WO2018030044A1 - Procédé de production d'une multitude de nanotubes de carbone - Google Patents

Procédé de production d'une multitude de nanotubes de carbone Download PDF

Info

Publication number
WO2018030044A1
WO2018030044A1 PCT/JP2017/024853 JP2017024853W WO2018030044A1 WO 2018030044 A1 WO2018030044 A1 WO 2018030044A1 JP 2017024853 W JP2017024853 W JP 2017024853W WO 2018030044 A1 WO2018030044 A1 WO 2018030044A1
Authority
WO
WIPO (PCT)
Prior art keywords
cnt array
cnt
gas
carbon monoxide
carbon
Prior art date
Application number
PCT/JP2017/024853
Other languages
English (en)
Japanese (ja)
Inventor
翼 井上
宏一 長岡
鉄春 三輪
Original Assignee
国立大学法人静岡大学
Jnc株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人静岡大学, Jnc株式会社 filed Critical 国立大学法人静岡大学
Priority to JP2018532876A priority Critical patent/JP6762542B2/ja
Publication of WO2018030044A1 publication Critical patent/WO2018030044A1/fr

Links

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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres

Definitions

  • the present invention relates to a method for producing a carbon nanotube array, a method for producing a spinning source member comprising a carbon nanotube array produced by the production method, and a method for producing a structure comprising carbon nanotubes spun from the spinning source member About.
  • a carbon nanotube array (also referred to as “CNT array” in this specification) means that a plurality of carbon nanotubes (also referred to as “CNT” in this specification) are constant in at least a part of the major axis direction. (As a specific example, it is an aggregate of CNTs grown so as to be oriented in a direction substantially parallel to one normal line of the surface of the substrate). Note that the length (height) of the CNT array grown from the substrate in the direction parallel to the normal of the substrate in a state of adhering to the substrate is referred to as “growth height”.
  • a plurality of CNTs are continuously taken out from the CNT array by picking a part of the CNT array and pulling the CNT away from the CNT array.
  • a structure having a structure in which a plurality of CNTs are entangled with each other is called a “CNT entangled body”, which is formed by a process similar to the process of manufacturing yarn from fibers according to the prior art.
  • CNT Since CNT has a specific structure of having an outer surface made of graphene, it is expected to be applied in various fields as a functional material and a structural material. Specifically, CNT has excellent properties such as high mechanical strength, light weight, good electrical conductivity, good thermal properties, high chemical corrosion resistance, and good field electron emission properties. Therefore, CNTs can be used as lightweight high-strength wires, scanning probe microscope (SPM) probes, field emission display (FED) cold cathodes, conductive resins, high-strength resins, corrosion-resistant resins, wear-resistant resins, Highly lubricious resins, secondary battery and fuel cell electrodes, LSI interlayer wiring materials, biosensors, and the like are considered.
  • SPM scanning probe microscope
  • FED field emission display
  • Patent Document 1 discloses that a solid-state metal catalyst layer is formed in advance on the surface of a substrate by means such as sputtering by depositing a thin film of a metal-based material.
  • a method is disclosed in which a substrate having a metal catalyst layer is installed in a reaction furnace and a hydrocarbon gas is supplied to the reaction furnace to form a CNT array on the substrate.
  • a method for producing a CNT array by forming a solid-phase catalyst layer on a substrate as described above and supplying a hydrocarbon-based material to a reactor provided with the substrate having the solid-phase catalyst layer. Is referred to as a solid-phase catalyst method.
  • Patent Document 2 discloses a raw material gas containing carbon and not containing oxygen, a catalyst activation material containing oxygen, and an atmosphere gas. , A method of supplying the catalyst while satisfying predetermined conditions and bringing it into contact with a solid catalyst layer is disclosed.
  • Patent Document 3 discloses a method in which iron chloride is sublimated and a CNT array is formed by a thermal CVD method in an environment where the iron chloride exists in a gas phase. This method is disclosed in Patent Documents 1 and 2 in that thermal CVD is performed without previously forming a solid catalyst layer on the surface of the substrate and that a halogen-based material such as chlorine is present in an environment where thermal CVD is performed. It is essentially different from the disclosed technology.
  • the method for producing a CNT array disclosed in Patent Document 3 is also referred to as a gas phase catalyst method.
  • Such a method for producing a CNT array by a gas phase catalyst method is naturally different from the above-described method for producing a CNT array by a solid phase catalyst method because the physical state of the catalyst is different. To do. Therefore, both are considered to be essentially different CNT array manufacturing methods. Therefore, it is completely unknown whether the technical method for improving the productivity in the method for producing a CNT array by the solid phase catalyst method can be applied as it is to the method for producing the CNT array by the gas phase catalyst method. There is a demand for a method for improving productivity suitable for the manufacturing method of the CNT array by the above.
  • the method for producing a CNT array by a gas phase catalyst method is essentially different from the method for producing a CNT array by a solid phase catalyst method. Therefore, the characteristics of the CNT array produced by each production method are also different. May be different from each other. Therefore, the ease of forming the CNT entangled body formed from the CNT array (also referred to as “spinnability” in this specification) may be different in the CNT arrays manufactured from the respective manufacturing methods. Therefore, technical guidelines for producing a CNT array excellent in spinnability need to be considered independently for each of a method for producing a CNT array by a solid-phase catalyst method and a method for producing a CNT array by a gas-phase catalyst method.
  • An object of the present invention is to provide means for increasing the productivity of a CNT array produced by the above gas phase catalytic method.
  • the second step is performed by supplying the raw material gas and the carbon monoxide to an atmosphere containing the gas phase catalyst while controlling the flow rates thereof, and the monoxide with respect to the supply flow rate of the raw material gas.
  • a method for manufacturing a spinning source member characterized by being manufactured using the carbon nanotube array manufactured by the method for manufacturing a carbon nanotube array according to any one of [1] to [7].
  • a method for producing a structure including carbon nanotubes comprising producing the carbon nanotubes from the spinning source member according to [8].
  • [12] A method for producing a composite structure comprising the structure according to any one of [9] to [11] as a skeleton structure.
