the catalyst particles is large, so the elongation ratio is also large, and the carbon nanotubes can be made sufficiently long.
- the average diameter of the catalyst particles is 1000 ⁇ m or less, the carbon nanotubes formed by the catalyst particles are easily stretched.
- a carbon-containing gas is supplied to the CNT synthesis furnace 60 from a carbon-containing gas supply port 62 .
- a reducing gas such as a hydrocarbon gas is used.
- a carbon-containing gas for example, a mixed gas of methane and hydrogen, a mixed gas of ethylene and hydrogen, a mixed gas of ethanol and hydrogen, or the like can be used.
- the carbon-containing gas contains carbon disulfide ( CS2 ) or thiophene as a co-catalyst.
- the lower limit of the flow velocity of the carbon-containing gas is preferably 0.05 cm/sec or more, more preferably 0.10 cm/sec or more, and still more preferably 0.20 cm/sec or more.
- the upper limit of the flow velocity of the carbon-containing gas is preferably 15.0 cm/sec or less.
- the flow velocity of the carbon-containing gas is preferably 0.05 cm/sec or more and 15.0 cm/sec or less, more preferably 0.10 cm/sec or more and 15.0 cm/sec or less, and 0.20 cm/sec or more and 15.0 cm/sec or less. is more preferred.
- the “flow rate of carbon-containing gas” means the average flow rate of carbon-containing gas in the area between the carbon-containing gas supply port 62 and the first flow path 41 inside the CTN synthesis furnace 60 .
- the lower limit of the Reynolds number of the flow in the CNT synthesis furnace 60 of the carbon-containing gas supplied from the carbon-containing gas supply port 62 is preferably 0.01 or more, more preferably 0.05 or more.
- the upper limit of the Reynolds number is preferably 1000 or less, more preferably 100 or less, and even more preferably 10 or less.
- the Reynolds number is 0.01 or more, the degree of freedom in device design is improved.
- the Reynolds number is 1000 or less, it is possible to prevent the flow of the carbon-containing gas from being disturbed and hindering the synthesis of carbon nanotubes between the catalyst particles 27 .
- the carbon nanotubes 1 obtained in the first step include single-walled carbon nanotubes in which only one carbon layer (graphene) is cylindrical, and carbon nanotubes in which a plurality of carbon layers are stacked to form a cylindrical shape. Examples include double-walled carbon nanotubes, multi-walled carbon nanotubes, and the like.
- the shape of the carbon nanotube is not particularly limited, and examples include those with closed ends and those with open holes at the ends.
- catalyst particles 27 used during synthesis of the carbon nanotube may be attached to one or both ends of the carbon nanotube 1 .
- one or both ends of the carbon nanotube 1 may be formed with a conical cone made of graphene.
- the length of the carbon nanotube is, for example, preferably 10 ⁇ m or longer, more preferably 100 ⁇ m or longer.
- carbon nanotubes with a length of 100 ⁇ m or more are preferable from the viewpoint of production of CNT-assembled wires.
- the upper limit of the length of the carbon nanotube is not particularly limited, it is preferably 600 mm or less from the viewpoint of manufacturing.
- the length of the CNT is preferably 10 ⁇ m or more and 600 mm or less, more preferably 100 ⁇ m or more and 600 mm or less. The length of CNT can be measured by observing with a scanning electron microscope.
- the diameter of the carbon nanotube is preferably 0.6 nm or more and 20 nm or less, more preferably 1 nm or more and 10 nm or less.
- carbon nanotubes with a diameter of 1 nm or more and 10 nm or less are preferable from the viewpoint of heat resistance under oxidation conditions.
- the diameter of a carbon nanotube means the average outer diameter of one CNT.
- the average outer diameter of the CNT is obtained by directly observing the cross section of the CNT at any two locations with a transmission electron microscope, and measuring the outer diameter, which is the distance between the two most distant points on the outer circumference of the CNT in the cross section, It is obtained by calculating the average value of the obtained outer diameters. If the CNT contains a cone on one or both ends, measure the diameter at the location excluding the cone.
- ⁇ Second step> In the second step, the plurality of carbon nanotubes 1 obtained in the first step are aligned in the longitudinal direction of the carbon nanotubes 1 in the first flow path 41 provided in the carbon nanotube synthesis furnace 60 and aggregated. This is a step of forming the carbon nanotube aggregated wire 21 by allowing the carbon nanotube aggregated wire 21 to be formed.
- a plurality of CNTs 1 synthesized in the CNT synthesis furnace 60 enter the first channel 41 with their longitudinal direction along the flow of the carbon-containing gas.
- the first flow path 41 is arranged such that its axial direction follows the flow of the carbon-containing gas.
- the plurality of first flow paths 41 are formed so as to penetrate the first structure 63, and are arranged such that the axial direction of each first flow path 41 follows the flow of the carbon-containing gas.
