WO2016208557A1 - Procédé de fabrication de forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite - Google Patents

Procédé de fabrication de forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite Download PDF

Info

Publication number
WO2016208557A1
WO2016208557A1 PCT/JP2016/068333 JP2016068333W WO2016208557A1 WO 2016208557 A1 WO2016208557 A1 WO 2016208557A1 JP 2016068333 W JP2016068333 W JP 2016068333W WO 2016208557 A1 WO2016208557 A1 WO 2016208557A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon nanotube
catalyst
nanotube forest
cnt
producing
Prior art date
Application number
PCT/JP2016/068333
Other languages
English (en)
Japanese (ja)
Inventor
翼 井上
中野　貴之
太宇人 中西
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 JP2017524907A priority Critical patent/JP6667849B2/ja
Publication of WO2016208557A1 publication Critical patent/WO2016208557A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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

Definitions

  • the present invention relates to a method for producing a carbon nanotube forest, a spinning source member, a structure, and a composite structure. Specifically, the present invention relates to a carbon nanotube forest manufacturing method, a spinning source member including the carbon nanotube forest manufactured by the manufacturing method, a structure formed from the spinning source member, and a composite structure including the structure as a skeleton structure. .
  • a carbon nanotube forest (also referred to as “CNT forest” in this specification) refers to a synthetic structure of a plurality of carbon nanotubes (also referred to as “CNT” in this specification).
  • Each shape of the given CNT is referred to as “primary structure”, and the above composite structure is also referred to as “secondary structure”).
  • secondary structure there is a direction substantially parallel to one normal line of the surface of the substrate, which means an aggregate of CNTs grown so as to be oriented.
  • the length (height) of the CNT forest grown from the substrate in the direction parallel to the normal line of the substrate in a state of adhering to the substrate is referred to as “growth height”.
  • a plurality of CNTs are continuously pulled out from the CNT forest by picking a part of the CNT forest and pulling the CNT away from the CNT forest.
  • 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 high mechanical strength, light weight, good electrical conductivity, good thermal properties such as heat resistance and thermal conductivity, high chemical corrosion resistance, and good field electron emission properties. It has excellent characteristics such as. Therefore, CNTs can be used as lightweight high-strength wires, scanning probe microscope (SPM) probes, field emission display (FED) cold cathodes, conductive resins, high-strength resins, corrosion-resistant resins, wear-resistant resins, Highly lubricious resins, secondary battery and fuel cell electrodes, LSI interlayer wiring materials, biosensors, and the like are considered.
  • SPM scanning probe microscope
  • FED field emission display
  • Patent Document 1 discloses that a solid metal catalyst film is formed on a surface of a substrate in advance by means such as sputtering by depositing a thin film of a metal-based material.
  • a substrate having a metal catalyst film is placed in a reaction furnace, catalyst particles serving as growth nuclei are formed on the substrate from the metal catalyst film, and a carbon source such as a hydrocarbon gas is supplied to the reaction furnace to form a CNT on the substrate.
  • a method of forming a forest is disclosed.
  • solid-phase catalyst particles as growth nuclei are formed on a substrate, and a carbon source containing a hydrocarbon-based material is provided in a reactor provided with a substrate on which the solid-phase catalyst particles are arranged.
  • a method of supplying and manufacturing a CNT forest is called a solid-phase catalyst method.
  • the metal catalyst film when forming catalyst particles as growth nuclei from the metal catalyst film on the substrate, the metal catalyst film is heated to melt the material constituting it on the substrate. The shape based on the obtained droplets becomes the shape of the catalyst particles. Since the material constituting the metal catalyst film inevitably oxidizes during the heating described above, it is necessary to reduce the oxide to catalyst particles. Specifically, a reducing gas such as an inert gas or hydrogen gas is often supplied to the reaction furnace.
  • a reducing gas such as an inert gas or hydrogen gas is often supplied to the reaction furnace.
  • the solid-phase catalyst method is generally performed in three steps: formation of a metal catalyst layer, formation of catalyst particles including a reduction process, and growth of a CNT forest by supplying a carbon source. .
  • a liquid composition containing a metal element-containing compound is misted, and the mist of the obtained liquid composition is supplied into a reaction chamber heated to a predetermined temperature and contained in the mist of the liquid composition.
  • the carbon nanotube forest manufacturing method characterized by the above-mentioned.
  • the gas phase promoter contains a halogen-containing substance, and the halogen-containing substance is supplied into the reaction chamber simultaneously with the supply of the carbon source or after the start of the supply of the carbon source.
  • a spinning source member comprising a carbon nanotube forest manufactured by the carbon nanotube forest manufacturing method described in any one of (1) to (16) above, and capable of spinning 1 mm or more. Spinning source member.
  • (21) A composite structure comprising the structure described in any one of (18) to (20) as a skeleton structure.
  • a CNT forest According to the method of manufacturing a CNT forest according to the present invention, it is possible to form catalyst particles without substantially performing a reduction process. Therefore, a CNT forest can be manufactured efficiently. Moreover, according to this invention, the spinning source member provided with the CNT forest efficiently manufactured by said method, the structure obtained from the said spinning source member, and the composite structure provided with this structure are also provided.
  • FIG. 1 It is a figure which shows roughly the structure of the manufacturing apparatus of the CNT forest which concerns on one Embodiment of this invention. It is a figure which shows roughly the structure of the gaseous-phase catalyst supply apparatus with which the manufacturing apparatus shown by FIG. 1 is provided. It is a figure which shows roughly the structure of the gaseous-phase promoter supply apparatus with which the manufacturing apparatus shown by FIG. 1 is provided. It is an image which shows the result of having observed the CNT forest manufactured with the manufacturing method which concerns on one Embodiment of this invention from the direction from which a side surface becomes in a visual field.