  • the growth rate of the CNT array is determined by the gas phase catalytic method not using carbon monoxide (also referred to as “conventional gas phase catalytic method” in this specification). It can be higher than the speed. Therefore, the productivity of the CNT array can be increased by implementing the manufacturing method according to the present invention.
  • 4 is a graph showing the relationship between the growth height and growth time of a CNT array manufactured by a manufacturing method according to tests 3-1 to 3-4.
  • 4 is a graph showing the relationship between the growth height and growth time of a CNT array manufactured by a manufacturing method according to Tests 4-1 to 4-4.
  • 7 is a graph showing the relationship between the growth height and growth time of a CNT array manufactured by the manufacturing method according to Tests 5-1 to 5-7.
  • 6 is a graph showing the relationship between the growth height and growth time of a CNT array manufactured by a manufacturing method according to tests 6-1 to 6-4.
  • 6 is a Raman spectrum of a CNT array manufactured by the manufacturing method according to Test 5-1. It is a Raman spectrum of a CNT array manufactured by the manufacturing method according to Test 5-3. 7 is a graph showing a G / D ratio obtained from a Raman spectrum of each CNT array manufactured by a manufacturing method according to Tests 5-1 to 5-7. 6 is a graph showing the relationship between the synthesis temperature of the CNT array manufactured by the manufacturing method according to Example 2 and the growth height of the CNT array. 6 is a graph showing the relationship between the synthesis temperature of a CNT array manufactured by the manufacturing method according to Example 2 and the catalyst life.
  • 6 is a graph showing the relationship between the synthesis temperature of a CNT array manufactured by the manufacturing method according to Example 2 and the initial growth rate of the CNT array.
  • 6 is a graph showing the relationship between the synthesis temperature of a CNT array manufactured by the manufacturing method according to Example 3 and the growth height of the CNT array.
  • 6 is a graph showing the relationship between the synthesis temperature of a CNT array produced by the production method according to Example 3 and the catalyst life.
  • 6 is a graph showing a relationship between a synthesis temperature of a CNT array manufactured by the manufacturing method according to Example 3 and an initial growth rate of the CNT array.
  • 6 is a graph showing a relationship between an acetylene flow rate and an initial growth rate of a CNT array in the manufacturing method according to Example 3.
  • FIG. 1 is a diagram schematically showing a configuration of a manufacturing apparatus used in a method for manufacturing a CNT array according to an embodiment of the present invention.
  • the manufacturing apparatus 10 includes an electric furnace 12.
  • the electric furnace 12 has a substantially cylindrical shape extending along a predetermined direction A (the direction in which the source gas flows).
  • a reaction vessel tube 14 as a carbon nanotube growth chamber is passed.
  • the reaction vessel tube 14 is a substantially cylindrical member made of a heat-resistant material such as quartz, has an outer diameter smaller than that of the electric furnace 12, and extends along a predetermined direction A.
  • a substrate 28 is installed in the reaction vessel tube 14.
  • the electric furnace 12 includes a heater 16 and a thermocouple 18.
  • the heater 16 is a certain region in the predetermined direction A of the reaction vessel tube 14 (in other words, a certain region in the axial direction of the substantially cylindrical reaction vessel tube 14, hereinafter also referred to as “heating region”). It is arrange
  • tube 14 is generate
  • the thermocouple 18 is disposed in the vicinity of the heating region of the reaction vessel tube 14 inside the electric furnace 12, and can output an electric signal representing a temperature related to the temperature of the atmosphere in the tube in the heating region of the reaction vessel tube 14.
  • the heater 16 and the thermocouple 18 are electrically connected to the control device 20.
  • a gas supply device 22 is connected to one end of the reaction vessel pipe 14 in the predetermined direction A.
  • the gas supply device 22 includes a source gas supply unit 30, a gas phase catalyst supply unit 31, a carbon monoxide supply unit 32, and an auxiliary gas supply unit 33.
  • the gas supply device 22 is electrically connected to the control device 20, and is also electrically connected to each supply unit included in the gas supply device 22.
  • the raw material gas supply unit 30 can supply a raw material gas (for example, a hydrocarbon gas such as acetylene) containing a carbon compound, which is a raw material of CNT constituting the CNT array, into the reaction vessel tube 14.
  • a raw material gas for example, a hydrocarbon gas such as acetylene
  • the supply flow rate of the source gas from the source gas supply unit 30 can be adjusted using a known flow rate adjusting device such as a mass flow.
  • the gas phase catalyst supply unit 31 can supply the gas phase catalyst to the inside of the reaction vessel tube 14.
  • gas phase catalyst is a halogen-containing catalyst precursor, which is formed on the basis of a substance that can be in a gas phase in the growth region of the reaction vessel 14 and the halogen-containing catalyst precursor. It is used as a general term for suspended substances.
  • the supply flow rate of the gas phase catalyst from the gas phase catalyst supply unit 31 can be adjusted using a known flow rate adjusting device such as mass flow.
  • the carbon monoxide supply unit 32 can supply carbon monoxide into the reaction vessel tube 14.
  • the supply flow rate of carbon monoxide from the carbon monoxide supply unit 32 can be adjusted using a known flow rate adjusting device such as mass flow.
  • the auxiliary gas supply unit 33 is a reaction vessel for the above-mentioned raw material gas, gas phase catalyst and gas other than carbon monoxide, for example, an inert gas such as argon (this gas is generically referred to as “auxiliary gas” in this specification). It can be supplied to the inside of the tube 14.
  • the supply flow rate of the auxiliary gas from the auxiliary gas supply unit 33 can be adjusted using a known flow rate adjusting device such as a mass flow.
  • a pressure regulating valve 23 and an exhaust device 24 are connected to the other end of the reaction vessel pipe 14 in the predetermined direction A.
  • the pressure adjustment valve 23 can adjust the pressure of the gas in the reaction vessel pipe 14 by changing the degree of opening and closing of the valve.
  • the exhaust device 24 evacuates the inside of the reaction vessel tube 14.
  • the specific type of the exhaust device 24 is not particularly limited, and a rotary pump, an oil diffusion pump, a mechanical booster, a turbo molecular pump, a cryopump, or the like can be used alone or in combination.
  • the pressure adjustment valve 23 and the exhaust device 24 are electrically connected to the control device 20.
  • a pressure gauge 13 for measuring the internal pressure is provided inside the reaction vessel tube 14.
  • the pressure gauge 13 is electrically connected to the control device 20 and can output an electric signal representing the pressure inside the reaction vessel pipe 14 to the control device 20.
