JP4132480B2 - Carbon nanofiber sliver thread and method for producing the same - Google Patents

Carbon nanofiber sliver thread and method for producing the same Download PDF

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JP4132480B2
JP4132480B2 JP29050599A JP29050599A JP4132480B2 JP 4132480 B2 JP4132480 B2 JP 4132480B2 JP 29050599 A JP29050599 A JP 29050599A JP 29050599 A JP29050599 A JP 29050599A JP 4132480 B2 JP4132480 B2 JP 4132480B2
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gas
carbon
discharge pipe
carbon nanofiber
sliver
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JP2001115348A (en
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孝 大崎
文夫 河村
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日機装株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a carbon nanofiber sliver thread and a method for producing the same, and more specifically, a carbon nanofiber formed by discontinuous carbon nanofibers being arranged in almost one direction and having excellent electrical conductivity and mechanical properties. The present invention relates to a fiber sliver thread and a simple manufacturing method thereof.
[0002]
[Prior art]
Fine carbon fibers are generally produced using a gas phase reaction. For example, a fine carbon fiber is produced by discharge of a graphite electrode under reduced pressure, a method called a discharge method, transition metal fine particles such as iron on a ceramic support are brought into contact with hydrocarbon gas in a high-temperature hydrogen atmosphere. A method called a supporting method for producing fine carbon fibers, a fluidized gas phase method for producing fine carbon fibers by bringing a transition metal compound-containing gas and a hydrocarbon-containing gas into contact with each other in a high-temperature hydrogen atmosphere. And the like method.
[0003]
The fluidized gas phase method is most suitable for industrial production of fine vapor grown carbon fibers.
[0004]
It is considered that the production mechanism of fine vapor-grown carbon fibers in this fluidized vapor phase method is as follows. That is, for example, when a gaseous transition metal compound is thermally decomposed, transition metal particles having a very small particle size are generated in the gas phase. When the organic compound is decomposed in the form of metal particles generated and suspended in the gas phase, carbon is deposited on the metal particles. Carbon deposited on the metal particles grows in one direction. As a result, vapor grown carbon fiber is produced.
[0005]
The fine carbon fiber as a product obtained by the discharge method is subjected to a purification operation for separating by-product soot, and the fine carbon fiber as a product obtained by the loading method is purified to separate from the carrier. After the operation, the fine carbon fiber as a product obtained by the fluidized gas phase method is subjected to a refining operation for removing the adhering tar, and then used.
[0006]
According to the fluidized vapor phase method, a vapor-grown carbon fiber having an outer diameter of 50 nm to 10 μm, a length of 200 nm to 2000 μm, and an aspect ratio of 100 or more can be easily produced industrially. (See M. Hatano, T. Ohsaki, K. Arakawa; 30th National SAMPE Symposiumu preprint 1467 (1985), Japanese Patent Publication No. 62-49363, etc.).
[0007]
Further, according to the fluidized gas phase method, a highly crystallized carbon fiber having a diameter of 50 nm to 2 μm can be produced (see Japanese Patent Publication No. 3-61768), and a high crystallization having a diameter of 10 nm to 500 nm. Carbon fiber can be produced (see Japanese Patent Publication No. 5-36521).
[0008]
However, the vapor-grown carbon fibers produced by these vapor-phase growth methods are obtained as a fiber mass in which the aspect ratio is at least 100 or more, usually 500 or more, and the vapor-grown carbon fibers are entangled with each other.
[0009]
The vapor-grown carbon fiber that is a fiber lump is limited in its application and use, so the vapor-grown carbon fiber that is a lump of fiber is cut by means such as pulverization and mixed with the resin. A method was also examined. However, in such a method, the fibers are randomly oriented. Therefore, using a fiber lump having such a random orientation makes it difficult to obtain a fiber reinforced resin in which the fibers are oriented in a specific direction.
[0010]
The fine carbon fiber is not usually used as it is, and is used in combination with a resin or the like. Therefore, when the fine carbon fiber is combined with the resin, it is important to uniformly disperse the resin in the resin. In order to uniformly disperse the fine carbon fibers in the resin, a method of further pulverizing the fine carbon fibers, a method of making the fine carbon fibers into a thin sheet using a papermaking technique, and the like have been proposed. The dispersion state of the fine carbon fibers in the resin is three-dimensional random orientation, and the thin sheet is two-dimensional random orientation. Since the fine carbon fiber is a discontinuous fiber, there are few proposals for one-dimensional orientation, and even if it exists, it is only necessary that the fine carbon fiber is oriented to some extent by shearing force after the fine carbon fiber is dispersed in a resin or the like. It was.
[0011]
By the way, in recent years, fine carbon fibers oriented in one direction have been desired as a part of an electron beam emitting member. A method of generating fine carbon fibers in the shape of flocking on a carrier is proposed for unidirectionally oriented fine carbon fibers, but there is a problem of removing the carrier, and the productivity is still not good There's a problem.
[0012]
Further, if there is a unidirectional array of fine carbon fibers, it is expected that a fiber-reinforced composite resin with even greater strength can be obtained by combining it with a resin.
[0013]
[Problems to be solved by the invention]
An object of the present invention is to provide a carbon nanofiber sliver thread.
[0014]
An object of the present invention is to provide a carbon nanofiber sliver yarn that is not twisted.
[0015]
Another object of the present invention is to provide a twisted carbon nanofiber sliver yarn.
[0016]
Another object of the present invention is to provide a method for producing a carbon nanofiber sliver yarn that focuses carbon nanofibers and is not twisted.
[0017]
Still another object of the present invention is to provide a method for producing a twisted carbon nanofiber sliver yarn by focusing carbon nanofibers.
[0018]
[Means for Solving the Problems]
  Means for achieving the object includes discontinuous carbon nanofibers having an average outer diameter of 3 to 200 nm.The fiber filling density is 0.0001 to 10% of the wrinkle density, and the strength is 0.01 to 100 g / mm 2 Is,It is a carbon nanofiber sliver thread that is substantially untwisted,
  Containing discontinuous carbon nanofibers with an average outer diameter of 3 to 200 nmThe fiber filling density is 0.0001 to 10% of the wrinkle density, and the strength is 0.01 to 100 g / mm 2 Is,The carbon nanofiber sliver yarn is characterized by being twisted so that the average value of the direction of the discontinuous carbon nanofibers relative to the length direction of the sliver yarn is 30 degrees at most.
[0019]
In a preferred embodiment of the carbon nanofiber sliver thread according to the present invention, the discontinuous carbon nanofiber is a vapor-grown carbon fiber that is hollow, and an average outer diameter thereof is 5 to 50 nm.