  • FIG. 1 It is a figure which shows roughly the structure of the manufacturing apparatus of the CNT forest which concerns on one Embodiment of this invention.
  • FIG. 2 is an observation image of CNTs constituting a CNT forest manufactured by a manufacturing method according to an embodiment of the present invention, and shows an observation result of CNTs located in the vicinity of half the height of the growth height of the CNT forest. It is. It is a graph which shows the outer diameter distribution of CNT which comprises the CNT forest produced in the Example (experiment number 2). It is an image which shows the state in which the CNT entanglement body was formed by pulling out (spinning) the CNT forest manufactured by the manufacturing method which concerns on one Embodiment of this invention to a fixed direction. It is an AFM image (plan view image) which shows the result of taking out the substrate after the catalyst placement step and measuring the surface on the growth base side with AFM.
  • AFM image plane view image
  • FIG. 9 is an image representing the AFM image of FIG. 8 as a perspective image. It is an observation image of a CNT forest according to Experiment No. 1. It is an observation image of a CNT forest according to Experiment No. 2. It is an observation image of a CNT forest according to Experiment No. 3. It is an observation image of a CNT forest according to Experiment No. 4. It is the observation image of CNT which comprises the CNT forest which concerns on experiment number 1, Comprising: (a) CNT near the position farthest from the growth base plane, (b) CNT near the position of half the height of growth (C) It is an observation image which shows the result of having observed CNT of the position proximal to the growth base face.
  • CNT which comprises the CNT forest which concerns on experiment number 2
  • CNT which comprises the CNT forest which concerns on experiment number 3
  • C It is an observation image which shows the result of having observed CNT of the position proximal to the growth base face.
  • CNT which comprises the CNT forest which concerns on experiment number 4
  • FIG. It is a figure which shows the result of having observed the growth base surface after peeling the CNT forest which concerns on the experiment number 1.
  • FIG. It is a figure which shows the result of having observed the growth base surface after peeling the CNT forest which concerns on the experiment number 2.
  • FIG. It is a figure which shows the result of having observed the growth base surface after peeling the CNT forest which concerns on the experiment number 3.
  • FIG. It is a figure which shows the result of having observed the growth base surface after peeling the CNT forest which concerns on the experiment number 4.
  • FIG. It is a figure which shows the result of spinning the CNT forest which concerns on experiment number 2 to 4.
  • CNT forest manufacturing apparatus A CNT forest manufacturing apparatus according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 1 is a diagram schematically showing a configuration of a manufacturing apparatus that can be used in a CNT forest manufacturing method according to an embodiment of the present invention.
  • the CNT forest 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 pipe 14 which is a reaction chamber having a growth region which is a region where CNTs are formed is passed.
  • the reaction vessel tube 14 is a substantially cylindrical member made of a heat-resistant material such as quartz, has an outer diameter smaller than that of the electric furnace 12, and extends along a predetermined direction A.
  • a substrate 28 having a growth base surface on which a CNT forest grows is disposed in the growth region of the reaction vessel tube 14. That is, the growth region in the CNT forest manufacturing apparatus 10 includes a region where the substrate 28 is disposed in the reaction vessel tube 14.
  • the position where the substrate is arranged in the growth region is not limited. In consideration of the shape of the reaction vessel tube 14, the arrangement of the heater 16, the exhaust capacity, the amount of the substance supplied into the reaction vessel tube 14, and the like, it may be arranged at a position where the CNT forest can be appropriately grown. .
  • the electric furnace 12 includes a heater 16 and a thermocouple 18.
  • the temperature adjustment apparatus includes a heater 16 and a thermocouple 18.
  • the heater 16 is a certain region in the predetermined direction A of the reaction vessel tube 14 (in other words, a certain region in the axial direction of the substantially cylindrical reaction vessel tube 14, hereinafter also referred to as “heating region”). Heat is generated to increase the temperature of the atmosphere in the tube in the heating region of the reaction vessel tube 14.
  • the thermocouple 18 is disposed in the vicinity of the heating region of the reaction vessel tube 14 inside the electric furnace 12, and can output an electric signal representing a temperature related to the temperature of the atmosphere in the tube in the heating region of the reaction vessel tube 14.
  • the heater 16 and the thermocouple 18 are electrically connected to the control device 20.
  • a supply device 22 is connected to the upstream side of the reaction vessel pipe 14 in the predetermined direction A (one end on the left side in FIG. 1).
  • the supply device 22 includes a raw material gas supply device 30, a catalyst raw material supply device 31, a gas phase promoter catalyst supply device 32, and an auxiliary gas supply device 33.
  • the supply device 22 is electrically connected to the control device 20 and is also electrically connected to each supply device included in the supply device 22.
  • the raw material gas supply device 30 supplies a carbon compound (for example, a hydrocarbon such as acetylene) that is a raw material of CNT constituting the CNT forest, that is, a raw material gas containing a carbon source to the inside of the reaction vessel pipe 14 (particularly the growth region).
  • a carbon compound for example, a hydrocarbon such as acetylene
  • the supply flow rate of the source gas from the source gas supply device 30 can be adjusted using a known flow rate adjusting device such as a mass flow.