  • control device 20 is electrically connected to the heater 16, the thermocouple 18, the gas supply device 22, the pressure gauge 13, the pressure adjustment valve 23 and the exhaust device 24, and electrical signals output from these devices and the like. Or the operation of these devices is controlled based on the input electrical signal.
  • control device 20 a specific operation of the control device 20 will be exemplified.
  • the control device 20 inputs an electrical signal regarding the internal temperature of the reaction vessel tube 14 output from the thermocouple 18 and outputs a control signal related to the operation of the heater 16 determined based on the electrical signal to the heater 16. can do.
  • the heater 16 receiving the control signal from the control device performs an operation of increasing or decreasing the amount of generated heat based on the control signal, and changes the internal temperature of the heating region of the reaction vessel pipe 14.
  • the control device 20 inputs an electric signal regarding the internal pressure of the heating region of the reaction vessel tube 14 output from the pressure gauge 13 and relates to the operation of the pressure adjusting valve 23 and the exhaust device 24 determined based on the electric signal.
  • a control signal can be output to the pressure regulating valve 23 and the exhaust device 24.
  • the pressure adjustment valve 23 and the exhaust device 24 that have received a control signal from the control device change the opening degree of the pressure adjustment valve 23 or change the exhaust capability of the exhaust device 24 based on the control signal. Perform the operation.
  • the control device 20 can output a control signal for controlling the operation of each device or the like to each device according to a preset time table. For example, the start and stop of the gas supply from each of the raw material gas supply unit 30, the gas phase catalyst supply unit 31, the carbon monoxide supply unit 32, and the auxiliary gas supply unit 33 included in the gas supply device 22 and the supply flow rate are determined.
  • a control signal can be output to the gas supply device 22.
  • the gas supply device 22 to which the control signal is input operates each supply unit according to the control signal, and starts or stops supplying each gas such as a raw material gas into the reaction vessel pipe 14.
  • CNT Array Manufacturing Method A CNT array manufacturing method according to an embodiment of the present invention will be described with reference to the drawings.
  • the manufacturing method of the CNT array according to the present embodiment includes first and second steps as shown in FIG.
  • a substrate 28 having a base surface as at least a part of its surface is present in an atmosphere containing a gas phase catalyst.
  • the base surface can be a surface made of a material containing an oxide of silicon, for example.
  • the specific configuration of the substrate 28 is not limited.
  • the shape is arbitrary, and may be a simple shape such as a flat plate or a cylinder, or may have a three-dimensional shape provided with complex irregularities.
  • the entire surface of the substrate may be the base surface, or only a part of the surface of the substrate may be the base surface, and the other part may not be the base surface.
  • the base surface is, for example, a surface made of a material containing silicon oxide, and the CNT array is formed on the base surface in the second step. Details of the material constituting the base surface are not limited. A specific example of the material constituting the base surface is quartz (SiO 2 ). Another example of the material constituting the base surface is SiO x (x ⁇ 2), which can be obtained by sputtering silicon in an atmosphere containing oxygen. Yet another example is a composite oxide containing silicon. Fe, Ni, Al, etc. are illustrated as elements other than the silicon and oxygen which comprise this complex oxide. Yet another example is a compound in which a non-metallic element such as nitrogen or boron is added to an oxide of silicon.
  • the material constituting the base surface may be the same as or different from the material constituting the substrate 28.
  • the material constituting the substrate 28 is made of quartz and the material constituting the base surface is also made of quartz, or the material constituting the substrate 28 is made of a silicon substrate mainly composed of silicon to constitute the base surface. The case where a material consists of the oxide film is illustrated.
  • the substrate 28 having the above base surface is present in the atmosphere containing the gas phase catalyst.
  • the gas phase catalyst according to the present embodiment include halides of iron group elements (that is, at least one of iron, cobalt, and nickel) (also referred to as “iron group element halides” in this specification).
  • iron group element halides include iron fluoride, cobalt fluoride, nickel fluoride, iron chloride, cobalt chloride, nickel chloride, iron bromide, cobalt bromide, nickel bromide, and iodide. Iron, cobalt iodide, nickel iodide and the like can be mentioned.
  • the iron group element halide may be a different compound depending on the valence of the iron group element ion, such as iron (II) chloride and iron (III) chloride. It may be comprised from several types of substance.
  • the method for supplying the gas phase catalyst into the reaction vessel tube 14 is not limited.
  • the gas may be supplied from the gas phase catalyst supply unit 31, or may be in a physical state other than the gas phase (typically a solid phase) that gives the gas phase catalyst to the inside of the heating region of the reaction vessel pipe 14.
  • the material in the phase state also referred to herein as “catalyst source” is installed, and the gas phase catalyst is removed from the catalyst source by heating and / or applying negative pressure inside the heating region of the reaction vessel tube 14.
  • the gas phase catalyst may be generated and exist inside the heating region of the reaction vessel tube 14.
  • a halogen-containing material that reacts with the iron group element-containing material M in the reaction vessel tube 14 by setting the iron group element-containing material M such as a lump, flat plate, steel wool, or powdered iron to a predetermined temperature in the reaction vessel tube 14.
  • a gas phase catalyst may be generated by supplying a substance. If a specific example in the case of producing
  • the pressure of the atmosphere in the reaction vessel tube 14 in the first step, specifically, the portion where the substrate is installed is not particularly limited. It may be atmospheric pressure (about 1.0 ⁇ 10 5 Pa), negative pressure, or positive pressure.
  • the second step when the reaction vessel tube 14 has a negative pressure atmosphere, it is preferable to reduce the transition time between steps by setting the atmosphere to a negative pressure also in the first step.
  • the specific total pressure of the atmosphere is not particularly limited. For example, the pressure may be 10 ⁇ 2 Pa or more and 10 4 Pa or less.