[0020]
  The method for producing a carbon nanofiber sliver thread according to the present invention includes a discontinuous carbon nanofiber generated from a carbon source gas and a catalyst metal source gas supplied together with a carrier gas from one end of a furnace core tube.By focusing the discontinuous carbon nanofibers focused on the center of the exhaust pipe outside the exhaust pipe with the guide gas.Discontinuous carbon nanofibersThe fiber packing density is 0.0001 to 10% of the wrinkle densityThe method for producing a carbon nanofiber sliver thread according to claim 1, characterized by comprising a step of converging.
  Another manufacturing method according to the present invention is a discontinuous carbon nanofiber formed from a carbon source gas and a catalytic metal source gas supplied together with a carrier gas from one end of a furnace core tube.By focusing the discontinuous carbon nanofibers focused on the center of the exhaust pipe outside the exhaust pipe with the guide gas.Discontinuous carbon nanofibersThe fiber packing density is 0.0001 to 10% of the wrinkle densityThe method for producing a carbon nanofiber sliver yarn according to claim 1, comprising a step of converging and a step of twisting the yarn collected inside or outside the discharge pipe.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
(1) Carbon nanofiber sliver thread
The carbon nanofiber sliver thread according to the present invention is a discontinuous carbon nanofiber converging body having an average outer diameter of 3 to 200 nm.
[0022]
Carbon nanofibers are vapor-grown carbon fibers whose outer diameter is in the above-mentioned range, are hollow, and have an annual ring structure in which the graphite network surface is parallel to the fiber axis. It has a length of several hundred μm. Carbon nanofibers having a diameter of 10 nm or less are sometimes referred to as nanotubes because the volume ratio occupied by the hollow portion is large.
[0023]
The average outer diameter of the carbon nanofibers is an average value of the outer diameters obtained by observing the carbon nanofibers with a scanning electron microscope and selecting 50 to 100 carbon nanofibers present in the visual field. The length is extremely approximate since it is difficult to measure to obtain an average value.
[0024]
In the carbon nanofiber, a hollow core portion is present at the center along the fiber axis, and a single-layer or multiple-layer carbon lattice plane is formed in parallel in an annual ring shape so as to surround the hollow core portion, Moreover, the lattice spacing d002Has a structure in the range of 0.34 to 0.36 nm.
[0025]
The carbon nanofiber sliver thread has a fiber filling density of 0.0001 to 10%, preferably 0.001 to 1% of the true density. When the fiber filling density of the carbon nanofiber sliver yarn is larger than the upper limit, the deviation of the fiber axis of each carbon nanofiber with respect to the longitudinal axis of the carbon nanofiber sliver yarn exceeds 30 degrees on average, and the orientation effect May not occur.
[0026]
This carbon nanofiber sliver thread is usually 0.01-100 g / mm in strength.2, Especially 0.1-10 g / mm2It is. If the strength of the carbon nanofiber sliver yarn is smaller than the lower limit, the fiber strength becomes smaller and difficult to handle. On the other hand, a carbon nanofiber sliver yarn having a fiber strength larger than the upper limit is produced. Have difficulty. The strength of the carbon nanofiber sliver thread can be obtained by a normal fiber strength measurement method.
[0027]
An example of the carbon nanofiber sliver yarn is a yarn that is not twisted.
[0028]
The carbon nanofiber sliver thread in the present invention will be described. In the textile industry such as spinning, in the process of producing twisted yarn, usually, a sliver yarn in which short single fibers are entangled loosely and oriented to some extent in the length direction is produced, and then it is pulled out while increasing the speed ratio. By giving a twist, it is a twisted yarn. The sliver yarn has a low bulk density and is not strongly twisted. Therefore, the sliver yarn is strong enough to pull out lightly, but if you look at the loose portion, the single fiber is the length of the sliver yarn. You can see that they are aligned in the direction.
[0029]
The carbon nanofiber sliver yarn of the present invention is not produced by the same process as the spinning process, but it has a low bulk density and is broken when pulled lightly. In other words, the sliver yarn is characterized in that the single fibers are oriented in the direction of the yarn to the extent that the twist is slightly applied.
[0030]
The ultrafine carbon fiber sliver thread-like yarn according to the present invention is suitably produced in vapor phase carbon fiber production by a fluidized vapor phase method. That is, the fine carbon fiber taken out as a fiber lump is not used as a sliver yarn, but when the fiber is in a state of being dispersed in the airflow immediately after generation or during the generation, By compressing, a sliver yarn without twist is obtained, and further, a sliver yarn with twist is obtained by rotating the airflow.
[0031]
However, in the carbon nanofiber sliver thread-like yarn according to the present invention, a bundling body as a yarn is formed even if it is not twisted. The reason for this is presumed to be that a minute amount of an adhesive component such as a tar component generated in the production process described later of the carbon nanofiber sliver yarn binds the carbon nanofibers to each other.
[0032]
The inclination angle of the carbon nanofiber single fiber forming the carbon nanofiber sliver thread of this invention is 30 degrees at most even if the average value is 0 degree with the length direction (thread axis) of the carbon nanofiber sliver thread as 0 degree. The angle is preferably 0.5 to 30 degrees, particularly preferably 1 to 20 degrees, and further preferably 2 to 10 degrees.
[0033]
If the orientation of the carbon nanofibers as a twist exceeds 30 degrees, even if the carbon nanofiber sliver thread is used as a composite material or as a component of an electron beam generator, mechanical properties (for example, mechanical properties ( Strength, elastic modulus, etc.), electrical characteristics (conductivity, discharge characteristics, etc.), thermal characteristics (thermal conductivity, etc.), physical characteristics (expansion coefficient, etc.), etc. may be reduced.
In particular, when unidirectional characteristic performance is exhibited, the crystallinity of the carbon nanofibers may be improved by heat treatment at a temperature of 2000 ° C. or higher, preferably 2500 ° C. or higher, more preferably 2500 ° C. or higher.
[0034]
The orientation of the carbon nanofibers is determined by measuring the inclination angle of each carbon nanofiber single fiber in the carbon nanofiber sliver thread by scanning electron microscope observation, and taking the average value as the inclination angle of the carbon nanofiber. More specifically, the carbon nanofiber sliver thread is observed at a magnification of about 30 to 50 times with a scanning electron microscope, and an electron micrograph is taken to the extent that the thread axis can be understood. Taking a photo of the carbon nanofiber sliver thread in the field of view of the electron microscope, focusing on a specific point in the carbon nanofiber sliver thread, raising the magnification to 100 times, 300 times, 1000 times, and 10,000 times, the carbon nanofiber sliver thread shape After the yarn axis of the yarn can be drawn as a straight line on the photograph, the inclination angle of the carbon nanofiber with respect to the length direction of the carbon nanofiber sliver yarn is measured. The number of measurement unit fibers is 50 at random. There are at least two measurement points, preferably 3-5.