- the cross-sectional area normal to the flow of the carbon-containing gas in the first flow path 41 is smaller than the cross-sectional area normal to the flow of the carbon-containing gas in the CNT synthesis furnace 60 . Therefore, the plurality of CNTs 1 that have entered the first channel 41 are oriented and aggregated along the longitudinal direction of the CNTs to form the CNT assembly line 21 within the first channel 41 .
- the shape of the carbon nanotube aggregated wire obtained by the second step is a thread shape in which a plurality of carbon nanotubes are aligned and aggregated in their longitudinal direction.
- the length of the carbon nanotube aggregated wire is not particularly limited, and can be appropriately adjusted depending on the application.
- the lower limit of the length of the CNT-assembled wire is, for example, preferably 100 ⁇ m or longer, more preferably 1000 ⁇ m or longer, and even more preferably 10 cm or longer.
- the upper limit of the length of the CNT-assembled wire is not particularly limited, it can be 100 cm or less from the viewpoint of manufacturing.
- the length of the CNT aggregate line is preferably 100 ⁇ m or more and 100 cm or less, more preferably 1000 ⁇ m or more and 100 cm or less, and still more preferably 10 cm or more and 100 cm or less.
- the length of CNT-assembled lines is measured by scanning electron microscopy, optical microscopy, or visual observation.
- the size of the diameter of the carbon nanotube aggregated wire is not particularly limited, and can be appropriately adjusted depending on the application.
- the lower limit of the diameter of the CNT-assembled wire is, for example, preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 100 ⁇ m or more, and even more preferably 300 ⁇ m or more.
- the upper limit of the diameter of the CNT-assembled wire is not particularly limited, it can be 1000 ⁇ m or less from the viewpoint of manufacturing.
- the diameter of the CNT-assembled wire is preferably 1 ⁇ m or more and 1000 ⁇ m or less, more preferably 10 ⁇ m or more and 1000 ⁇ m or less, still more preferably 100 ⁇ m or more and 1000 ⁇ m or less, and still more preferably 300 ⁇ m or more and 1000 ⁇ m or less.
- the diameter of the CNT-assembled wire is smaller than the length of the CNT-assembled wire. That is, the longitudinal direction corresponds to the lengthwise direction of the CNT-aggregated wire.
- the diameter of the carbon nanotube aggregated wire means the average outer diameter of one CNT aggregated wire.
- the average outer diameter of one CNT-assembled wire is obtained by observing a cross section at any two points of one CNT-assembled wire with a transmission electron microscope or a scanning electron microscope, It is obtained by measuring the outer diameter, which is the distance between two points, and calculating the average value of the obtained outer diameters.
- TEM Transmission electron microscope
- JEM2100 product name
- Imaging conditions magnification of 50,000 to 1,200,000 times, acceleration voltage of 60 kV to 200 kV.
- Image processing program Nondestructive paper surface fiber orientation analysis program "FiberOri8single03" (http://www.enomae.com/FiberOri/index.htm) Processing procedure: 1. Histogram average luminance correction 2 . 3. background subtraction; 4. Binarization with a single threshold; Brightness inversion.
- Orientation (180°-full width at half maximum)/180° (1)
- degree of orientation 0
- a degree of orientation of 1 means complete orientation.
- the degree of orientation is 0.8 or more and 1.0 or less, it is determined that a plurality of CNTs are aligned and aggregated in the longitudinal direction on the CNT assembly line.
- the CNT assembly line is elongated while maintaining the electrical conductivity and mechanical strength characteristics of the CNTs. .
- the carbon nanotube assembly line 21 obtained in the second step is transferred from the second end opposite to the first end of the carbon nanotube synthesis furnace 60 (the left end in FIG. 1) to This is a recovery step using a recovery gas stream flowing away from the carbon nanotube synthesis furnace 60 .
- the movement of the carbon nanotube-assembled wire 21 to the downstream side of the CNT synthesis furnace 60 can be promoted, and the collection efficiency of the CNT-assembled wire is improved.
- the collection gas flow can suppress deposition of CNTs and CNT aggregate lines in the first channel and clogging of the first channel due to the deposition. Therefore, the collection efficiency of the CNT aggregated wire is improved.
- the flow velocity of the recovery gas flow is not particularly limited, it is preferably higher than the flow velocity of the carbon-containing gas. According to this, the collection efficiency of the CNT aggregated wire is further improved.
- the “flow velocity of the recovery gas flow” refers to the second hole 74 of the recovery gas flow generator 70 provided on the second end side (downstream side) of the CNT synthesis furnace 60 (see FIG. 2 ) means the mean flow velocity of the recovery gas stream through
- the lower limit of the flow velocity of the recovery gas flow is not particularly limited, but from the viewpoint of improving the collection efficiency of the CNT assembly wire, the flow velocity is preferably twice or more, more preferably five times or more, and even more preferably ten times or more than the flow velocity of the carbon-containing gas.
- the upper limit of the flow velocity of the recovery gas stream is not particularly limited, it can be, for example, 100 times or less the flow velocity of the carbon-containing gas.