  • the catalyst raw material supply device 31 supplies fine droplets (catalyst supply mist) M of the catalyst supply liquid L formed by atomizing the catalyst supply liquid L accommodated in the catalyst raw material supply device 31 to the reaction vessel tube 14. Can be supplied inside. Since the catalyst supply mist M contains the metal element-containing compound contained in the liquid L, the catalyst raw material supply device 31 can supply the metal element-containing compound to the inside (particularly the growth region) of the reaction vessel tube 14. it can.
  • the catalyst raw material supply device 31 has a unit structure. That is, the catalyst raw material supply device 31 mists the supply liquid chamber L containing the catalyst supply liquid L made of the liquid composition containing the metal element-containing compound and the supply liquid L in the supply unit chamber 31A.
  • An atomizing device 31B is provided. In FIG. 2, the atomizing device 31B includes a water bath 31B1 and an ultrasonic vibration generator 31B2 attached thereto.
  • the catalyst raw material supply device 31 can release the catalyst supply mist M in the gas supply device 31C and the supply unit chamber 31A for the purpose of transporting the catalyst supply mist M to the outside of the supply unit chamber 31A.
  • a discharge device 31D is provided.
  • the catalyst supply mist M generated by the atomization device 31B is transported by a gas (an inert gas such as argon is exemplified) supplied from the gas supply device 31C. It is supplied into the reaction vessel tube 14 from the discharge device 31D.
  • the gas supply device 31C and the discharge device 31D may include means for adjusting the amount of the substance that passes through each of them.
  • the catalyst raw material supply device 31 may have a mechanism for additionally supplying the catalyst supply liquid L, or may have a mechanism for controlling the pressure in the supply unit chamber 31A.
  • the vapor phase promoter supply device 32 can supply the vapor phase promoter to the inside of the reaction vessel pipe 14 (particularly, the growth region).
  • the gas phase promoter will be described later.
  • the supply flow rate of the gas phase promoter from the gas phase promoter supply device 32 can be adjusted using a known flow rate adjusting device such as mass flow.
  • the gas phase promoter supplying device 32 may be capable of supplying a plurality of gas phase promoters.
  • the gas phase promoter supplying device 32 includes a plurality of supplying devices such as a first gas phase promoter supplying device 32a, a second gas phase promoter supplying device 32b,. It may be.
  • the auxiliary gas supply device 33 is a gas other than the raw material gas, the catalyst supply mist M and the gas phase promoter, for example, an inert gas such as argon (this gas is generically referred to as “auxiliary gas” in this specification). It can supply to the inside (especially growth region) of the reaction vessel tube 14.
  • the supply flow rate of the auxiliary gas from the auxiliary gas supply device 33 can be adjusted using a known flow rate adjusting device such as a mass flow.
  • a pressure regulating valve 23 and an exhaust device 24 are connected to the other end on the downstream side (right side in FIG. 1) of the reaction vessel pipe 14 in the predetermined direction A.
  • the pressure adjusting valve 23 can adjust the pressure in the reaction vessel pipe 14 by changing the degree of opening and closing of the valve.
  • the exhaust device 24 evacuates the inside of the reaction vessel tube 14.
  • the specific type of the exhaust device 24 is not particularly limited, and a rotary pump, an oil diffusion pump, a mechanical booster, a turbo molecular pump, a cryopump, or the like can be used alone or in combination.
  • the pressure adjustment valve 23 and the exhaust device 24 are electrically connected to the control device 20.
  • a pressure gauge 13 for measuring the internal pressure is provided inside the reaction vessel tube 14.
  • the pressure gauge 13 is electrically connected to the control device 20 and can output an electric signal representing the pressure inside the reaction vessel pipe 14 to the control device 20.
  • control device 20 is electrically connected to the heater 16, the thermocouple 18, the supply device 22, the pressure gauge 13, the pressure adjustment valve 23, and the exhaust device 24, and outputs electrical signals output from these devices and the like. It inputs or controls the operation of these devices and the like based on the inputted electric signal.
  • control device 20 a specific operation of the control device 20 will be exemplified.
  • the control device 20 inputs an electrical signal regarding the internal temperature of the reaction vessel tube 14 output from the thermocouple 18 and outputs a control signal related to the operation of the heater 16 determined based on the electrical signal to the heater 16. can do.
  • the heater 16 receiving the control signal from the control device performs an operation of increasing or decreasing the amount of generated heat based on the control signal, and changes the internal temperature of the heating region of the reaction vessel pipe 14.
  • the control device 20 inputs an electric signal regarding the internal pressure of the heating region of the reaction vessel tube 14 output from the pressure gauge 13 and relates to the operation of the pressure adjusting valve 23 and the exhaust device 24 determined based on the electric signal.
  • a control signal can be output to the pressure regulating valve 23 and the exhaust device 24.
  • the pressure adjustment valve 23 and the exhaust device 24 that have received the control signal from the control device 20 change the opening degree of the pressure adjustment valve 23 or change the exhaust capability of the exhaust device 24 based on the control signal. Perform operations such as.
  • the control device 20 can output a control signal for controlling the operation of each device or the like to each device according to a preset time table. For example, control signals for starting and stopping substance supply from each of the raw material gas supply device 30, the catalyst raw material supply device 31, the gas phase cocatalyst supply device 32, and the auxiliary gas supply device 33 included in the supply device 22 and the supply flow rate are determined. It can be output to the supply device 22.
  • the supply device 22 to which the control signal is input operates each supply device in accordance with the control signal, and starts or stops the supply of each material such as the source gas into the reaction vessel tube 14.
  • the control device 20 can control the operation of each part constituting the catalyst raw material supply device 31. That is, the control device 20 can output a control signal related to the operation of the atomization device 31B included in the catalyst raw material supply device 31.