  • the temperature of the atmosphere in the reaction vessel tube 14 in the first step is not particularly limited. It may be normal temperature (about 25 ° C.), may be heated, or may be cooled. As will be described later, since the atmosphere inside the heating region of the reaction vessel tube 14 is preferably heated in the second step, the atmosphere in that region is also heated in the first step, and the transition between steps is performed. It is preferable to shorten the time.
  • the temperature of the heating region is not particularly limited. For example, it is 8 ⁇ 10 2 K or more and 1.3 ⁇ 10 3 K or less, and preferably 9 ⁇ 10 2 K or more and 1.2 ⁇ 10 3 K or less.
  • the atmosphere inside the heating region of the reaction vessel tube 14 is also heated in the first step, and the conditions under which the catalyst source sublimes are set. It is preferable to satisfy.
  • the sublimation temperature of iron (II) chloride is 950 K at atmospheric pressure (about 1.0 ⁇ 10 5 Pa), but the sublimation temperature can be reduced by setting the atmosphere inside the heating region of the reaction vessel tube 14 to a negative pressure. Can be reduced.
  • An iron (II) chloride anhydride may be used as a catalyst source, and iron (II) chloride vapor may be supplied from the gas phase catalyst supply unit 31 as part of the gas phase catalyst.
  • the iron (II) chloride anhydride disposed in the gas phase catalyst supply unit 31 is heated to sublimate the iron (II) chloride.
  • the first step can be completed by guiding it into the installed reaction vessel tube 14.
  • the kind of source gas is not specifically limited, Usually, a hydrocarbon-type material is used and acetylene is mentioned as a specific example.
  • the method for causing the source gas to exist in the atmosphere inside the reaction vessel tube 14 is not particularly limited. Like the manufacturing apparatus 10 described above, it may be present by supplying a source gas from the source gas supply unit 30, or a material capable of generating the source gas is previously present in the reaction vessel pipe 14. The second step may be started by generating a raw material gas from the material and diffusing the raw material gas into the reaction vessel tube 14. When supplying the source gas from the source gas supply unit 30, it is preferable to control the supply flow rate of the source gas into the reaction vessel pipe 14 using a flow rate adjusting device.
  • the supply flow rate is expressed in units of sccm, and 1 sccm means a flow rate of 1 ml per minute for a gas converted into an environment of 273 K and 1.01 ⁇ 10 5 Pa.
  • 1 sccm means a flow rate of 1 ml per minute for a gas converted into an environment of 273 K and 1.01 ⁇ 10 5 Pa.
  • the flow rate of the gas supplied to the inside of the reaction vessel pipe 14 is based on the inner diameter of the reaction vessel pipe 14, the pressure measured by the pressure gauge 13, and the like. Is set.
  • a preferable supply flow rate of the source gas containing acetylene is 10 sccm or more and 1000 sccm or less when the pressure of the pressure gauge 13 is 1 ⁇ 10 3 Pa or more and 1 ⁇ 10 4 Pa or less, and in this case, 20 sccm or more and 500 sccm or less. More preferably, it is 50 sccm or more and 300 sccm or less.
  • the content of the raw material gas in the total gas supplied as the atmosphere inside the reaction vessel tube 14 in the second step is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.
  • carbon monoxide has a function of increasing the growth rate of the CNT array produced by the above-described gas phase catalytic method (hereinafter, also referred to as “growth promoting function”).
  • the manufactured CNT array has a function of improving the spinnability (hereinafter also referred to as “spinnability improving function”).
  • spinnability improving function includes reducing the activation energy of the reaction related to the growth of the CNT array, improving the growth rate of the CNT array, extending the life of the gas phase catalyst by removing amorphous carbon that is the cause of deactivation, etc. Can be mentioned. Further, details of the spinnability improving function are not particularly limited.
  • the method for causing carbon monoxide to exist in the atmosphere in the reaction vessel tube 14 in the second step is not particularly limited.
  • the carbon monoxide may be present by supplying carbon monoxide from the carbon monoxide supply unit 32, and a material capable of generating carbon monoxide is previously stored in the reaction vessel pipe 14.
  • the carbon monoxide may be diffused into the reaction vessel tube 14 by being present and generating carbon monoxide from the material by means such as heating or decompression.
  • the second step is a dry process in which carbon monoxide is present (a process in which there is no intentionally formulated water), so it is simpler than the process in which a trace amount (about several hundred ppm) of water is added to the source gas. Can be implemented.
  • the preferable supply flow rate of carbon monoxide in the case where the pressure of the pressure gauge 13 is 1 ⁇ 10 3 Pa or more and 1 ⁇ 10 4 Pa or less is exemplified as 10 sccm or more and 1000 sccm or less, and in this case, 20 sccm or more and 500 sccm or less may be set. More preferred is 50 sccm or more and 300 sccm or less.
  • the content of carbon monoxide in the total gas supplied as the atmosphere inside the reaction vessel tube 14 in the second step is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 10% by mass or more. .
  • the supply flow rate of carbon monoxide with respect to the supply flow rate (unit: sccm) of the source gas is preferably 1000% or less, more preferably 1% or more and 600% or less, and particularly preferably 10% or more and 100% or less. preferable. By setting it as this ratio, the growth rate of a CNT array can be increased more stably and a CNT array with a high growth height can be manufactured.
  • supplying carbon monoxide includes supplying a raw material capable of forming carbon monoxide.
  • raw materials that can form carbon monoxide include carbon dioxide and carbonyl complexes. These raw materials can produce (produce) carbon monoxide in the reaction vessel tube 14 and achieve the same effect as when carbon monoxide is supplied.
  • the degree of the growth promoting function of carbon monoxide varies depending on the quantitative relationship with the raw material gas, and the effect of containing carbon monoxide is relatively higher in the initial reaction. Since it is remarkably confirmed, carbon monoxide may be more strongly involved at a relatively early stage in the process of growing the CNT array by the interaction of the source gas with the catalyst.
  • the timing at which the source gas is present in the atmosphere in the reaction vessel tube 14 and the timing at which carbon monoxide is present are not particularly limited. Any of them may be first or simultaneously. However, if only the source gas is present and carbon monoxide is not present, the growth of the CNT array based on the interaction between the source gas and the gas phase catalyst is started, that is, the CNT array by the conventional gas phase catalyst method. In this case, there is a possibility that the benefit of containing carbon monoxide cannot be obtained sufficiently. Therefore, it is preferable to set the carbon monoxide so that it exists in the atmosphere in the reaction vessel pipe 14 prior to the source gas or simultaneously with the source gas.
  • an auxiliary gas may be present for the purpose of adjusting the total pressure to a predetermined range.