[0035]
Since the carbon nanofiber sliver yarn according to the present invention has an inclination angle of at most 30 degrees with respect to the length direction of the carbon nanofiber sliver yarn of the carbon nanofiber, the carbon nanofiber is substantially in one direction. It can be said that they are arranged in Therefore, this carbon nanofiber sliver thread can be made into a fiber lump aligned in one direction by cutting it to a predetermined length. That is, from the carbon nanofiber sliver thread according to the present invention, a fiber lump of carbon nanofibers aligned in one direction, which has not been obtained so far, can be easily obtained. The carbon nanofibers aligned in one direction are useful as a reinforcing material in a composite material containing a resin, rubber, metal, and ceramic as a base material, or as a field emission electron source. Further, the carbon nanofiber sliver yarn can be used alone or in bundles and strongly twisted to obtain a twisted yarn similar to the spun yarn.
(2) Production method of carbon nanofiber sliver thread
In the carbon nanofiber sliver yarn according to the present invention, discontinuous carbon nanofibers generated from a carbon source gas and a catalyst metal source gas supplied together with a carrier gas from one end of the furnace core tube are arranged in the furnace core tube. It can be manufactured through a fiber bundling process for bundling in the discharge pipe.
[0036]
In the fiber focusing step, the discontinuous carbon nanofibers are wrapped with a high-temperature guide gas, the discontinuous carbon nanofibers are collected at the center of the discharge pipe, and the discontinuous carbon nanofibers are collected at the center of the discharge pipe. A carbon nanofiber sliver thread, which is a converging body of discontinuous carbon nanofibers, is produced by pulling out of the discharge pipe with a guide gas in the state. In this step, when the guide gas drawn into the discharge pipe and sucked out of the discharge pipe is not a swirl flow but a piston flow, the carbon nanofiber sliver yarn that is focused by the guide gas is twisted. It is in a state that does not take. As described above, the discontinuous carbon nanofibers are bonded to each other by an adhesive component such as tar generated as a by-product when generating the discontinuous carbon nanofibers, or by the entanglement between the discontinuous carbon nanofibers, This forms a carbon nanofiber sliver thread.
[0037]
The furnace core tube may be a vertical furnace core tube that is erected vertically or substantially straight, or a horizontal furnace tube that is horizontally or substantially horizontally disposed.
[0038]
In another aspect of the method according to the present invention, the discontinuous carbon nanofibers generated from the carbon source gas and the catalytic metal source gas supplied together with the carrier gas from one end of the furnace core tube are discharged in the furnace core tube. A method for producing a carbon nanofiber sliver yarn, characterized by comprising a step of converging in a tube, and a step of twisting the yarn collected inside or outside the discharge tube. According to this method, a twisted fine carbonaceous sliver yarn can be produced.
[0039]
Next, a carbon nanofiber sliver thread-like yarn manufacturing apparatus in which the furnace core tube is a vertical furnace core tube will be described as an example. FIG. 1 is an explanatory view showing an example of the carbon nanofiber sliver thread-like yarn manufacturing apparatus.
In FIG. 1, 1 is an apparatus for producing a carbon nanofiber sliver yarn that is an example of the present invention, 2 is a raw material tank that contains a mixture of a carbon source and a catalytic metal source, for example, an organometallic compound, and 3 is a suction of the mixture in the raw material tank. A pump for discharging and adjusting the flow rate, 4 is a preheater for preheating the mixture to a predetermined temperature, 5 is vaporized by further heating the preheated mixture, and has the same composition as the sent mixture A heating vaporizer that generates gas, 6 is a first mass flow controller that adjusts the flow rate of a carrier gas that is circulated with the vaporized mixture, and 7 is an example of a nozzle of a raw material supply means in the carbon nanofiber sliver yarn production apparatus according to the present invention. The cooling gas supplied to the cooling jacket attached to the source gas supply nozzle is air or nitrogen 8 is a second mass flow controller for adjusting the flow rate of the carrier gas, 9 is a heat tube for maintaining the gas of the heated mixture at a predetermined temperature, and 10 is an internal portion from the top of the vertical furnace core tube. A cylindrical tubular source gas supply nozzle 11 for introducing a mixed gas into a vertical furnace core tube, which is a reaction tube in which a reaction region and a temperature lowering region are formed by an electric furnace described later, A cooling jacket surrounding the source gas supply nozzle, 13 is a cooling gas supply port, 13A is a cooling gas discharge port for discharging the cooling gas supplied into the cooling jacket, 14 is a carrier gas supply nozzle, and 14A is the above-mentioned Gas rectifying means mounted at the tip of the carrier gas supply nozzle, 15 is an electric furnace as heating means, and 18 is a raw material gas supply port in the raw material gas supply nozzle Reference numeral 19 is a pipe, 20 is a pipe, 21 is a raw material supply pipe for sending the mixture discharged from the pump to the vaporizer, 22 is a pipe, 23 is a pipe, 30 is a discharge means, 31 is a discharge pipe, 31A is an opening in the discharge pipe 31 , 32 is a drive gas ejection nozzle, 33 is an ejector pipe, 40 is a guide gas supply means, 41 is a gas uniform supply tank, 42 is a guide gas supply pipe, and 43 is a flow adjusting section.
[0040]
Hereinafter, preferred embodiments of the present invention will be further described with reference to FIG.
[0041]
Here, the catalyst metal source is not particularly limited as long as it is a substance or compound that generates a metal that becomes a catalyst by thermal decomposition. Examples of the catalyst metal source that can be used include organic transition metal compounds described in JP-A-60-54998, page 3, upper left column, line 9 to upper right column, lowermost line, paragraph of JP-A-9-324325. And organic transition metal compounds described in paragraph [0049] of JP-A-9-78360, and the like.
[0042]
Preferred examples of the catalyst metal source include organic transition metal compounds such as ferrocene and nickelocene, and transition metal compounds such as metal carbonyl including iron carbonyl. A catalyst metal source can also be used individually by 1 type, and can also use multiple types together.
[0043]
The catalytic metal source can also be used with a cocatalyst. As such a co-catalyst, any catalyst can be used as long as it can interact with the catalyst metal generated from the catalyst metal source to promote the formation of carbon nanofibers, and paragraph number [0051] of JP-A-9-78360. And sulfur-containing heterocyclic compounds and sulfur compounds described in paragraph [0061] of JP-A-9-324325 can be used without limitation. Suitable promoters include sulfur compounds, particularly thiophene and hydrogen sulfide.