  • the atomization device 31B that has input the control signal can start or stop atomization of the catalyst supply liquid L in the supply unit chamber 31A according to the control signal.
  • the control device 20 can output a control signal related to the operation of the gas supply device 31C.
  • the gas supply device 31C having received the control signal changes the amount of gas supplied into the supply unit chamber 31A in accordance with the control signal.
  • the control device 20 can output a control signal related to the operation of the discharge device 31D.
  • the release device 31D receiving the control signal adjusts the timing and amount of supplying the catalyst supply mist M outside the supply unit chamber 31A, that is, in the reaction vessel pipe 14 in FIG. 1, according to the control signal. Can do.
  • the control device 20 can output control signals related to these operations.
  • CNT Forest Manufacturing Method A CNT forest manufacturing method according to an embodiment of the present invention will be described.
  • the manufacturing method of the CNT forest according to the present embodiment includes a catalyst placement step and a growth step.
  • the case of manufacturing using the manufacturing apparatus 10 is taken as a specific example.
  • Catalyst placement step In the method for producing a CNT forest according to this embodiment, as the catalyst placement step, a liquid composition (catalyst supply liquid L) containing a metal element-containing compound is misted to obtain a liquid obtained. Metal element contained in mist of liquid composition (mist M for catalyst supply) by supplying mist of composition (mist M for catalyst supply) into reaction chamber (reaction vessel tube 14) heated to a predetermined temperature A metal-based solid phase catalyst is produced from the contained compound in the reaction chamber (reaction vessel tube 14), and the metal-based solid phase catalyst is formed on the growth base surface of the substrate 28 located in the reaction chamber (reaction vessel tube 14). Deploy.
  • 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 28 may be a growth base surface, or only a part of the surface of the substrate 28 is a growth base surface and the other part is not a growth base surface, and is in a so-called patterned state. Also good.
  • the material constituting the growth base surface is not limited as long as the CNT forest can be grown.
  • Examples of the material constituting the growth base surface include compounds containing at least one of a metal element such as aluminum and a metalloid element such as silicon. Specific examples include silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, and composite compounds thereof.
  • the material constituting the growth base surface may contain a transition metal element such as Fe or Ni, or may contain a nonmetallic element such as boron or carbon.
  • the material constituting the growth 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 growth base is also made of quartz
  • the material constituting the substrate 28 is made of a silicon substrate mainly composed of silicon, and the growth base surface is made.
  • the constituent material include the oxide film.
  • catalyst supply mist M is supplied into the reaction vessel tube 14.
  • the catalyst supply mist M can be generated from the catalyst supply liquid L by using the catalyst raw material supply apparatus 31.
  • the catalyst raw material supply device 31 performs mist formation using an ultrasonic vibration generator. That is, the mist formation of the catalyst supply liquid L is mechanical.
  • the method for misting the catalyst supply liquid L is not limited to this. It may be performed by allowing gas to pass through the catalyst supply liquid L (bubbling).
  • the catalyst supply mist M contains a metal element-containing compound, and a metal-based solid phase catalyst is formed from the metal element-containing compound.
  • the metal element contained in the metal element-containing compound is not limited as long as it is an element constituting the catalyst material of the CNT forest. Preferred examples include iron group elements such as Fe, Ni, and Co. In addition, Mo and the like are also exemplified as metal elements contained in the metal element-containing compound.
  • the composition of the metal element-containing compound is not limited as long as a metal-based solid phase catalyst can be formed.
  • a preferable example is a metal element-containing coordination compound.
  • Specific examples of the metal element-containing coordination compound include metallocene compounds such as ferrocene, nickelocene and cobaltcene, carbonyl complexes such as iron carbonyl complexes, and iron-methanol complexes.
  • the solvent contained in the catalyst supply liquid L is not limited as long as the metal element-containing compound can be dissolved.
  • the catalyst supply liquid L may contain an organic compound as a solvent. Examples of such a solvent include alcohols such as ethanol and methanol.
  • Such an organic compound as a solvent preferably does not function as a carbon source for growing carbon nanotubes. That is, it is preferable that the CNT forest is grown only in the growth step without forming the CNT forest on the growth base surface of the substrate 28 in the catalyst placement step. By doing so, process controllability can be improved.
  • a metal-based solid phase catalyst is formed from the metal element-containing compound.
  • the metal element-containing compound is ferrocene
  • iron atoms are generated from ferrocene, the iron atoms are clustered and deposited on the growth base surface of the substrate 28, and are arranged as a metal-based solid phase catalyst.
  • the atmosphere in the reaction vessel tube 14 in the catalyst arranging step is an inert atmosphere.
  • the metal-based solid phase catalyst placed in the catalyst placement step is hardly oxidized, and the growth of the CNT forest can be stably started in the growth step.
  • the pressure of the atmosphere in the reaction vessel pipe 14 in the catalyst placement step is not particularly limited. It may be atmospheric pressure (about 1.0 ⁇ 10 5 Pa), negative pressure, or positive pressure.
  • the inside of the reaction vessel tube 14 is set to a negative pressure atmosphere in the growth step, it is preferable to reduce the transition time between steps by setting the atmosphere to a negative pressure also in the catalyst arrangement step.
  • the specific total pressure of the atmosphere is not particularly limited. As an example, it may be set to 1 ⁇ 10 ⁇ 2 Pa or more and 1 ⁇ 10 5 Pa or less.