- the flow velocity of the recovery gas flow is preferably 2 to 100 times, more preferably 5 to 100 times, even more preferably 10 to 100 times the flow velocity of the carbon-containing gas.
- the lower limit of the flow velocity of the recovery gas flow is preferably 2000 cm/sec or more, more preferably 3000 cm/sec or more, and even more preferably 4000 cm/sec or more.
- the upper limit of the flow velocity of the recovery gas flow is preferably 10000 cm/sec or less.
- the flow velocity of the recovery gas flow is preferably 2000 cm/sec to 10000 cm/sec, more preferably 3000 cm/sec to 10000 cm/sec, and even more preferably 4000 cm/sec to 10000 cm/sec.
- the third step it is preferable to orient and assemble a plurality of carbon nanotube assembly lines along their longitudinal direction. According to this, it is possible to obtain a twisted wire (bundle) 31 of fused carbon nanotube wires in which a plurality of fused carbon nanotube wires are oriented and aggregated along the longitudinal direction.
- a method for aligning and assembling multiple carbon nanotube assembly lines along their longitudinal direction is to converge the recovery gas flow downstream. According to this, with the convergence of the recovery gas flow, a plurality of CNT-aggregated wires approach each other and aggregate to form a stranded wire 31 of CNT-aggregated wires.
- the recovery gas stream using an inert gas. More specifically, it is preferable to generate, downstream of the CNT synthesis furnace, a high-speed inert gas stream flowing away from the CNT synthesis furnace. According to this, the high-speed gas flow generates a suction force that draws in the air inside the CNT synthesis furnace, generating a recovery gas flow that flows away from the CNT synthesis furnace from the second end of the CNT synthesis furnace. Since the recovery gas stream contains a large amount of inert gas components, the reaction between the carbon nanotube assembly wire and the recovery gas flow is unlikely to occur, and the quality of the carbon nanotube assembly wire is maintained while maintaining the quality of the CNT assembly wire. Collection efficiency can be improved.
- the carbon nanotube assembly wire manufacturing apparatus 100 of the present embodiment includes a tubular carbon nanotube synthesis furnace 60 and one first end of the carbon nanotube synthesis furnace 60 (the right end in FIG. 1). part), the first flow path 41 provided in the carbon nanotube synthesis furnace 60, and the second end opposite to the first end of the carbon nanotube synthesis furnace 60. a recovery gas flow generator 70 provided.
- a carbon nanotube synthesis furnace (hereinafter also referred to as “CNT synthesis furnace”) 60 has a tubular shape made of, for example, a quartz tube. Carbon nanotubes 1 are formed on catalyst particles 27 in a CNT synthesis furnace 60 using a carbon-containing gas.
- the carbon nanotube synthesis furnace 60 is heated by a heating device 61 .
- the internal temperature of the CNT synthesis furnace 60 during heating is preferably 800° C. or higher and 1200° C. or lower.
- the heated carbon-containing gas may be supplied from the carbon-containing gas supply port 62 to the CNT synthesis furnace 60 , or the carbon-containing gas may be heated in the CNT synthesis furnace 60 .
- the cross-sectional area of the CNT synthesis furnace 60 is not particularly limited as long as it is large enough to provide the first flow path 41 inside the CNT synthesis furnace.
- the lower limit of the cross-sectional area of the carbon nanotube synthesis furnace 60 is preferably, for example, 50 mm 2 or more, more preferably 500 mm 2 or more, and even more preferably 1500 mm 2 or more, from the viewpoint of improving the production efficiency of CNT-assembled wires.
- the upper limit of the cross-sectional area of the CNT synthesis furnace is not particularly limited, it can be, for example, 20000 mm 2 or less from the viewpoint of manufacturing equipment.
- the cross-sectional area of the CNT synthesis furnace is preferably 50 mm 2 or more and 20000 mm 2 or less, more preferably 500 mm 2 or more and 20000 mm 2 or less, and even more preferably 1500 mm 2 or more and 20000 mm 2 or less.
- the cross-sectional area of the CNT synthesis furnace 60 means the area of the hollow portion of the CNT synthesis furnace in a cross section normal to the longitudinal direction (center line) of the CNT synthesis furnace.
- the carbon-containing gas supply port 62 is provided at one end of the carbon nanotube synthesis furnace 60 (the right end in FIG. 1), and the carbon-containing gas is supplied from the carbon-containing gas supply port 62 into the CNT synthesis furnace 60. be done.
- a catalyst (not shown) is placed near the carbon-containing gas supply port in the CNT synthesis furnace 60 .
- the carbon-containing gas supply port 62 can be configured to have a gas cylinder (not shown) and a flow control valve (not shown).
- the first channel 41 is provided inside the carbon nanotube synthesis furnace 60 .
- the cross-sectional area of the first channel is smaller than the cross-sectional area of the carbon nanotube synthesis furnace 60 .