  • the auxiliary gas include a gas having a relatively low influence on the generation of the CNT array, specifically, an inert gas such as an argon gas.
  • the method for causing the auxiliary gas to exist in the atmosphere in the reaction vessel tube 14 is not particularly limited.
  • the supply apparatus includes the auxiliary gas supply unit 33, and it is simple to supply the auxiliary gas from the auxiliary gas supply unit 33 into the atmosphere in the reaction vessel tube 14, and the controllability is excellent. ,preferable.
  • the total pressure of the atmosphere in the reaction vessel tube 14 in the second step is not particularly limited. It may be atmospheric pressure (about 1.0 ⁇ 10 5 Pa), negative pressure, or positive pressure. What is necessary is just to set suitably considering the composition (partial pressure ratio) of the substance which exists in the atmosphere in the reaction container pipe
  • tube 14 is made into a negative pressure, it will be 1 * 10 ⁇ 1 > Pa or more and 1 * 10 ⁇ 4 > Pa or less, 2 * 10 ⁇ 1 > Pa or more and 7 X10 3 Pa or less is preferable, 5 ⁇ 10 1 Pa or more and 5 ⁇ 10 3 Pa or less is more preferable, and 1 ⁇ 10 2 Pa or more and 3 ⁇ 10 3 Pa or less is particularly preferable.
  • the temperature of the atmosphere inside the heating region of the reaction vessel tube 14 in the second step is not particularly limited as long as the CNT array can be formed using the raw material gas in the atmosphere where the gas phase catalyst and carbon monoxide are present.
  • a gas phase catalyst is obtained by heating a catalyst source such as iron chloride (II)
  • the temperature of the atmosphere inside the heating region of the reaction vessel tube 14 is set to be higher than the temperature at which the gas phase catalyst is formed. Is done.
  • the temperature of the base surface during the second step is preferably heated to 8 ⁇ 10 2 K or higher.
  • the temperature of the base surface is 8 ⁇ 10 2 K or higher, the interaction between the gas phase catalyst and carbon monoxide and the source gas is likely to occur on the base surface, and the CNT array is likely to grow on the base surface. From the viewpoint of making this interaction more likely to occur, the temperature of the base surface during the second step is preferably heated to 9 ⁇ 10 2 K or higher.
  • the upper limit of the temperature of the base surface during the second step is not particularly limited, but if it is excessively high, the material constituting the base surface and the material constituting the substrate (these may be the same) may be solid. Therefore, the upper limit is preferably set in consideration of the melting point and sublimation temperature of these materials. Considering the load on the reaction vessel, the upper limit temperature is preferably up to about 1.5 ⁇ 10 3 K.
  • CNT Array An example of a CNT array manufactured by the manufacturing method according to the present embodiment includes a portion having a structure in which a plurality of CNTs are aligned in a certain direction, as shown in FIG. When the diameters of a plurality of CNTs in this part are measured, as shown in FIG. 4, the diameter of the CNTs is about 20 nm to 40 nm. Therefore, the CNTs are considered to have a multilayer structure.
  • the CNT array manufactured by the manufacturing method according to this embodiment is excellent in spinnability. Specifically, a structure (CNT entangled body) including a plurality of CNTs entangled with each other is obtained by picking CNTs constituting the CNT array and pulling (spinning) them in a direction away from the CNT array. Can do.
  • FIG. 5 is an image showing a state in which a CNT entangled body is formed from the CNT array
  • FIG. 6 is an enlarged image of a part of the CNT entangled body. As shown in FIG. 5, CNTs constituting the CNT array are continuously drawn out to form a CNT entangled body.
  • FIG. 5 is an image showing a state in which a CNT entangled body is formed from the CNT array
  • FIG. 6 is an enlarged image of a part of the CNT entangled body.
  • CNTs constituting the CNT array are continuously drawn out to form a CNT entangled body.
  • FIG. 5 is an image showing
  • the CNTs constituting the CNT entangled body are entangled with each other while being oriented in the direction (spinning direction) drawn from the CNT array to form a coupled body.
  • a member including a CNT array and capable of forming a CNT entangled body is also referred to as a “spinning source member”.
  • CNT arrays can be spinning source members, and CNT arrays that can form CNT entangled bodies have geometric limitations.
  • One of the restrictions is the growth height of the CNT array (the height when the CNT array is formed). That is, when the growth height of the CNT array is excessively low, it becomes difficult for the drawn CNTs to be entangled, and it becomes difficult to obtain a CNT entangled body.
  • the ease of forming a CNT entangled body from this CNT array spinnability
  • the length in the spinning direction of the CNT entangled body formed from the CNT array the length in the direction in which CNTs are drawn from the CNT array). it can.
  • the CNT entangled body In the case of a CNT array inferior in spinnability, the CNT entangled body is detached from the CNT array before reaching a sufficient spinning length. In contrast, in the case of a CNT array that is particularly excellent in spinnability, the CNT entangled body does not detach from the CNT array until all the CNTs constituting the CNT array become the CNT entangled body.
  • the CNT array manufactured by the manufacturing method according to the present embodiment is a CNT array in which spinnability is lower than that of a manufacturing method according to the prior art, that is, a CNT array manufactured by a gas phase catalytic method without using carbon monoxide. Wide growth height range. That is, by using the CNT array manufactured by the manufacturing method according to the present embodiment as the spinning source member, the CNT entangled body in which individual CNTs have various lengths compared to the case of using the CNT array according to the conventional method. Can be manufactured more stably.
  • CNT entangled body The CNT entangled body obtained from the spinning source member can have various shapes. A specific example is a linear shape, and another example is a web-like shape.
  • the linear CNT entangled body can be handled in the same manner as a fiber and can also be used as an electrical wiring. Further, the web-like CNT entangled body can be handled as it is as a non-woven fabric.
  • the length of the CNT entangled body in the spinning direction is not particularly limited, and may be set as appropriate depending on the application. In general, when the spinning length is 2 mm or more, the CNT entangled body can be applied to a component level such as a contact portion and an electrode.
  • the web-like CNT entangled body can arbitrarily control the degree of orientation of the CNTs constituting the web-like CNT entangled body by changing the spinning method from the spinning source member. Therefore, by changing the spinning method from the spinning source member, it is possible to manufacture CNT entangled bodies having different mechanical characteristics and electrical characteristics.