  • the temperature of the atmosphere in the reaction vessel tube 14 in the catalyst placement step is not particularly limited. It may be normal temperature (about 25 ° C.), may be heated, or may be cooled. When the atmosphere in the reaction vessel tube 14 is heated, the metal-based solid phase catalyst may be easily disposed on the growth base surface. As will be described later, since the growth region of the reaction vessel tube 14 is preferably heated in the growth process, the transition region between steps can be shortened by heating the growth region also in the catalyst placement step. It may be preferable.
  • reaction vessel tube 14 a carbon source is supplied into the reaction chamber (reaction vessel tube 14), and carbon nanotubes are grown from a metal-based solid phase catalyst on the growth base surface of the substrate 28. A CNT forest is formed.
  • the kind of carbon source is not particularly limited, usually a hydrocarbon-based material is used, and acetylene is given as a specific example.
  • the method for causing the carbon source to exist in the reaction vessel tube 14 (particularly the growth region) is not particularly limited.
  • the carbon source may be present by supplying a carbon source from the source gas supply apparatus 30, or a material capable of generating the carbon source is previously present in the reaction vessel pipe 14.
  • the growth process may be initiated by generating a carbon source from the material and diffusing it into the reaction vessel 14.
  • the carbon source is supplied from the source gas supply device 30, it is preferable to control the supply flow rate of the carbon source 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 into 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 carbon source containing acetylene in the case where the pressure of the pressure gauge 13 is 1 ⁇ 10 2 Pa or more and 1 ⁇ 10 4 Pa or less is exemplified by 10 sccm or more and 1000 sccm or less. In this case, 20 sccm or more and 500 sccm or less More preferably, it is 50 sccm or more and 300 scc
  • the “gas phase co-catalyst” has a function of promoting the growth of the CNT forest in the growth process (hereinafter also referred to as “growth promoting function”). It means a substance that has a function of improving the spinnability of a member having a forest (hereinafter also referred to as “spinnability improving function”) and is supplied into the reaction vessel tube 14 in a gas phase. Details of the growth promoting function are not particularly limited.
  • the specific composition of the gas phase co-catalyst is not particularly limited as long as it fulfills the above growth promoting function and preferably further the spinnability improving function.
  • a halogen-containing substance that is a substance containing a halogen element can be given.
  • the halogen-containing material include chlorine (Cl 2 ), bromine (Br 2 ), hydrogen chloride (HCl), hydrogen bromide (HBr), and the like.
  • the halogen-containing substance is preferably supplied into the reaction chamber (reaction vessel tube 14) simultaneously with the supply of the carbon source or after the start of the supply of the carbon source.
  • the supply amount of the halogen-containing substance is preferably 0.05 volume% to 5 volume% of the supply amount of the carbon source, preferably 0.1 volume% to 3 volume%. It is more preferable that the amount is equal to or less than volume%, and it is particularly preferable that the amount is equal to or greater than 0.2 volume% and equal to or less than 1 volume%.
  • gas phase promoter is a reducing substance.
  • the reducing substance include acetone, hydrogen, and carbon monoxide, and the reducing substance preferably contains one or more substances selected from the group consisting of these substances.
  • the supply amount of the reducing substance is preferably 5 volume% to 50 volume% of the supply amount of the carbon source, and preferably 10 volume% to 30 volume%. More preferably, the amount is
  • the gas phase promoter can be supplied using the gas phase promoter supply device 32.
  • the gas phase promoter may be supplied alone or may be supplied together with another gas (inert gas is exemplified).
  • the relationship with the supply timing of the gas phase promoter is appropriately set according to the function of the gas phase promoter.
  • the halogen-containing substance is preferably supplied into the reaction chamber (reaction vessel tube 14) simultaneously with the supply of the carbon source or after the start of the supply of the carbon source.
  • the metal-based solid phase catalyst is affected by the halogen-containing substance and the function as a catalyst is lowered.
  • the total pressure of the atmosphere in the reaction vessel tube 14 in the growth process is not particularly limited. It may be atmospheric pressure (about 1.0 ⁇ 10 5 Pa), negative pressure, or positive pressure. What is necessary is just to set suitably considering the composition (partial pressure ratio) of the substance which exists in the reaction container pipe
  • tube 14 is made into a negative pressure, it will be 1 * 10 ⁇ 1 > Pa or more and 1 * 10 ⁇ 4 > Pa or less, 2 * 10 ⁇ 1 > Pa or more and 5 X10 3 Pa or less is preferable, 5 ⁇ 10 1 Pa or more and 2 ⁇ 10 3 Pa or less is more preferable, and 1 ⁇ 10 2 Pa or more and 1 ⁇ 10 3 Pa or less is particularly preferable.
  • the temperature of the growth region of the reaction vessel tube 14 in the growth step is such that the substrate 28 is grown using a carbon source under the condition that an appropriate amount of the metal-based solid phase catalyst and the gas phase promoter used as needed exists in the growth region.
  • a CNT forest can be formed on the base surface.
  • the temperature of the growth base surface in the growth process may be controlled by adjusting the temperature of the growth region of the reaction vessel tube 14.
  • the temperature of the growth base surface of the substrate 28 during the growth process is preferably heated to 600 ° C. or higher.
  • the temperature of the growth base surface of the substrate 28 is 600 ° C. or higher, the interaction between the vapor phase promoter used as necessary and the carbon source tends to occur on the growth base surface, and the growth base surface of the substrate 28 CNT forest is easy to grow.
  • the temperature of the growth base surface during the growth process is preferably heated to 650 ° C. or higher, more preferably 700 ° C. or higher, and to 750 ° C. or higher. It is particularly preferred that it is heated.
  • the upper limit of the temperature of the growth base surface of the substrate 28 during the growth process is not particularly limited, but if it is excessively high, the material constituting the growth base surface and the material constituting the substrate 28 (these may be the same). )) May lack stability as a solid, it is preferable to set an upper limit in consideration of the melting point and sublimation temperature of these materials. Considering the load on the reaction vessel, the upper limit temperature of the substrate 28 is preferably about 1200 ° C.