- a plurality of carbon nanotubes are oriented along their longitudinal direction and gathered to form a carbon nanotube assembly line.
- a pulling force can be applied to the carbon nanotubes in a direction toward the downstream side of the carbon-containing gas.
- a tensile force acts on the ends of the carbon nanotubes, the carbon nanotubes extending from the catalyst particles 27 are pulled and elongated in the longitudinal direction while being plastically deformed and reduced in diameter. Therefore, it is easy to lengthen the CNT-assembled wire.
- the cross-sectional area of the first channel 41 can be appropriately set according to the desired diameter of the CNT-assembled wire.
- the lower limit of the cross-sectional area of the first flow path 41 is preferably 0.005 mm 2 or more, more preferably 0.01 mm 2 or more, and even more preferably 0.5 mm 2 or more, from the viewpoint of suppressing CNT clogging.
- the upper limit of the cross-sectional area of the first channel 41 is preferably 100 mm 2 or less, more preferably 50 mm 2 or less, and even more preferably 10 mm 2 or less, from the viewpoint of promoting the formation of CNT aggregate lines.
- the cross-sectional area of the first flow path 41 is preferably 0.005 mm 2 or more and 100 mm 2 or less, more preferably 0.01 mm 2 or more and 50 mm 2 or less, and still more preferably 0.5 mm 2 or more and 10 mm 2 or less.
- the cross-sectional area of the first flow path 41 means the area of the first flow path in a cross section normal to the center line of the first flow path.
- the lower limit of the length of the first flow path 41 is preferably 1 mm or more, more preferably 10 mm or more, from the viewpoint that the carbon nanotubes are easily subjected to a tensile force in the direction toward the downstream side of the carbon-containing gas and the CNTs are easily elongated. , more preferably 15 mm or more.
- the upper limit of the length of the first channel 41 is preferably 100 cm or less, more preferably 50 cm or less, and even more preferably 10 cm or less, from the viewpoint of suppressing CNT clogging in the first channel.
- the length of the first flow path 41 is preferably 1 mm or more and 100 cm or less, more preferably 10 mm or more and 50 cm or less, and even more preferably 15 mm or more and 10 cm or less. In this specification, the length of the first flow path 41 means the length along the centerline of the first flow path 41 .
- the first flow path 41 is preferably provided at a position separated from the first end of the CNT synthesis furnace 60 by 20 cm or more and 1000 cm or less. According to this, the CNTs flowing into the first channel have an appropriate length, and CNT assembly lines are easily formed in the first channel.
- a plurality of first flow paths 41 are preferably provided in parallel along the longitudinal direction of the CNT synthesis furnace 60 in the CNT synthesis furnace 60 .
- one first structure 63 may be provided with a plurality of first flow paths 41 .
- one CNT synthesis furnace 60 can produce a plurality of CNT assembly wires 21 .
- that the plurality of first flow paths 41 are provided in parallel along the longitudinal direction of the CNT synthesis furnace 60 means that the center line of each first flow path 41 and the longitudinal direction of the CNT synthesis furnace 60 It means that the angle formed with the direction is 0° or more and 5° or less.
- first flow paths 41 are provided in parallel in FIG. 1, the number of first flow paths is not limited to four, and any number of two or more can be employed.
- the number of first flow paths provided in parallel corresponds to the number of CNT-assembled wires to be manufactured. Therefore, by increasing the number of first flow paths provided in parallel, the number of CNT assembly lines 21 manufactured using one CNT synthesis furnace can be increased.
- the recovery gas flow generator 70 is provided at the second end (the left side in FIG. 1) opposite to the first end of the CNT synthesis furnace 60 .
- An example of the recovery gas flow generator will be described with reference to FIGS. 2 to 5.
- FIG. 1 An example of the recovery gas flow generator will be described with reference to FIGS. 2 to 5.
- FIG. 2 is a perspective view showing the recovery gas flow generator 70a.
- FIG. 3 is a perspective view of the recovery gas flow generator 70a shown in FIG. 2 as viewed from the direction of arrow A1 (the right side in FIG. 2).
- FIG. 4 is a view of the recovery gas flow generator 70a shown in FIG. 2 as viewed from the direction of arrow B1 (left side in FIG. 2).
- FIG. 5 is a sectional view taken along line XI-XI of the recovery gas flow generator 70a shown in FIG.
- the recovery gas flow generator 70a includes a through hole configured to allow the carbon nanotube assembly line to flow from the first hole 73 toward the second hole 74, and an induction gas discharge port provided outside the second hole 74. 72 and.
- the shape of the through hole of the recovery gas flow generator 70a is a truncated cone with the first hole 73 as the bottom surface and the second hole 74 as the top surface.
- the induction gas When the induction gas is discharged from the induction gas discharge port 72 in a direction away from the carbon nanotube synthesis furnace 60, the induction gas generates a suction force, and the recovery gas flows from the first hole 73 toward the second hole 74. flow occurs.