[0044]
The carbon source gas is not particularly limited as long as it is a compound that can generate carbon by pyrolysis to generate carbon nanofibers. Examples of usable carbon sources include carbon compounds described in JP-B-60-54998, page 2, lower left column, line 4 to same page, lower right column, line 10; JP-A-9-324325, paragraph number And organic compounds described in paragraph [0050] of JP-A-9-78360. Preferable examples of various carbon sources include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane, propane, ethane, and methane, and alicyclic hydrocarbons such as cyclohexane. In addition, the carbon source can also use the single type individually, and can also use multiple types together.
[0045]
The ratio of the carbon source gas and the catalyst metal source gas charged into the vertical furnace core tube to the total mixed gas is preferably 0 to 40% and 0.01 to 40%, respectively, more preferably 0.5 to each. 10% and 0.05 to 10%. Here, the concentration of the carbon source gas may be 0 because the carbon source gas is not necessarily required when, for example, the organometallic compound that is the catalyst metal source contains sufficient carbon in the molecule. Meaning. Therefore, in the present invention, the carbon source and the catalytic metal source may be the same compound.
[0046]
In addition, when carbon nanofibers are formed, they grow in thickness and contain a large amount of pyrolytic carbon. Therefore, in order to obtain carbon nanofibers that are fine and have a high degree of graphitization without the deposition of pyrolytic carbon, carbon It is preferable to reduce the concentration of the source and increase the concentration of the catalytic metal source.
[0047]
As the carrier gas, a known gas used for the production of carbon nanofibers and the like can be appropriately employed, and hydrogen can be mentioned as a suitable example.
[0048]
The heating temperature in the reaction region by the electric furnace 15 is preferably 900 to 1300 ° C, particularly 1000 to 1250 ° C, and more preferably 1050 to 1200 ° C.
[0049]
In addition, as a reaction furnace provided with a vertical furnace core tube, a heating means, and a raw material supply means, it describes in the Example in Unexamined-Japanese-Patent No. 9-78360, Unexamined-Japanese-Patent No. 9-229918, Unexamined-Japanese-Patent No. 9-324325, etc. A suitable reactor can be employed.
[0050]
For example, (1) the discharge pipe 31 can be arranged so that the upper opening 31A of the discharge pipe 31 faces the lower end of the vertical furnace core pipe 11, and (2) However, the carbon fiber material generated in the reaction region, such as carbon nanofibers and / or carbon nanotubes, is discharged to an appropriate position in the temperature lowering region where the carbon fiber material can be taken in before reaching the tube wall in the temperature lowering region. The discharge pipe can be arranged so that there is an upper opening in the pipe, but (3) the discharge pipe is inserted inside the vertical furnace core pipe and discharged so that the upper opening is located facing the reaction area. Tubes can also be placed. When the discharge pipe is inserted into the vertical furnace core tube so that the upper opening is located in the temperature lowering region, the temperature is lower by 200 ° C. than the temperature of the reaction region (soaking temperature), preferably by 100 ° C. It is preferable to arrange the discharge pipe so that the upper opening is located.
[0051]
The position of the discharge pipe is preferably the case (3). In this case, the possibility that the source gas reaches the inner wall of the vertical core tube is reduced.
[0052]
When the discharge pipe is a straight pipe having the same diameter from the opening to the rear end, the inner diameter of the opening of the discharge pipe is 1.3 to 10 times the inner diameter of the source gas supply nozzle, preferably 1.5 to It is preferably 8 times, more preferably 1.7 to 6 times. When the inner diameter of the opening of the discharge pipe is in the above range, the raw material gas and the carrier gas supplied from above are introduced into the discharge pipe while being wrapped in the guide gas in a state of little disturbance, and the vertical furnace core There is an advantage that fiber formation on the inner wall of the tube is prevented.
[0053]
Further, the discharge pipe is not limited to a straight pipe, but may be a pipe body having a diameter different from that of the opening and a pipe portion other than the opening of the discharge pipe.
[0054]
In this case, the internal diameter of the insertion portion other than the opening in the discharge pipe, that is, the inner diameter of the pipe portion is 1.1 to 10 times, preferably 1.3 to 8 times, most preferably 1.5 to 6 times the inner diameter of the source gas supply nozzle. Double is desirable. When the discharge pipe is in such a ratio, the air flow linear velocity in the discharge pipe is suitable, and the air flow in the discharge pipe does not have to be disturbed.
[0055]
In order to efficiently suck the raw material gas supplied from the raw material gas supply nozzle and the carbon nanofiber generated from a part of this raw material gas into the discharge pipe from the opening, the shape of the discharge pipe is the center of the discharge pipe in the opening. It is preferable to form the shape which spreads from a part (it is also called a straight pipe part) toward the edge of an opening part in a funnel shape. Here, the funnel shape means a shape in which the inner diameter of the opening edge is larger than the inner diameter of the central portion of the discharge pipe. For example, as shown in FIG. 2, the conical shape 31B and FIG. A trumpet shape 31C as shown in FIG. 4, a saddle shape 31D as shown in FIG. That is, the line from the edge of the opening to the center of the discharge pipe may be a straight line (in this case, a conical shape) or a curved line. This funnel-shaped part is also called a reducer.
[0056]
A preferable shape when the line from the edge of the opening of the discharge pipe to the center of the discharge pipe is a curve is a shape known as a wind tunnel contracting nozzle. That is, when the flow coming from a wide upstream area is narrowed downstream, the flow velocity in the cross section is made steady, parallel, and uniform in the contraction change portion, and the strength of the turbulence of the airflow is reduced. (For example, Ryoji Kobayashi “Design of a wind tunnel contraction nozzle”; Report of Research Institute for High-Speed Mechanics, Tohoku University, Vol. 46 (1981), No. 400, P17 to P37, FIGS. 2, 3, and 4 (The curve shape is indicated as R / D1 in Fig. 9.) Also, the shape of the reducer used when welding a large-diameter gas pipe to a small-diameter gas pipe is similarly smooth. Therefore, it can be said that this is a preferable shape.
[0057]
The discharge means includes an exhaust device that exhausts the gas in the exhaust pipe, and is coupled to a collection device that collects the carbon nanofibers sucked into the exhaust pipe as carbon nanofiber sliver yarns.