  • CNT Forest An example of a CNT forest manufactured by a manufacturing method according to an embodiment of the present invention is that a plurality of CNTs are aligned in a certain direction (normal to the growth base surface) as shown in FIG. 4 and FIG. A portion having a structure arranged to be oriented in a direction).
  • the outer diameters of a plurality of CNTs in this portion are measured and their distribution is obtained, the outer diameters of the CNTs constituting the CNT forest are mostly in the range of 5 to 30 nm as shown in FIG. .
  • the CNT constituting the CNT forest can be observed with an electron microscope or the like, and the outer diameter of the CNT can be measured from the obtained observation image.
  • FIG. 7 is an image showing a state in which a CNT entangled body B is formed by pulling (spinning) a CNT forest F manufactured by the manufacturing method according to an embodiment of the present invention in the direction S.
  • the CNTs constituting the CNT entangled body are intertwined with each other to form a coupled body while being oriented in the direction (spinning direction) drawn from the CNT forest.
  • a member having a CNT forest and capable of forming a CNT entangled body is also referred to as a “spinning source member”.
  • 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 if twisting is applied when the spinning source member is pulled out to obtain this. 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 linear CNT entangled body can arbitrarily control the degree of orientation of the CNTs constituting the linear CNT entangled body by changing the spinning method from the spinning source member (specific examples include the degree of twisting). Can do. 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.
  • 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, gaps exist between the entangled CNTs, as in the case of the plurality of fibers constituting the unwoven cloth.
  • 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.
  • Example 1 Preparation of catalyst supply liquid L Ferrocene as a metal element-containing coordination compound, which is a kind of metal element-containing compound, is dissolved in ethanol, and the concentration of ferrocene is 10 g / L (1.3% by mass). A solution was obtained as catalyst supply liquid L.
  • a silicon substrate (10 mm ⁇ 5 mm ⁇ thickness 0.6 mm) having a thermal oxide film (thickness: 400 nm) was prepared as a substrate. Therefore, in this example, the material constituting the growth base surface was SiO 2 . With the substrate placed on a quartz boat, the substrate was placed in a reaction vessel tube as a reaction chamber together with this boat.
  • the inside of the reaction vessel tube was evacuated to 300 Torr (40 kPa) using an exhaust device. Subsequently, while maintaining the pressure in the reaction vessel tube at 300 Torr (40 kPa), the inside of the reaction vessel tube is heated to 820 ° C. (1.09 ⁇ 10 3 K) using a heater, and the temperature of the bakeware and the substrate is increased. The temperature was about 820 ° C. (1.09 ⁇ 10 3 K).
  • the catalyst supply liquid L is placed in the supply unit chamber of the catalyst raw material supply apparatus having the structure shown in FIG. 2, and the atomization apparatus (including the ultrasonic vibration generator) is operated to supply the catalyst. Mist M was produced. While supplying argon at 500 sccm from the gas supply device, the valve as the release device was opened for 1 minute, and the catalyst supply mist M was supplied into the reaction chamber. As a result, a metal-based solid phase catalyst was formed on the growth base surface of the substrate.
  • the production of the metal-based solid phase catalyst was separately confirmed as follows.
  • the inside of the reaction chamber was returned to room temperature, and then the substrate was taken out from the reaction chamber with the pressure in the reaction chamber set to atmospheric pressure.
  • the surface on the growth base side of the substrate taken out was measured by AFM (measurement size: 0.5 ⁇ m ⁇ 0.5 ⁇ m).
  • An AFM image was obtained based on the measurement data (FIGS. 8 and 9).
  • a substance having a diameter of several tens of nm and a height of several nm was arranged on the growth base so as to cover the growth base.
  • This AFM image is measured by AFM in the atmosphere on the surface on which a metal-based solid-phase catalyst obtained by performing a general metal-based solid-phase catalyst manufacturing method consisting of iron sputtering, hydrogen reduction, and heating is formed. It was equivalent to the AFM image obtained. Therefore, it was confirmed by the AFM images shown in FIGS. 8 and 9 that the metal-based solid phase catalyst was appropriately arranged on the growth base surface by the catalyst arranging step.
  • FIGS. 10 to 17 are observation images obtained at a magnification capable of confirming the synthetic structure of the CNT forest.
  • FIGS. 14 to 17 show (a) a CNT in the vicinity of a position farthest from the growth base surface, and (b) a position at a half height of the growth height, in order to confirm the growth state of the CNT constituting the CNT forest. It is an observation image which shows the result of having observed the near CNT and (c) CNT of a position proximal to a growth base face.
  • each CNT constituting each CNT forest was measured to obtain a frequency distribution.
  • the results are shown in FIG. 6 (experiment number 2) and FIGS. 18 to 20 (experiment numbers 1, 3 and 4). From the obtained frequency distribution, the average outer diameter (unit: nm) of CNTs constituting the CNT forest according to each experiment number was determined. The results are shown in Table 2.
  • the CNT forest in the growth process was photographed with a camera, and the growth height (unit: mm / 20 minutes) and the growth rate (unit: ⁇ m / minute) were determined from the photographed images. The results are shown in Table 2.
  • the CNT forest was peeled from the growth base surface by applying a thin blade near the interface with the growth base surface and moving it in a direction parallel to the growth base surface.
  • traces from which the CNTs were removed were confirmed as holes (FIGS. 21 to 24).
  • the density of the holes was measured to obtain the density of CNT in the CNT forest (unit: 10 10 cm ⁇ 2 ). The results are shown in Table 2.
  • the CNT entangled body obtained from the CNT forest manufactured by the CNT forest manufacturing method according to the present invention is suitably used as, for example, an electric wiring, a heating element, a strain sensor, a transparent electrode sheet, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inorganic Fibers (AREA)