- the carbon nanotube aggregated wires 21 emitted from the first flow path 41 flow from the first hole 73 of the through-hole toward the second hole 74 along with the recovery gas flow, and the recovery gas flow generating device It is discharged to the outside of 70a and collected.
- the recovery gas flow generator 70a includes a second structure 75 having a shape surrounding the through hole.
- An internal channel 76 is preferably provided that connects the port 71 and the induction gas discharge port 72 . According to this, the flow velocity of the induction gas discharged from the induction gas discharge port 72 can be controlled by controlling the flow velocity of the induction gas introduced into the induction gas introduction port 71 .
- the lower limit of the flow velocity of the induction gas is preferably 400 cm/sec or more, more preferably 600 cm/sec or more, and even more preferably 800 cm/sec or more.
- the upper limit of the flow velocity of the induction gas is preferably 2000 cm/sec or less.
- the flow velocity of the induction gas is preferably 400 cm/sec to 2000 cm/sec, more preferably 600 cm/sec to 2000 cm/sec, and even more preferably 800 cm/sec to 2000 cm/sec.
- the induction gas discharge port 72 is ring-shaped, and the upper limit of the width d is preferably 1 mm or less. According to this, even if the amount of gas introduced from the induction gas introduction port 71 is small, the flow velocity of the gas discharged from the induction gas discharge port 72 can be increased.
- the upper limit of the width d is more preferably 0.5 mm or less, still more preferably 0.25 mm or less.
- the lower limit of the width d can be, for example, 0.05 mm or more.
- the width d is preferably 0.05 mm or more and 1 mm or less, more preferably 0.05 mm or more and 0.5 mm or less, and still more preferably 0.05 mm or more and 0.25 mm or less.
- the induction gas preferably consists of an inert gas. According to this, reaction between the carbon nanotube aggregated wire and the recovery gas flow is less likely to occur, and the collection efficiency of the CNT aggregated wire can be improved while maintaining the quality of the carbon nanotube aggregated wire.
- the shape of the through hole of the recovery gas flow generator 70a shown in FIG. 2 is a truncated cone with the first hole 73 as the bottom surface and the second hole 74 as the top surface. Therefore, the recovery gas flow flowing through the through holes converges from the first hole 73 toward the second hole 74 . For this reason, the plurality of carbon nanotube aggregated wires 21 flowing along the recovery gas flow approach each other and are aggregated to form a twisted wire 31 of CNT aggregated wires.
- the diameter of the first hole is preferably 8 mm or more and 160 mm or less
- the diameter of the second hole is preferably 4 mm or more and 80 mm or less
- the diameter of the through hole is along the axial direction of the through hole.
- the length is preferably 5 mm or more and 100 mm or less.
- FIG. 6 is a perspective view showing the recovery gas flow generator 70b.
- FIG. 7 is a XII-XII sectional view of the recovery gas flow generator 70b shown in FIG. 1, the side (right side in FIG. 6) provided with the first hole (not shown) is arranged to be connected to the CNT synthesis furnace 60. As shown in FIG.
- the recovery gas flow generator 70b basically has the same configuration as the recovery gas flow generator 70a, except that the shape of the through hole is cylindrical. Also, the flow rate and type of the induction gas introduced into the recovery gas flow generator 70b can be the same as the induction gas used in the recovery gas flow generator 70a.
- the induction gas When the induction gas is discharged from the induction gas discharge port 72 in a direction away from the carbon nanotube synthesis furnace 60, the induction gas generates a suction force, and the recovery gas flow flows from the first hole toward the second hole 74. occurs.
- the carbon nanotube aggregated wires 21 discharged from the first flow path 41 flow from the first hole of the through hole toward the second hole 74 along with the recovery gas flow, and the recovery gas flow generator 70b released to the outside and collected.
- the diameter of the first hole is preferably 8 mm or more and 160 mm or less
- the diameter of the second hole is preferably 8 mm or more and 160 mm or less.
- the thickness is preferably 5 mm or more and 100 mm or less.
- Example 1 As the apparatus 1, a carbon nanotube stranded wire manufacturing apparatus having the same configuration as the carbon nanotube stranded wire manufacturing apparatus shown in FIG. 1 is prepared. A specific configuration is as follows.
- the apparatus 1 is provided at a carbon nanotube synthesis furnace (quartz tube, hollow diameter 45 mm (cross-sectional area 1590 mm 2 ), length 1000 mm) and one first end side (right side in FIG. 1) of the carbon nanotube synthesis furnace.
- a carbon-containing gas supply port provided in the carbon nanotube synthesis furnace, four first flow paths (cylindrical shape, diameter 1 mm, length 50 mm) provided in the carbon nanotube synthesis furnace, and the second end of the carbon nanotube synthesis furnace (in FIG. 1 a recovery gas flow generator provided on the left side).
- the four first flow paths are provided in parallel along the longitudinal direction of the carbon nanotube synthesis furnace.