[0058]
The exhaust device may be formed so as to be able to form an air flow for sucking and conveying the carbon nanofibers generated in the vertical furnace core tube or the discharge tube together with the guide gas, for example, an opening of the discharge tube. It is possible to employ a fan, an ejector, or the like disposed inside the discharge pipe sufficiently away from the outlet, the outlet of the discharge pipe, or a position slightly away from the outlet of the discharge pipe.
[0059]
The ejector is designed to introduce a high-speed airflow from the outside into the airflow in the discharge pipe at high speed, and this high-speed airflow is used to deliver the airflow in the discharge pipe at high speed. 1 to −100 mm water column, preferably −1 to −50 mm water column, particularly preferably −3 to −30 mm water column decompression is formed at the position where the water column joins, for example, as shown in FIG. The ejector body with the lower end of the discharge pipe inserted so that the lower opening is located inside, the high-speed air flow introduction pipe inserted into the ejector body, the ejector body, concentric with the discharge pipe, and A discharge pipe provided facing the lower opening of the discharge pipe, and the inner diameter of the discharge pipe and the high-speed airflow guide so that the air pressure in the lower opening of the discharge pipe is within the above range. Flow rate of the high-speed air flow ejected from the tubes, the inner diameter or the like of the outlet pipe is designed.
[0060]
The collecting device may be provided upstream of the exhaust device, whether it is an ejector or a fan. If it is downstream, the sliver thread form is often lost by the exhaust device.
As this collection device, various known machines, instruments, devices, etc. can be adopted as long as the device can collect the carbon nanofiber sliver yarns formed of carbon nanofibers. A collection box may be provided after (in front of the exhaust device) and collected in a cross or a net installed in the box. In addition, winding by a winder, accumulation in a drum tube by a shake-off device, and the like are possible. In order to collect some of the carbon nanofibers that did not become sliver filaments, spray a dry collector such as an electrostatic precipitator, bag filter, or cyclone, and water or organic liquid after the sliver collector. It is recommended to install a wet type collecting device.
A suitable collection device is shown in FIG. In FIG. 8, 31 is a discharge pipe, and 34 is a discharge pipe guiding duct. This discharge pipe guiding duct has a rear end portion of the discharge pipe 31 in a driving gas introduction port 35 which is an inlet opening thereof. 51 is a nanofiber collection box that also serves as a sliver thread collection box, 52 is an exhaust fan, 53 is a sliver thread collection bar for collecting the sliver thread on the cross, and 54 is This is a nanofiber collection net for collecting nanofibers that have passed through the sliver filament collection bar 53 without forming a sliver filament.
[0061]
The guide gas supply means does not form an air flow, for example, a swirl flow, which flows so that the guide gas swirls along the outer periphery of the discharge pipe from one end of the discharge pipe to the opening of the discharge pipe, and therefore substantially. The piston flow is made to flow along the outer peripheral wall of the discharge pipe, and the guide gas is uniformly supplied into the opening over the entire periphery of the edge of the opening. In this guide gas supply means, the guide gas is directed toward the opening of the discharge pipe at a uniform flow rate in an air flow substantially parallel to the center axis of the discharge pipe in any plane perpendicular to the center axis of the discharge pipe. And a gas uniform supply tank for storing the guide gas introduced from the outside.
[0062]
An example of the guide gas supply means 40 is combined with a vertical discharge pipe 31 inserted and arranged inside the vertical furnace core pipe 11 as shown in FIG. The guide gas supply means 40 includes a gas uniform supply tank 41, a guide gas introduction pipe 42 for introducing a guide gas into the gas uniform supply tank 41, and a discharge pipe 31 while rectifying the gas in the gas uniform supply tank 41. And a flow adjusting unit 43 for guiding the guide gas to the opening 31A.
[0063]
When the gas uniform supply tank 41 has a cylindrical shape, the inner diameter thereof is 1.1 to 4 times, preferably 1.3 to 3 times, particularly preferably 1.5 to 2 times the inner diameter of the vertical core tube 11. It is desirable to design 5 times. If the inner diameter of the uniform gas supply tank 41 is set within the above range, the amount of guide gas supplied to the opening of the discharge pipe becomes excessive, and the guide gas is opened without disturbing the air flow in the vertical core tube. It can supply uniformly over the perimeter of a part.
[0064]
In order to supply the guide gas uniformly over the entire circumference of the opening, the flow rate of the guide gas is 0.1 to 10 times the total flow rate of the raw material gas and the carrier gas flowing from the upper part of the vertical core tube, preferably It is also preferable to adjust to 0.3 to 5 times, more preferably 0.5 to 3 times.
[0065]
The optimum value of the amount of the guide gas and the amount of gas descending the vertical furnace core tube is related to the inner diameter of the vertical furnace core tube, the diameter of the discharge tube, and the diameter of the opening of the discharge tube. However, generally speaking, the ascending linear velocity of the guide gas between the outer peripheral surface of the discharge pipe and the inner wall of the vertical furnace core tube is the average descending line of the gas descending the vertical furnace core tube. 0.1 to 10 times the speed, preferably 0.3 to 5 times, and further 0.5 to 3 times, the guide gas does not disturb the air flow of the gas descending in the vertical furnace core tube by the piston flow In addition, it is preferable in that the descending gas does not descend outside the opening of the discharge pipe and does not cause fiber adhesion to the inner wall of the vertical furnace core pipe.
[0066]
The flow adjusting unit 43 has a function of adjusting the guide gas flowing into the opening of the discharge pipe into an upward air flow parallel to the central axis of the discharge pipe when a swirling flow of the guide gas is generated in the gas uniform supply tank 41. And when the reaction gas flow swirls between the source gas supply nozzle 10 and the opening 31A of the discharge pipe, the guide gas is formed so as to cancel the swirl of the reaction gas and form a direct downstream. It is also possible to have a function of turning the.
[0067]
When the opening 31 </ b> A of the discharge pipe 31 is inserted into the vertical core tube 11, the space between the inner wall of the vertical core tube 11 and the outer wall of the discharge pipe 31 serves as a flow adjustment unit. obtain. When a uniform ascending current is formed in any plane perpendicular to the central axis of the discharge pipe 31 by the flow adjusting unit 43, as shown in FIG. 5, the inner wall surface of the vertical core tube 11 and A rectifying plate 44 is preferably provided between the outer peripheral surface of the discharge pipe 31. As shown in FIG. 6, the rectifying plate 44 is formed in the center of the discharge pipe 31 in a horizontal cross-section annular space formed between the outer peripheral surface of the discharge pipe 31 and the inner peripheral surface of the vertical core tube 11. It is good to arrange | position so that it may become radial centering on an axis line.