  • the CNT entangled body becomes thinner in the case of a linear shape and becomes thinner in the case of a web shape. If the degree progresses, it becomes difficult to visually confirm the CNT entangled body, and at this time, the CNT entangled body can be used as a transparent fiber, a transparent wiring, and a transparent web (transparent sheet-like member).
  • the CNT entangled body may be composed only of CNT or a composite structure with other materials.
  • the CNT entangled body has a structure in which a plurality of CNTs are entangled with each other, voids exist between the plurality of entangled CNTs, like the plurality of fibers constituting the nonwoven fabric.
  • powder inorganic particles such as metal fine particles and silica, and organic particles such as ethylene polymers
  • a composite structure can be formed.
  • the surface of the CNT constituting the CNT entangled body may be modified. Since the outer surface of CNT is composed of graphene, the CNT entangled body is hydrophobic as it is, but the CNT entangled body is hydrophilized by performing a hydrophilic treatment on the surface of the CNT constituting the CNT entangled body. can do. An example of such hydrophilic means is plating. In this case, the obtained CNT entangled body becomes a composite structure of CNT and plated metal.
  • a CNT array having a high growth height can be obtained by allowing the source gas and carbon monoxide to be present in an atmosphere containing a gas phase catalyst.
  • CNTs constituting a CNT array having a high growth height are easy to maintain a long diameter when a composite structure of other materials is used. Therefore, a composite structure having excellent mechanical properties is obtained. Moreover, since the electrical resistance is lowered, it is suitable as a raw material for a transparent electrode having a low resistance.
  • the composite structure may include a structure including a CNT entangled body as a skeleton structure.
  • the “skeleton structure” refers to a basic structure.
  • the composite structure includes the structure as a skeleton structure.
  • Example 1 Using the manufacturing apparatus having the structure shown in FIG. 1, a CNT array was manufactured by the manufacturing method shown in FIG. Specifically, first, the first step was performed as follows. A quartz plate (20 mm ⁇ 5 mm ⁇ thickness 1 mm) was placed on a quartz boat in a reaction vessel tube of a manufacturing apparatus having the structure shown in FIG. Therefore, in this example, the material constituting the base surface and the material constituting the substrate were both quartz. Further, an anhydrous iron (II) chloride (120 mg) as a catalyst source was placed on a portion other than the boat in the reaction vessel tube.
  • II anhydrous iron
  • the inside of the reaction vessel tube (including the substrate) was heated to 1.1 ⁇ 10 3 K using a heater.
  • the anhydride of iron (II) chloride sublimates in the reaction vessel tube, and the inside of the heating region of the reaction vessel tube contains a gas phase catalyst formed from the anhydride of iron (II) chloride as a catalyst source. It became an atmosphere including.
  • the atmospheric pressure is maintained at 2.7 ⁇ 10 3 Pa (20 torr) using the pressure adjusting valve, and the temperature in the reaction vessel tube (including the substrate) is set to 1 using the heater.
  • the temperature in the reaction vessel tube is set to 1 using the heater.
  • acetylene as the source gas from the source gas supply unit, carbon monoxide from the carbon monoxide supply unit, and argon from the auxiliary gas supply unit at the flow rates shown in Table 1, respectively.
  • the second step was performed by supplying the reaction vessel tube with a total flow rate of 500 sccm.
  • the second step that is, by starting the supply of carbon monoxide and acetone, a CNT array was grown on the base surface in a test in which the flow rate of acetylene was 50 sccm or more.
  • the CNT array was photographed from the direction parallel to the base surface every other minute with a camera, and the growth height of the CNT array was measured from the start of the second step until the growth of the CNT array stopped.
  • the results are shown in Table 1 and FIGS.
  • the catalyst life (minutes) in Table 1 is a value obtained by reading the time (minutes) from the start of the second step to the deactivation of the gas phase catalyst from the graphs of FIGS.
  • the growth height (mm) of the CNT array indicates the height of the CNT array at the catalyst lifetime.
  • the initial growth rate indicates the growth rate ( ⁇ m / min) of the CNT array from 1 minute to 5 minutes after the start of the second step.
  • the acetylene flow rate is 30 sccm or more, preferably 40 sccm or more, more preferably 50 sccm or more under the conditions of a reaction vessel pressure of 2.7 ⁇ 10 3 Pa and a total flow rate of 500 sccm. It can be said.
  • the flow rate of acetylene is preferably 100 to 350 sccm, and more preferably 125 to 300 sccm. From the viewpoint that a CNT array having a growth height of 3 mm or more can be produced in a short time, the flow rate of acetylene is more preferably 150 to 250 sccm.
  • FIG. 7 to 10 show CNT arrays manufactured by the manufacturing methods according to tests 3-1 to 3-4, 4-1 to 4-4, 5-1 to 5-7, and 6-1 to 6-4. It is a graph which shows the relationship between growth height and growth time.
  • the horizontal axis indicates the elapsed time since the start of the second step, that is, the growth time (Growth time [min]) of the CNT array, and the vertical axis indicates the CNT array.
  • the height (Array height [mm]) is shown, and the number attached to the right shoulder of each graph shows the flow rate (sccm) of carbon monoxide. As indicated by a triangle in FIG.
  • the time from the start of the second step after reading the growth termination point in the graph of the growth profile of the CNT array until the growth of the CNT array stops is the catalyst stop time. It was.
  • the height of the CNT array during the catalyst stop time was defined as the growth height of the CNT array.
  • all of the test examples in which acetylene (raw material gas) and carbon monoxide were present in the atmosphere containing the gas phase catalyst had only the source gas present in the atmosphere containing the gas phase catalyst.
  • the growth height of the CNT array was higher than that of the test example, the catalyst life of the gas phase catalyst was longer, and the initial growth rate of the CNT array was higher. Therefore, the presence of carbon monoxide can increase the productivity of the CNT array produced by the gas phase catalytic method.
  • FIGS. 7 to 10 show that the growth profile of the CNT array varies depending on the flow rate of acetylene, but the preferable flow rate of carbon monoxide was approximately the same regardless of the flow rate of acetylene. From this result, it is considered that the relationship with the gas phase catalyst is important in specifying the optimum flow rate of carbon monoxide.
  • the flow rate of carbon monoxide is preferably 10 to 350 sccm, more preferably 30 to 300 sccm, and even more preferably 50 to 250 sccm.
  • the production method of the present invention can increase the productivity of the CNT array produced by the gas phase catalyst method.
  • 11 and 12 are Raman spectra of the CNT array manufactured by the manufacturing method according to Tests 5-1 and 5-3 in Table 1.