- the distance from the end of the CNT synthesis furnace on the side of the carbon-containing gas supply port to the end of the first channel on the side of the carbon-containing gas supply port is 950 mm.
- a catalyst (ferrocene) and an auxiliary catalyst (thiophene) are placed near the carbon-containing gas supply port inside the CNT synthesis furnace.
- the recovery gas flow generator has the configuration of the recovery gas flow generator shown in FIG. 2, and the shape of the through hole is a truncated cone.
- the first hole (the bottom of the truncated cone) is circular with a diameter of 35 mm.
- the second hole (the upper surface of the truncated cone) is circular with a diameter of 30 mm.
- the axial length of the through hole (the height of the truncated cone) is 50 mm.
- the induction gas outlet is ring-shaped and has a width d of 0.3 mm.
- the second structure of the recovery gas flow generator is provided with an internal flow path connecting the induced gas inlet and the induced gas outlet.
- the carbon nanotube stranded wire of the sample 1 and the stranded wire of the carbon nanotube stranded wire are produced.
- apparatus 1 while supplying argon gas with an argon gas concentration of 100% by volume from the carbon-containing gas supply port into the CNT synthesis furnace at a flow rate of 1000 cc / min (flow rate of 1.0 cm / sec) for 50 minutes, The temperature is increased to 1200°C.
- argon gas is stopped, and hydrogen gas is supplied at a flow rate of 10000 cc/min (flow rate of 10.5 cm/sec) and methane gas is supplied at a flow rate of 50 cc/min (flow rate of 0.05 cm/sec) for 120 minutes.
- the flow velocity of the entire mixed gas (carbon-containing gas) containing hydrogen gas and methane gas is 11.55 cm/sec.
- the CNT aggregate line formed in the first flow path flows from the first hole toward the second hole along with the flow of the recovery gas flow. Since the shape of the through-hole is a truncated cone, a plurality of stranded carbon nanotube wires are brought close to each other inside the through-hole and are gathered to form a strand of CNT stranded wires. A twisted wire of the CNT-assembled wire is recovered. The collection efficiency of the stranded wire of the CNT-assembled wire is improved as compared with the case where the collection gas flow generator is not used.
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Abstract
Description
管状のカーボンナノチューブ合成炉の一方の第1端部から炭素含有ガスを供給し、前記カーボンナノチューブ合成炉内の浮遊状態の複数の触媒粒子のそれぞれからカーボンナノチューブを成長させて、複数のカーボンナノチューブを合成する第1工程と、