Abstract

L'invention fournit un procédé de fabrication de forêt de nanotubes de carbone qui est destiné à fabriquer de manière efficace une forêt de nanotubes de carbone par un procédé catalytique en phase solide. Ce procédé de fabrication de forêt de nanotubes de carbone comporte : une étape de disposition de catalyseur au cours de laquelle une composition liquide comprenant un composé à teneur en élément métallique, est transformée en brouillard, le brouillard ainsi obtenu de ladite composition liquide est amené à l'intérieur d'une chambre de réaction chauffée à une température prédéfinie, un catalyseur en phase solide à base de métal est produit à l'intérieur de ladite chambre de réaction à partir dudit composé à teneur en élément métallique compris dans le brouillard de ladite composition liquide, et ledit catalyseur en phase solide à base de métal est disposé sur une face de base de croissance d'un substrat positionné à l'intérieur de ladite chambre de réaction ; et une étape de croissance au cours de laquelle une source de carbone est amenée à l'intérieur de ladite chambre de réaction, des nanotubes de carbone sont mis en croissance à partir dudit catalyseur en phase solide à base de métal sur ladite face de base de croissance, et la forêt de nanotubes de carbone se forme sur ledit substrat.
PCT/JP2016/068333 2015-06-25 2016-06-21 Procédé de fabrication de forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite WO2016208557A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017524907A JP6667849B2 (ja) 2015-06-25 2016-06-21 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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-128083 2015-06-25
JP2015128083 2015-06-25

Publications (1)

Publication Number Publication Date
WO2016208557A1 true WO2016208557A1 (fr) 2016-12-29

Family

ID=57585746

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/068333 WO2016208557A1 (fr) 2015-06-25 2016-06-21 Procédé de fabrication de forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite

Country Status (2)

Country Link
JP (1) JP6667849B2 (fr)
WO (1) WO2016208557A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023182813A1 (fr) * 2022-03-22 2023-09-28 한국재료연구원 Appareil de fabrication de fibre de nanotubes de carbone et fibre de nanotubes de carbone fabriquée à l'aide de celui-ci