  • a peak appears in the vicinity of 1350 cm -1 and near 1600 cm -1. It refers to a peak appearing in the vicinity of 1350 cm -1 and D-band ', the peak appearing in the vicinity of 1600 cm -1 called G-band'.
  • the crystallinity of the CNT array can be evaluated by the peak intensity ratio (G / D ratio) of D-band and G-band. The higher the G / D ratio, the higher the crystallinity.
  • Table 2 and FIG. 13 show the G / D ratio obtained from the Raman spectrum of each CNT array manufactured by the manufacturing method according to Tests 5-1 to 5-7 in Table 1.
  • the horizontal axis represents the flow rate (sccm) of carbon monoxide
  • the vertical axis represents G / D of the CNT array.
  • Table 2 and FIG. 13 show that when the flow rate of carbon monoxide was changed in the range of 50 to 300 (sccm), a CNT array having almost the same G / D ratio, that is, crystallinity was obtained. Yes. From this result, it can be said that the presence of the source gas and carbon monoxide in the atmosphere containing the gas phase catalyst can increase the productivity of the CNT array while maintaining good crystallinity.
  • Example 2 In order to investigate the temperature dependence of the method for producing a CNT array using carbon monoxide, the temperature (synthesis temperature, base surface temperature) in the reaction vessel tube (including the substrate) is 1043 K ⁇
  • the second step was carried out with variation in the range of 1123K.
  • the acetylene flow rate is fixed at 200 sccm, the remaining 300 sccm is adjusted so that the total gas flow rate is 500 sccm, and the carbon monoxide and argon are adjusted to the flow rates shown in Table 3 to obtain the CNT array.
  • the first step and the second step were performed in the same manner as in Example 1 except for the synthesis temperature and the flow rate.
  • the growth height of the CNT array was measured from the start of the second step until the growth of the CNT array stopped. The results are shown in (Table 3) and FIGS.
  • the synthesis temperature is 1.07 at a carbon monoxide flow rate of 200 sccm.
  • the effect of increasing the growth height (Array height (mm)) of the CNT array by adding carbon monoxide was recognized by setting it to ⁇ 10 3 K or more. Therefore, from the viewpoint of increasing the growth height of the CNT array, the synthesis temperature is preferably 1.06 ⁇ 10 3 K or more, more preferably 1.07 ⁇ 10 3 K or more, and 1.08 ⁇ 10 3 K or more. Is more preferable. From the same viewpoint, the synthesis temperature is preferably 1.13 ⁇ 10 3 K or less in light of the tendency of FIG.
  • the graphs of FIGS. 15 and 16 show that the catalyst life (Life time (min), minutes) and the initial growth rate (Growth rate ( ⁇ m / min)) are simultaneously increased by adding carbon monoxide to acetylene (raw gas). It shows improvement.
  • the growth height of the CNT array is affected by the catalyst life and the growth rate, but the catalyst life and the growth rate are usually in an inversely proportional relationship. For this reason, it has been difficult for conventional CNT array manufacturing methods to simultaneously improve catalyst life and growth rate.
  • the synthesis temperature is preferably 1.07 ⁇ 10 3 K or more and 1.12 ⁇ 10 3 K or less. Further, from the viewpoint of increasing the growth rate of the CNT array, the synthesis temperature is preferably 1.08 ⁇ 10 3 K or higher.
  • the rate at which the CNT array is synthesized from the carbon raw material is high, so that carbon monoxide functions as the carbon raw material, thereby compensating for the shortage of the carbon raw material and promoting the growth of the CNT array. .
  • the growth rate of the CNT array is improved as compared with the case of using only acetylene.
  • Example 3 In order to investigate the dependence of the acetylene flow rate as the source gas in the method of manufacturing a CNT array using carbon monoxide, as shown in Table 4, the acetylene flow rate was changed in the range of 100 to 500 sccm and the synthesis temperature was changed in the range of 1043 to 1123K. Thus, a CNT array was manufactured.
  • the inside of the heating region of the reaction vessel tube was an atmosphere containing a gas phase catalyst formed from an anhydride of iron (II) chloride as a catalyst source.
  • the second step was performed as follows after the first step was performed. While maintaining the atmospheric pressure at 3.2 ⁇ 10 3 Pa (24 torr) using the pressure adjusting valve and maintaining the temperature in the reaction vessel tube (including the substrate) at a predetermined synthesis temperature using the heater, Acetylene as a raw material gas is supplied from the gas supply unit, carbon monoxide is supplied from the carbon monoxide supply unit, and argon is supplied from the auxiliary gas supply unit into the reaction vessel tube at the flow rates shown in Table 4, respectively, and the total flow rate is 600 sccm. It was. From the start of the second step until the growth of the CNT array stopped, the growth height of the CNT array was measured in the same manner as in Example 1. The results are shown in Table 4 and FIGS.
  • the growth height (Array height (mm)) of the CNT array depends on the synthesis temperature (Temperature (K)).
  • the CNT array height tended to increase with increasing synthesis temperature and decrease after peaking.
  • the acetylene flow rate was 400 sccm and 500 sccm
  • the height of the CNT array at the synthesis temperature 1123 K slightly increased from that at the synthesis temperature 1113 K. This result shows that the reaction rate at which acetylene precipitates as CNTs is sufficiently increased by increasing the synthesis temperature.
  • the synthesis temperature is preferably 1.08 ⁇ 10 3 K or more, and more preferably 1.10 ⁇ 10 3 K or more.
  • the catalyst life (Lifetime (min), minutes) tends to decrease as the synthesis temperature (Temperature (K)) increases.
  • the decrease in the catalyst life due to the increase in the synthesis temperature is due to the fact that the reaction rate increases due to the activation of thermal motion, and the catalyst surface is covered with amorphous carbon, preventing the supply of the carbon raw material.
  • the initial growth rate (GrowthCNTrate ( ⁇ m / min)) of the CNT array increased as the synthesis temperature (Temperature (K)) increased. This is due to the fact that when the synthesis temperature increases, the carbon diffusion rate inside the catalyst increases and the deposition rate of the CNT array increases.
  • the initial growth rate (ln (growth rate ( ⁇ m / min)) of the CNT array increases with an increase in the acetylene flow rate at a synthesis temperature of 1.10 ⁇ 10 3 K or higher.
  • it was less than 1.10 ⁇ 10 3 K it tended to decrease with an increase in the acetylene flow rate, because the reaction rate was low at a synthesis temperature of less than 1.10 ⁇ 10 3 K, so that the carbon raw material supplied as acetylene This is because the catalyst surface was covered with amorphous carbon without completely decomposing the catalyst.
  • the CNT entangled body obtained from the CNT array manufactured by the CNT array manufacturing method according to the present invention is suitably used as, for example, an electric wiring, a heating element, a stretchable sheet-shaped strain sensor, a transparent electrode sheet, and the like.