[0068]
The number of rectifying plates 44 arranged radially is usually 2 to 8. The arrangement position of the rectifying plate 44 is not particularly limited as long as the above functions are performed. For example, as shown in FIG. 5, the upper end portion and the lower end portion of the rectifying plate 44 are positioned in the middle portion of the discharge pipe 31. The rectifying plate 44 may be disposed as shown in FIG. 7, and the upper end of the rectifying plate 44 may be disposed so as to coincide with the edge of the opening 31A as shown in FIG. The length of the rectifying plate 44 is not particularly limited as long as it is designed so that the rising air flow having substantially the same flow velocity is formed on any plane orthogonal to the central axis.
[0069]
Further, when a swirling flow of the guide gas is generated in the gas uniform supply tank 41, the baffle plate 45 is provided below the rectifying plate 44 so as to prevent the swirling flow from flowing into the flow adjusting unit as shown in FIG. It is good also to arrange | position. For example, as shown in FIG. 7, the baffle plate 45 is provided on the inner peripheral surface of the vertical core tube 11, and is provided on the outer peripheral surface of the discharge pipe 31. It can be formed in combination with an annular plate inclined downward.
[0070]
The guide gas used in the guide gas supply means is not particularly limited as long as the object of the present invention can be achieved, but an inert gas in the reaction region is preferable. Examples of the inert guide gas include noble gases such as argon and nitrogen. If the difference between the molecular weight of the guide gas and that of the carrier gas is large, the guide gas completely wraps them with little mixing with the source gas and carrier gas, resulting in the formation of carbon fibers on the inner wall of the exhaust pipe. A situation without any can be realized. This situation is significant when hydrogen is used as the carrier gas and nitrogen is used as the guide gas. It is preferable that the guide gas and the carrier gas have the same or approximate composition in terms of gas recovery and reuse.
[0071]
When the furnace core tube is a horizontal furnace core tube, that is, a horizontal furnace core tube, the flow of gas inside the furnace core tube and the discharge pipe is rectified in the same manner as in the case of the vertical furnace core tube. As described above, the inner diameter of the gas uniform supply tank, the flow rate of the guide gas, the flow linear velocity of the guide gas, and the like can be determined.
[0072]
When producing a twisted carbon nanofiber sliver yarn, it is necessary to rotate the carbon nanofiber to focus it. In order to give rotation to the carbon nanofibers, (1) a method of giving rotation to the guide gas itself circulating in the discharge pipe, (2) the condition of the carbon nanofibers focused on the center of the discharge pipe by the guide gas in the discharge pipe When the body is pulled out from the discharge pipe by an ejector or a fan, a method of forcibly applying a rotational force to the carbon nanofiber strip, and (3) the raw material gas itself ejected from the raw gas supply nozzle into the vertical furnace core pipe Giving rotational force, generating a rotating airflow in the reaction region, generating carbon nanofibers in the reaction region, taking the generated carbon nanofibers into the discharge tube together with the rotating airflow from the opening of the discharge tube, etc. be able to.
[0073]
When the method (1) is adopted, for example, in FIG. 1, the flow adjustment unit 43, the baffle plate 44 shown in FIGS. 5 to 7 and the baffle plate 45 shown in FIG. Is preferably a fine carbon fiber sliver manufacturing apparatus having the same structure as shown in FIG.
[0074]
According to the fine carbon fiber sliver manufacturing apparatus that is not provided with the baffle plate and the flow adjustment unit according to the above method (1), as shown in FIG. The raw material gas is combined with the guide gas that has risen without being rectified while being heated in the gap between the vertical furnace core tube 11 and the discharge tube 31, and the guide gas and the raw material gas are wrapped so that the guide gas wraps the raw material gas. Is sucked into the discharge pipe 31 from the opening 31A of the discharge pipe 31 in a vortex. The reason why the gas flows into the opening 31 </ b> A in a vortex is not certain, but it is assumed that the guide gas rising to the opening 31 receives the Coriolis force. When the gas is sucked into the opening 31A, the source gas is collected at the center of the vortex. The source gas introduced into the discharge pipe 31 from the opening 31A is immediately decomposed by heat to generate carbon nanofibers. The generated carbon nanofibers are subjected to a rotational force by a gas flow swirling, and are transported through the vicinity of the center of the discharge pipe 31 by the guide gas sucked. As a result, the twisted carbon nanofiber sliver thread is discharged from the outlet of the discharge pipe 31. When a guide plate having a predetermined inclination angle with respect to a plane perpendicular to the central axis of the vertical furnace core tube 11 is mounted between the upper portion of the discharge pipe 31 and the inner surface of the vertical furnace core tube 11, The twist in the carbon nanofiber sliver yarn, that is, the inclination angle of the carbon nanofiber with respect to the length direction of the carbon nanofiber sliver yarn can be adjusted according to the inclination angle and the rectifying surface of the guide plate.
[0075]
When the method (2) is adopted, the carbon nanofiber sliver yarn-like yarn manufacturing apparatus shown in FIG. 1 is used to discharge carbon from the central portion of the discharge pipe 31 by gas ejection from the driving gas ejection nozzle 32. It is desirable to provide a driving gas ejection nozzle 32 having a gas ejection angle adjusted so that a rotational force is applied to the nanofiber sliver thread. Note that the method (2) may be adopted for a carbon nanofiber sliver yarn-like yarn manufacturing apparatus that employs the method (1).
[0076]
When the method (3) is adopted, in the fine carbon fiber sliver manufacturing apparatus shown in FIG. 1, a raw material gas supply nozzle that ejects the rectified raw material gas from the raw material gas supply port 18 into the vertical furnace core tube 11. Instead of 10, a source gas supply nozzle that is directed in a predetermined direction so that the source gas is ejected in a spiral or spiral shape, and for generating a rotating airflow that is driven so that the airflow in the source gas supply nozzle rotates. It is preferable to use a fine carbon fiber sliver manufacturing apparatus provided with a source gas supply nozzle formed by mounting a fan inside or outside the inner tube 12A.
[0077]
The carbon nanofiber sliver yarn-like yarn manufacturing apparatus similar to that shown in FIG. 1 except that an exhaust fan is used in place of the ejector 33 is operated as follows, for example, so that the carbon nanofiber sliver yarn-like yarn is obtained. Manufactured.
[0078]
As shown in FIG. 1, when the gas is introduced into the gas uniform supply tank 41 from the guide gas introduction pipe 42, the swirl flow around the discharge pipe 31 is usually performed in the gas uniform supply tank 41 depending on the volume. May occur.
[0079]
On the other hand, the gas in the exhaust pipe 31 is exhausted from the lower opening of the exhaust pipe by the exhaust fan. Therefore, gas is sucked from the outside to the inside of the opening 31 </ b> A of the discharge pipe 31.