前記複数のカーボンナノチューブを、前記カーボンナノチューブ合成炉内に設けられた第1流路内で、前記カーボンナノチューブの長手方向に沿って配向して集合させて、カーボンナノチューブ集合線を形成する第2工程と、
前記カーボンナノチューブ集合線を、前記カーボンナノチューブ合成炉の前記第1端部とは反対側の第2端部から、前記カーボンナノチューブ合成炉から離れる方向に流れる回収用ガス流を用いて回収する第3工程と、を備える、カーボンナノチューブ集合線の製造方法である。
管状のカーボンナノチューブ合成炉と、
前記カーボンナノチューブ合成炉の一方の第1端部に設けられた炭素含有ガス供給口と、
前記カーボンナノチューブ合成炉内に設けられた第1流路と、
前記カーボンナノチューブ合成炉の前記第1端部と反対側の第2端部に設けられた回収用ガス流発生装置と、を備える、カーボンナノチューブ集合線製造装置である。
カーボンナノチューブ合成炉内で作製されたカーボンナノチューブ集合線は、原料ガスの流れにのって、カーボンナノチューブ合成炉の下流側へ移動する。同一のカーボンナノチューブ合成炉を用いてカーボンナノチューブ集合線を効率的に回収するための方法として、原料ガスの流量を増加させ、ガスの流速を大きくすることが考えられる。一方、原料ガスの流量の上限は、カーボンナノチューブ合成のための触媒反応を考慮して決定される。従って、同一のカーボンナノチューブ合成炉を用いる場合、カーボンナノチューブの回収効率を向上させるために、原料ガスの流量を、触媒反応を考慮して決定された原料ガスの流量の上限よりも増加させるという方策を採用することができない。
本開示によれば、カーボンナノチューブ合成炉内で作製されたカーボンナノチューブ集合線を効率的に回収することが可能となる。
最初に本開示の実施態様を列記して説明する。
(1)本開示のカーボンナノチューブ集合線の製造方法は、
管状のカーボンナノチューブ合成炉の一方の第1端部から炭素含有ガスを供給し、前記カーボンナノチューブ合成炉内の浮遊状態の複数の触媒粒子のそれぞれからカーボンナノチューブを成長させて、複数のカーボンナノチューブを合成する第1工程と、
前記複数のカーボンナノチューブを、前記カーボンナノチューブ合成炉内に設けられた第1流路内で、前記カーボンナノチューブの長手方向に沿って配向して集合させて、カーボンナノチューブ集合線を形成する第2工程と、
前記カーボンナノチューブ集合線を、前記カーボンナノチューブ合成炉の前記第1端部とは反対側の第2端部から、前記カーボンナノチューブ合成炉から離れる方向に流れる回収用ガス流を用いて回収する第3工程と、を備える、カーボンナノチューブ集合線の製造方法である。
管状のカーボンナノチューブ合成炉と、
前記カーボンナノチューブ合成炉の一方の第1端部に設けられた炭素含有ガス供給口と、
前記カーボンナノチューブ合成炉内に設けられた第1流路と、
前記カーボンナノチューブ合成炉の前記第1端部と反対側の第2端部に設けられた回収用ガス流発生装置と、を備える、カーボンナノチューブ集合線製造装置である。
前記カーボンナノチューブ合成炉側に設けられた第1穴から、前記カーボンナノチューブ合成炉の反対側に設けられた第2穴に向けてカーボンナノチューブ集合線が流れるように構成された貫通孔と、
前記第2穴の外側に設けられた誘導ガス放出口と、を含むことが好ましい。
本開示のカーボンナノチューブ集合線の製造方法及びカーボンナノチューブ集合線製造装置の具体例を、以下に図面を参照しつつ説明する。本開示の図面において、同一の参照符号は、同一部分または相当部分を表すものである。また、長さ、幅、厚さ、深さなどの寸法関係は図面の明瞭化と簡略化のために適宜変更されており、必ずしも実際の寸法関係を表すものではない。
本開示の一実施の形態(以下、「本実施形態」とも記す。)に係るカーボンナノチューブ集合線の製造方法について、図1を用いて説明する。図1は、本実施形態のカーボンナノチューブ集合線の製造方法に用いられるカーボンナノチューブ集合線製造装置の一例を示す図である。
該複数のカーボンナノチューブ1を、該カーボンナノチューブ合成炉60内に設けられた第1流路41内で、該カーボンナノチューブ1の長手方向に沿って配向して集合させて、カーボンナノチューブ集合線21を形成する第2工程と、
該カーボンナノチューブ集合線21を、該カーボンナノチューブ合成炉60の該第1端部とは反対側の第2端部から、該カーボンナノチューブ合成炉60から離れる方向に流れる回収用ガス流を用いて回収する第3工程と、を備える。
第1工程は、管状のカーボンナノチューブ合成炉60の一方の第1端部(図1において、炭素含有ガス供給口62の設けられた右側の端部)から炭素含有ガスを供給し、該カーボンナノチューブ合成炉60内の浮遊状態の複数の触媒粒子27のそれぞれからカーボンナノチューブ1を成長させて、複数のカーボンナノチューブ1を合成する工程である。
第2工程は、第1工程で得られた複数のカーボンナノチューブ1をカーボンナノチューブ合成炉60内に設けられた第1流路41内で、該カーボンナノチューブ1の長手方向に沿って配向して集合させて、カーボンナノチューブ集合線21を形成する工程である。
下記の機器を用いて、下記の条件で、CNT集合線を撮像する。
撮像条件:倍率5万倍~120万倍、加速電圧60kV~200kV。
上記(a1)で撮像された画像に対して、下記の画像処理プログラムを用いて、下記の手順に従い二値化処理を施す。
処理手順:
1.ヒストグラム平均輝度補正
2.バックグラウンド除去
3.単一閾値による二値化
4.輝度反転。
上記(a2)で得られた画像に対して、上記と同一の画像処理プログラム(非破壊による紙の表面繊維配向解析プログラム「FiberOri8single03」(http://www.enomae.com/FiberOri/index.htm))を用いてフーリエ変換を行う。
フーリエ変換画像で、X軸正方向を0°として、反時計回りの角度(θ°)に対する平均振幅を計算する。フーリエ変換画像から得られた配向角度と配向強度との関係をグラフ化する。