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003171108A (ja) * 2001-12-03 2003-06-17 Ricoh Co Ltd カーボンナノチューブの作製方法
JP2010254507A (ja) * 2009-04-23 2010-11-11 Fujitsu Semiconductor Ltd 線状構造体の成長方法及び成長装置
WO2012153816A1 (fr) * 2011-05-10 2012-11-15 国立大学法人静岡大学 Procédé et appareil de fabrication de nanotubes de carbone
JP2015078120A (ja) * 2008-12-30 2015-04-23 独立行政法人産業技術総合研究所 単層カーボンナノチューブ配向集合体、バルク状単層カーボンナノチューブ配向集合体、粉体状単層カーボンナノチューブ配向集合体
WO2015083701A1 (fr) * 2013-12-03 2015-06-11 国立大学法人静岡大学 Fil torsadé de nanotubes de carbone et procédé de production et source de filage pour un fil torsadé de nanotubes de carbone

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8409768B2 (en) * 2009-10-12 2013-04-02 Board Of Regents, The University Of Texas Systems Tuning of Fe catalysts for growth of spin-capable carbon nanotubes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003171108A (ja) * 2001-12-03 2003-06-17 Ricoh Co Ltd カーボンナノチューブの作製方法
JP2015078120A (ja) * 2008-12-30 2015-04-23 独立行政法人産業技術総合研究所 単層カーボンナノチューブ配向集合体、バルク状単層カーボンナノチューブ配向集合体、粉体状単層カーボンナノチューブ配向集合体
JP2010254507A (ja) * 2009-04-23 2010-11-11 Fujitsu Semiconductor Ltd 線状構造体の成長方法及び成長装置
WO2012153816A1 (fr) * 2011-05-10 2012-11-15 国立大学法人静岡大学 Procédé et appareil de fabrication de nanotubes de carbone
WO2015083701A1 (fr) * 2013-12-03 2015-06-11 国立大学法人静岡大学 Fil torsadé de nanotubes de carbone et procédé de production et source de filage pour un fil torsadé de nanotubes de carbone

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
INOUE, YOKU: "Direct Dry Spinning of Millimeter- long Carbon Nanotube Arrays for Aligned Sheet and Yarn", NANOTUBE SUPERFIBER MATERIALS., 16 September 2013 (2013-09-16), pages 389 - 414 *
YOKU INOUE ET AL.: "Lightweight and Strong Carbon Nanotube Structures Using Ultra-Long Carbon Nanotubes Grown by Chloride Mediated Chemical Vapor Deposition", ANNUAL REPORT OF THE MURATA SCIENCE FOUNDATION, December 2011 (2011-12-01), pages 186 - 195 *
YOKU INOUE: "Cho Bosekisei CNT Array kara no Kanshiki Boseki ni yoru CNT Bosekishi", JOURNAL OF THE TEXTILE MACHINERY SOCIETY OF JAPAN, vol. 66, no. 4, April 2013 (2013-04-01), pages 233 - 237 *

Also Published As

Publication number Publication date
JPWO2016208557A1 (ja) 2018-05-31
JP6667849B2 (ja) 2020-03-18

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
KR101289256B1 (ko) 탄소 나노튜브의 성장 및 수득 방법
US10343919B2 (en) Production method for carbon nanotubes
JP5409345B2 (ja) ブラシ状カーボンナノ構造物製造用触媒体、その製造方法及びブラシ状カーボンナノ構造物製造方法
JP2013509504A (ja) Ｃｎｔ浸出金属繊維材料及びそのための方法
JP5860547B2 (ja) 長尺なカーボンナノチューブの製造方法および製造装置
CN103889890A (zh) 用于在可重复使用的基材上连续生产碳纳米结构的系统和方法
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
JP5364904B2 (ja) カーボンナノファイバー集合体の製造方法
WO2016208557A1 (fr) Procédé de fabrication de forêt de nanotubes de carbone, élément de source de repoussage, structure, et structure composite
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
CN111094179A (zh) 由排列碳纳米管制成的电缆的制造方法
KR101415228B1 (ko) 1차원 탄소 나노섬유의 합성 방법
JP6667848B2 (ja) 構造体、ｃｎｔフォレストの製造方法および構造体の製造方法
JP5942069B2 (ja) カーボンナノチューブの製造装置および当該製造装置の一部となる供給ユニットならびにカーボンナノチューブの製造方法
JP2019151515A (ja) カーボンナノチューブフォレストの製造方法
Sehrawat et al. Floating catalyst chemical vapour deposition (FCCVD) for direct spinning of CNT aerogel: A review
JPWO2016117198A1 (ja) 開口基板
KR101349041B1 (ko) 탄소나노섬유로 구성된 탄소박막 합성방법 및 그 구조체
KR20190082713A (ko) 그래핀의 결정립 경계 탐지 방법 및 이러한 방법을 사용하는 장치
Ren et al. Chemical Vapor Deposition of Carbon Nanotubes

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: 16814327

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017524907

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: 16814327

Country of ref document: EP

Kind code of ref document: A1