[0080]
In the vicinity of the opening 31A of the discharge pipe 31, gas is sucked into the opening 31A, so that the guide gas in the gas uniform supply tank 41 is sucked upward. When the guide gas in the uniform gas supply tank 41 rises, the flow adjustment unit 43 causes the swirling flow to disappear and an upward air flow parallel to the central axis of the discharge pipe 31 is formed.
[0081]
On the other hand, when the carbon source gas and the catalytic metal source gas are supplied from the source gas supply nozzle 10 together with the carrier gas into the vertical furnace core tube 11, the catalytic metal source is immediately decomposed in the reaction region and the catalytic metal becomes the nucleus. Discontinuous carbon nanotubes are formed. The discontinuous carbon nanotubes are drawn into the discharge pipe 31 from the opening 31 </ b> A of the discharge pipe 31 by the guide gas that has risen through the gap between the outer peripheral face of the discharge pipe 31 and the inner peripheral face of the vertical furnace core tube 11. It is.
[0082]
The carbon nanofibers drawn into the discharge pipe 31 are collected at the center of the discharge pipe 31 to become a carbon nanofiber sliver thread, and are transported along with the guide gas in the discharge pipe 31, and finally collected by the collecting device. Is done.
[0083]
In the above, the manufacturing method of the carbon nanofiber sliver thread-like yarn has been described centering on the manufacturing apparatus having the vertical furnace core tube according to the present invention. However, the carbon nanofiber having the horizontal furnace core tube instead of the vertical furnace core tube has been described. Even in the case of a fiber sliver filament yarn production device, by taking measures to effectively prevent convection generation in the furnace core tube and in the discharge tube, the carbon nanofiber sliver yarn shape is provided in the same manner as in the case of having a vertical furnace core tube. Yarn can be manufactured.
[0084]
【Example】
Example 1
The carbon nanofiber sliver yarn production apparatus shown in FIG. 1 uses the carbon nanofiber sliver yarn production apparatus using the collection device shown in FIG. 8 instead of the ejector, and the carbon nanofiber sliver under the following conditions: A thread was produced.
[0085]
(1) Vertical furnace core tube 11
・ Inner diameter: 90 mm, outer diameter: 100 mm, length: 2 m pipe made of silicon carbide,
-Length from source gas supply nozzle to lower end opening: 1000 mm,
・ Temperature distribution in the vertical furnace core tube:
-Temperature in a region (soaking region) from the source gas supply nozzle to 80 cm below: temperature gradient of 1120 to 1100 ° C,
-Temperature (temperature reduction region) from the soaking region to 20 cm below: 1100 to 900 ° C,
Raw material gas composition: ferrocene 0.12 mol%, thiophene 0.10 mol%, toluene 5.80 mol%, hydrogen 93.98 mol%,
・ Gas supply amount from raw material gas supply nozzle: 2.6 liters / minute,
-Gas supply amount of carrier gas (hydrogen gas) from the first carrier gas supply nozzle: 8 liters / minute,
-Gas supply amount of carrier gas (hydrogen gas) from the second carrier gas supply nozzle: 7 liters / minute.
(2) Drain pipe 31
-Length from the upper opening of the discharge pipe to the lower end opening: 120 cm,
-Length of the rectifying plate having an upper end at the edge and height of the upper opening of the discharge pipe: 5 cm,
・ Number of rectifying plates: 4
-Arrangement state of rectifying plate: Arranged radially around the central axis of the discharge pipe,
-Length from the source gas supply nozzle to the upper opening of the discharge pipe: 80 cm,
-Inner diameter of the discharge pipe: 4 cm
-Inner diameter of the information opening of the discharge pipe: 4.4 cm,
-Outside diameter of duct for guiding exhaust pipe: 15cm,
・ Exhaust pipe guide duct length: 1m,
-The exhaust pipe induction duct is connected to the exhaust fan via a cushion box (1mx1m). Supply driving gas (mixture of air and nitrogen) 100ml / min through the duct side rectifier.
[0086]
(3) Guide gas supply means 40
Inner diameter of gas uniform supply tank 41: 20 cm,
Volume of gas uniform supply tank 41: 15 liters,
Supply amount of guide gas (nitrogen) from the guide gas supply nozzle: 15 liters / minute (20 ° C.),
Pressure in gas uniform supply tank 41: -5 mm water column
Under the above conditions, the carbon nanofiber sliver thread-yarn manufacturing apparatus was operated for 10 minutes, and the carbon nanofiber sliver thread-yarn was attached to a bar (in the cushion tank) provided on the outlet side of the discharge pipe guiding duct and collected. This carbon nanofiber sliver thread has a diameter of about 3 mm, and a hollow sliver thread has a bundle of about 1 cm.2It was a bundle of about 50 cm in length.
Since the carbon nanofiber sliver thread is lightly bonded by the by-product tar-like material, the carbon nanofiber sliver thread cannot be separated one by one. The average orientation angle of the carbon nanofiber sliver yarns with respect to the fiber axis of a total of 50 carbon nanofibers (average outer diameter 20 nm) was measured by observing three places per piece, and it was 9 degrees. Met.
[0087]
(Example 2)
Remove the four guide gas rectifier plates radially arranged outside the exhaust pipe so that the guide gas flows into the exhaust pipe while rotating, instead of the entrance side rectifier of the duct for guiding the exhaust pipe outside the system The carbon nanofiber sliver yarn-like yarn production apparatus was operated under the same conditions as in Example 1 except that a guide spring having an angle of 45 degrees was attached and the driving gas was allowed to flow.
[0088]
One of the carbon nanofiber sliver filaments adhering to the crosspiece was taken out and investigated. The diameter of the carbon nanofiber sliver thread was about 1.5 mm, the length was 30 cm, and the weight was about 0.0002 g. The true density of carbon nanofiber sliver thread is 2g / cmThreeThe bulk density was about 0.02% of the true density. The tensile strength of this carbon nanofiber sliver thread is about 5 g / mm2Met. The average orientation angle of the carbon nanofibers constituting the carbon nanofiber sliver thread was 13 degrees.
[0089]
【The invention's effect】
According to the present invention, carbon nanofiber sliver yarns, which are bundles of carbon nanofibers that are substantially aligned in one direction, are useful as electron beam emission sources, as reinforcing materials for resins, ceramics, and metals. Can be provided. When the carbon nanofiber sliver thread-like yarn according to the present invention is further twisted, the carbon nanofiber sliver thread-like yarn can be made into a yarn, and the thus obtained yarn and the carbon nanofiber sliver yarn-like yarn can be further graphitized for various uses. it can.