上記グラフに基づき、半値全幅(FWHM:full width at half maximum)を測定する。
上記の半値全幅に基づき、下記式(1)により、配向度を算出する。
配向度が0の場合は、完全無配向を意味する。配向度が1の場合は完全配向を意味する。本明細書において、配向度が0.8以上1.0以下の場合、CNT集合線において、複数のCNTがこれらの長手方向に配向して集合していると判定する。
第3工程は、第2工程で得られたカーボンナノチューブ集合線21を、カーボンナノチューブ合成炉60の第1端部とは反対側の第2端部(図1において、左側の端部)から、カーボンナノチューブ合成炉60から離れる方向に流れる回収用ガス流を用いて回収する工程である。これにより、カーボンナノチューブ集合線21のCNT合成炉60の下流側への移動を促進することができ、CNT集合線の回収効率が向上する。また、回収用ガス流により、第1流路内におけるCNTやCNT集合線の堆積や、該堆積に起因する第1流路の目詰まりを抑制することができる。よって、CNT集合線の回収効率が向上する。
実施形態1に係るカーボンナノチューブ集合線の製造方法に用いられるカーボンナノチューブ集合線製造装置の一例について、図1~図7を用いて説明する。
カーボンナノチューブ合成炉(以下、「CNT合成炉」とも記す。)60は、例えば石英管からなる管状の形状を有する。CNT合成炉60において、炭素含有ガスを用いて、触媒粒子27上にカーボンナノチューブ1が形成される。
炭素含有ガス供給口62は、カーボンナノチューブ合成炉60の一方の端部(図1において右側の端部)に設けられ、炭素含有ガスは該炭素含有ガス供給口62からCNT合成炉60内に供給される。CNT合成炉60内の炭素含有ガス供給口付近に、触媒(図示せず)が配置される。
第1流路41は、カーボンナノチューブ合成炉60内に設けられる。第1流路の断面積は、カーボンナノチューブ合成炉60の断面積よりも小さい。これによると、第1流路内で、複数のカーボンナノチューブがそれらの長手方向に沿って配向して集合し、カーボンナノチューブ集合線を形成する。更に、第1流路内で、カーボンナノチューブに炭素含有ガスの下流側に向かう方向の引張力を加えることができる。カーボンナノチューブの端部に引張力が作用することで、触媒粒子27から延びるカーボンナノチューブが引っ張られ、塑性変形して縮径しつつ長手方向に伸長される。よって、CNT集合線を長尺化しやすい。
回収用ガス流発生装置70は、CNT合成炉60の第1端部と反対側の第2端部(図1において、左側)に設けられる。回収用ガス流発生装置の一例について、図2~図5を用いて説明する。
回収用ガス流発生装置の他の一例について、図6及び図7を用いて説明する。図6は、回収用ガス流発生装置70bを示す斜視図である。図7は、図6に示される回収用ガス流発生装置70bのXII-XII断面図である。図1のCNT集合線製造装置に適用される場合は、第1穴(図示せず)の設けられた側(図6において右側)がCNT合成炉60に接続されるように配置される。
装置1として、図1に示されるカーボンナノチューブ集合線製造装置と同様の構成を有するカーボンナノチューブ集合線製造装置を準備する。具体的な構成は以下の通りである。
今回開示された実施の形態および実施例はすべての点で例示であって、制限的なものではないと考えられるべきである。本発明の範囲は上記した実施の形態および実施例ではなく請求の範囲によって示され、請求の範囲と均等の意味、および範囲内でのすべての変更が含まれることが意図される。
Claims (8)
- 管状のカーボンナノチューブ合成炉の一方の第1端部から炭素含有ガスを供給し、前記カーボンナノチューブ合成炉内の浮遊状態の複数の触媒粒子のそれぞれからカーボンナノチューブを成長させて、複数のカーボンナノチューブを合成する第1工程と、
前記複数のカーボンナノチューブを、前記カーボンナノチューブ合成炉内に設けられた第1流路内で、前記カーボンナノチューブの長手方向に沿って配向して集合させて、カーボンナノチューブ集合線を形成する第2工程と、
前記カーボンナノチューブ集合線を、前記カーボンナノチューブ合成炉の前記第1端部とは反対側の第2端部から、前記カーボンナノチューブ合成炉から離れる方向に流れる回収用ガス流を用いて回収する第3工程と、を備える、カーボンナノチューブ集合線の製造方法。 - 前記回収用ガス流の流速は、前記炭素含有ガスの流速の2倍以上100倍以下である、請求項1に記載のカーボンナノチューブ集合線の製造方法。
- 前記第3工程において、複数の前記カーボンナノチューブ集合線をそれらの長手方向に沿って配向して集合させる、請求項1又は請求項2に記載のカーボンナノチューブ集合線の製造方法。
- 前記回収用ガス流を、不活性ガスを用いて発生させる、請求項1から請求項3のいずれか1項に記載のカーボンナノチューブ集合線の製造方法。
- 管状のカーボンナノチューブ合成炉と、
前記カーボンナノチューブ合成炉の一方の第1端部に設けられた炭素含有ガス供給口と、
前記カーボンナノチューブ合成炉内に設けられた第1流路と、
前記カーボンナノチューブ合成炉の前記第1端部と反対側の第2端部に設けられた回収用ガス流発生装置と、を備える、カーボンナノチューブ集合線製造装置。 - 前記回収用ガス流発生装置は、
前記カーボンナノチューブ合成炉側に設けられた第1穴から、前記カーボンナノチューブ合成炉の反対側に設けられた第2穴に向けてカーボンナノチューブ集合線が流れるように構成された貫通孔と、
前記第2穴の外側に設けられた誘導ガス放出口と、を含む、請求項5に記載のカーボンナノチューブ集合線製造装置。 - 前記貫通孔の形状は円錐台である、請求項6に記載のカーボンナノチューブ集合線製造装置。
- 前記貫通孔の形状は円柱である、請求項6に記載のカーボンナノチューブ集合線製造装置。
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