Abstract

L'invention concerne un procédé pour augmenter la productivité de réseaux de CNT produits par un procédé catalytique en phase gazeuse. Le procédé de production comprend : une première étape consistant à amener un substrat à être présent dans une atmosphère contenant un catalyseur en phase gazeuse; et une seconde étape consistant à amener un gaz de matière première et du monoxyde de carbone à être présents dans l'atmosphère contenant le catalyseur en phase gazeuse, amenant ainsi une pluralité de nanotubes de carbone à croître sur une surface de base du substrat, et permettant d'obtenir un réseau de nanotubes de carbone comprenant une pluralité de nanotubes de carbone sur la surface de base.
PCT/JP2017/024853 2016-08-12 2017-07-06 Procédé de production d'une multitude de nanotubes de carbone WO2018030044A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018532876A JP6762542B2 (ja) 2016-08-12 2017-07-06 カーボンナノチューブアレイの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016158391 2016-08-12
JP2016-158391 2016-08-12

Publications (1)

Publication Number Publication Date
WO2018030044A1 true WO2018030044A1 (fr) 2018-02-15

Family

ID=61161936

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/024853 WO2018030044A1 (fr) 2016-08-12 2017-07-06 Procédé de production d'une multitude de nanotubes de carbone

Country Status (2)

Country Link
JP (1) JP6762542B2 (fr)
WO (1) WO2018030044A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009196873A (ja) * 2008-02-25 2009-09-03 National Univ Corp Shizuoka Univ カーボンナノチューブの製造方法及び製造装置
WO2014080707A1 (fr) * 2012-11-22 2014-05-30 Jnc株式会社 Procédé de production d'un réseau de nanotubes de carbone, élément de source de filage, et structure pourvue de nanotubes de carbone
WO2015177401A1 (fr) * 2014-05-23 2015-11-26 Canatu Oy Procédé et appareil de production de nanomatériau

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5995108B2 (ja) * 2011-08-24 2016-09-21 日本ゼオン株式会社 カーボンナノチューブ配向集合体の製造装置及び製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009196873A (ja) * 2008-02-25 2009-09-03 National Univ Corp Shizuoka Univ カーボンナノチューブの製造方法及び製造装置
WO2014080707A1 (fr) * 2012-11-22 2014-05-30 Jnc株式会社 Procédé de production d'un réseau de nanotubes de carbone, élément de source de filage, et structure pourvue de nanotubes de carbone
WO2015177401A1 (fr) * 2014-05-23 2015-11-26 Canatu Oy Procédé et appareil de production de nanomatériau

Also Published As

Publication number Publication date
JP6762542B2 (ja) 2020-09-30
JPWO2018030044A1 (ja) 2019-07-11

Similar Documents

Publication Publication Date Title
JP6287787B2 (ja) カーボンナノチューブアレイの製造方法
US10343919B2 (en) Production method for carbon nanotubes
WO2009107603A1 (fr) Procédé et appareil de fabrication de nanotubes de carbone, fibre de nanotubes de carbone et similaires
JP6554727B2 (ja) カーボンナノチューブ撚糸、カーボンナノチューブ撚糸の製造方法および紡績源
CN110734053B (zh) 碳纳米管的制备方法，碳纳米管纤维
JP2017019718A (ja) カーボンナノチューブの製造方法
WO2018030044A1 (fr) Procédé de production d'une multitude de nanotubes de carbone
JP6699517B2 (ja) 紡績源部材、ウェブ状構造体、紡績源部材の製造方法およびウェブ状構造体の製造方法
JP6600891B2 (ja) カーボンナノチューブフォレストを備える紡績源部材の製造方法
US10464814B2 (en) Production method for carbon nanotubes
JP6667849B2 (ja) カーボンナノチューブフォレストを備える紡績源部材の製造方法
WO2016117197A1 (fr) Forêt de nanotubes de carbone ainsi que procédé de fabrication de celle-ci, élément de source de repoussage, et structure ainsi que procédé de fabrication de celle-ci
JP2019151515A (ja) カーボンナノチューブフォレストの製造方法
WO2016117198A1 (fr) Substrat à ouverture
JP4723228B2 (ja) ムスターシュ繊維
JP2014166936A (ja) カーボンナノチューブ集合体の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17839118

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018532876

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17839118

Country of ref document: EP

Kind code of ref document: A1