[0090]
According to the present invention, a method for producing the carbon nanofiber sliver thread can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic explanatory view showing an example of an apparatus for carrying out the method of the present invention.
FIG. 2 is a schematic explanatory view showing an example of a discharge pipe in one manufacturing apparatus for carrying out the method of the present invention.
FIG. 3 is a schematic explanatory view showing another example of a discharge pipe in one manufacturing apparatus for carrying out the method of the present invention.
FIG. 4 is a schematic explanatory view showing another example of the discharge pipe in one manufacturing apparatus for carrying out the method of the present invention.
FIG. 5 is a schematic explanatory view showing a current plate in one manufacturing apparatus for carrying out the method of the present invention.
FIG. 6 is a schematic explanatory view showing an arrangement state of rectifying plates in one manufacturing apparatus for carrying out the method of the present invention.
FIG. 7 is a schematic explanatory view showing another example of a current plate in one manufacturing apparatus for carrying out the method of the present invention.
FIG. 8 is a schematic explanatory view showing a collecting apparatus in one manufacturing apparatus for carrying out the method of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Vapor growth carbon fiber manufacturing apparatus, 2 ... Raw material tank, 3 ... Pump, 4 ... Vaporizer, 5 ... Heat block, 6 ... 1st mass flow controller, 7 ... 2nd mass flow controller, 8 ... 3rd mass flow controller, DESCRIPTION OF SYMBOLS 9 ... Heat tube, 10 ... Raw material gas supply nozzle, 11 ... Vertical furnace core pipe, 12 ... Outer cylinder pipe, 12A ... Inner cylinder pipe, 13 ... Cooling gas supply nozzle, 13A ... Cooling gas discharge pipe, 14 ... Carrier gas Supply nozzle, 14A ... gas rectifying means, 15 ... electric furnace, 18 ... raw material gas supply port, 19 ... branch pipe, 20 ... piping, 21 ... raw material supply pipe, 22 ... piping, 23 ... piping, 30 ... discharge means, 31 DESCRIPTION OF SYMBOLS ... Exhaust pipe, 31A ... Opening part, 32 ... Drive gas ejection nozzle, 33 ... Ejector pipe, 40 ... Guide gas supply means, 41 ... Gas uniform supply tank, 42 ... Guide gas supply pipe, 43 ... Flow adjustment , 44 ... rectifying plate, 34 ... exhaust pipe induction, 51 ... sliver thread yarn collection boxes shared nanofibers collection box, 52 ... exhaust fan, 53 ... sliver thread yarn collection crosspiece, 54 ... nanofibers collecting net.

Claims (5)

  1. Containing discontinuous carbon nanofibers having an average outer diameter of 3 to 200 nm , the fiber packing density is 0.0001 to 10% of the wrinkle density, and the strength is 0.01 to 100 g / mm 2 . A carbon nanofiber sliver thread that is substantially untwisted.
  2. Containing discontinuous carbon nanofibers having an average outer diameter of 3 to 200 nm , the fiber packing density is 0.0001 to 10% of the wrinkle density, and the strength is 0.01 to 100 g / mm 2 . A carbon nanofiber sliver yarn, wherein the average value of the direction of the discontinuous carbon nanofiber with respect to the length direction of the sliver yarn is twisted to 30 degrees at most.
  3.   The carbon nanofiber sliver yarn according to claim 1 or 2, wherein the discontinuous carbon nanofiber is a vapor-grown carbon fiber that is hollow and has an average outer diameter of 5 to 50 nm.
  4. Discontinuous carbon nanofibers generated from the carbon source gas and the catalyst metal source gas supplied together with the carrier gas from one end of the furnace core tube are focused on the center of the exhaust pipe arranged in the furnace core tube, and the center of the exhaust pipe A step of focusing the discontinuous carbon nanofibers in a state of being focused on the section so that the fiber filling density is 0.0001 to 10% of the soot density by pulling out the discontinuous carbon nanofibers outside the discharge pipe with a guide gas. The method for producing a carbon nanofiber sliver thread-like yarn according to claim 1, comprising:
  5. Discontinuous carbon nanofibers generated from the carbon source gas and the catalyst metal source gas supplied together with the carrier gas from one end of the furnace core tube are focused on the center of the exhaust pipe arranged in the furnace core tube, and the center of the exhaust pipe A step of focusing the discontinuous carbon nanofibers in a state of being focused on the section so that the fiber filling density is 0.0001 to 10% of the soot density by pulling out the discontinuous carbon nanofibers outside the discharge pipe with a guide gas. And a step of twisting the yarn focused inside the discharge pipe or outside the discharge pipe. The method for producing a carbon nanofiber sliver thread-like yarn according to claim 2 .
JP29050599A 1999-10-13 1999-10-13 Carbon nanofiber sliver thread and method for producing the same Expired - Fee Related JP4132480B2 (en)

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WO2005102924A1 (en) * 2004-04-19 2005-11-03 Japan Science And Technology Agency Carbon-based fine structure group, aggregate of carbon based fine structures, use thereof and method for preparation thereof
US20100297441A1 (en) * 2004-10-18 2010-11-25 The Regents Of The University Of California Preparation of fibers from a supported array of nanotubes
KR101536669B1 (en) * 2004-11-09 2015-07-15 더 보드 오브 리전츠 오브 더 유니버시티 오브 텍사스 시스템 The fabrication and application of nanofiber ribbons and sheets and twisted and non-twisted nanofiber yarns
CA2897320A1 (en) * 2005-07-28 2007-01-28 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
JP2007124789A (en) * 2005-10-27 2007-05-17 Bussan Nanotech Research Institute Inc Contact strip for pantograph
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TWI383952B (en) * 2006-04-24 2013-02-01 Nat Inst Of Advanced Ind Scien Single-layered carbon nanotube, carbon fiber aggregation containing the same and manufacturing method thereof
JP5299884B2 (en) * 2007-10-23 2013-09-25 地方独立行政法人大阪府立産業技術総合研究所 Method for producing fine carbon fiber yarn, fine carbon fiber-forming substrate used in the production method, and fine carbon fiber yarn produced by the production method
CA2703084A1 (en) * 2008-01-31 2009-08-06 Nikkiso Co., Ltd. Apparatus for carbon nanotube synthesis
JP5229732B2 (en) * 2008-11-11 2013-07-03 地方独立行政法人大阪府立産業技術総合研究所 Apparatus and method for producing fine carbon fiber twisted yarn
US10526707B2 (en) * 2012-08-29 2020-01-07 The University Of Tokyo Heat exchanger type reaction tube

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