WO2016208170A1 - ナノ炭素複合材料およびその製造方法 - Google Patents
ナノ炭素複合材料およびその製造方法 Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C01P2006/40—Electric properties
Definitions
- the present invention relates to a nanocarbon composite material or the like, for example, a material composed of carbon nanohorns.
- Carbon materials are generally widely used for applications such as conductive materials, catalyst carriers, adsorbents, separating agents, inks, and toners.
- Patent Document 1 Carbon Nanohorn
- Patent Document 2 DDS: Drug Delivery System (Drug Delivery System)
- Patent Document 3 Solid Lubricant
- Patent Document 4 Metal Gas Occlusion
- Patent Document 5 adsorbent
- Patent Document 6 methane decomposition catalyst
- Patent Document 7 catalyst carrier
- Patent Document 8 conductive material
- thermoplastic resin and a plastic molded product exhibiting excellent conductivity are realized by adding a thermoplastic resin and an organically modified layered silicate to carbon nanotubes.
- Patent Document 11 proposes a carbon nanohorn aggregate as a highly dispersible conductive material. According to the technique described in Patent Document 11, an excellent conductive paste is realized by mixing carbon nanohorn aggregates with metal particles and resin.
- This carbon nanohorn aggregate has a spherical structure of about 100 nm in which single-walled carbon nanohorns having a diameter of about 2-5 nm and a length of about 40-50 nm are gathered radially. Further, this carbon nanohorn aggregate is different from the conventional spherical conductive material such as carbon black. Radial single-walled carbon nanohorn aggregates have many contact points with the base material (matrix) and have the property of being easily entangled.
- carbon nanotubes have a problem of low dispersibility and low affinity with other materials. For this reason, when a resin, an elastomer, or the like is mixed, a complicated pretreatment process or the like is required to extract the excellent characteristics of the carbon nanotube, and the manufacturing cost becomes expensive.
- the carbon nanohorn aggregate has an excellent dispersibility but has a spherical structure. For this reason, when the carbon nanohorn aggregate is used as a composite material, there is a problem that it is difficult to obtain a good conductive path as compared with a high aspect ratio needle-like structure such as a carbon nanotube. That is, since the carbon nanotubes having a needle-like structure can form a conductive path of about several ⁇ m, the effect of imparting conductivity is great. In contrast, a carbon nanohorn aggregate having a spherical structure cannot form a long conductive path like a carbon material having a needle-like structure.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a nanocarbon composite material and the like excellent in imparting conductivity. Moreover, this invention is providing the nanocarbon composite material etc. which were excellent also in thermal conductivity provision and mechanical strength in addition to electroconductivity provision.
- the nanocarbon composite material of the present invention is formed by dispersing a fibrous carbon nanohorn aggregate in which single-walled carbon nanohorn aggregates are connected in a fibrous form in a base material.
- the method for producing a nanocarbon composite material of the present invention includes an atmosphere setting step in which the inside of a container in which a catalyst-containing carbon target is arranged is placed in an inert gas, nitrogen gas, or mixed atmosphere, and the catalyst-containing carbon target is rotated. While evaporating the catalyst-containing carbon target by laser ablation, in the process of evaporating the catalyst-containing carbon target, a gas flow rate control step for controlling the gas flow rate constant, the atmosphere setting step, the evaporation step, and the gas And a mixing step of mixing a fibrous carbon nanohorn aggregate, in which a plurality of single-walled carbon nanohorns are connected in a fibrous form, obtained through a process including a flow rate control step, with a base material.
- nanocarbon composite material and the like according to the present invention it is possible to provide a nanocarbon composite material having excellent conductivity.
- FIG. 2 is a scanning electron micrograph of fibrous carbon nanohorn aggregates and spherical carbon nanohorn aggregates produced according to the present invention. It is a transmission electron micrograph of the fibrous carbon nanohorn aggregate
- the present inventor has also found that the fibrous carbon nanohorn aggregate can be formed simultaneously with a spherical carbon nanohorn aggregate excellent in dispersibility.
- fibrous carbon nanohorn aggregates and spherical carbon nanohorn aggregates have a radial structure, they have a large number of contact points at the interface and strongly adsorb, and the matrix (matrix) also strongly adsorbs. To do.
- the fibrous carbon nanohorn aggregate has higher dispersibility than other carbon materials having a needle-like structure.
- the present inventor has high electrical conductivity, high thermal conductivity, and mechanical strength by dispersing the fibrous and spherical carbon nanohorn aggregates in a high ratio (high dispersion) in the base material.
- the inventors have found that it is possible to produce a nanocarbon composite material having excellent durability and the like.
- FIG. 1 is a perspective view schematically showing the configuration of the nanocarbon composite material 100.
- the nanocarbon composite material 100 includes a fibrous carbon nanohorn aggregate 11, a spherical carbon nanohorn aggregate 12, and a base material (matrix) 13.
- the fibrous carbon nanohorn aggregates 11 are dispersed in the base material 13.
- the fibrous carbon nanohorn aggregate 11 is formed by connecting a plurality of single-walled carbon nanohorns in a fibrous form.
- the fibrous carbon nanohorn aggregate 11 is formed by collecting a plurality of single-walled carbon nanohorns in a fibrous form.
- the single-walled carbon nanohorn has a conical shape in which the tip portion of the tubular single-walled carbon nanotube is sharpened like a horn, and is composed mainly of a carbon atom surface of a graphite structure like the carbon nanotube. Yes.
- Each single-walled carbon nanohorn constituting the fibrous carbon nanohorn aggregate 11 is the same as the single-walled carbon nanohorn constituting the spherical carbon nanohorn aggregate 12.
- each of the single-walled carbon nanohorn aggregates is gathered radially with the corners (horns) outward.
- each of the single-walled carbon nanohorns is connected in a one-dimensional direction in a fibrous manner with the tips gathering radially outward.
- the fibrous carbon nanohorn aggregate 11 includes a seed-type aggregate structure, a bud-type aggregate structure, a dahlia-type aggregate structure, a petal-dahlia-type (mixed petal and dahlia) aggregate structure, a petal-type ( It is formed of at least one type of carbon nanohorn aggregate among the aggregate structure of several graphene sheet structures). Seed type assembly structure, bud type assembly structure, dahlia type assembly structure, petal dahlia type (mixed petal and dahlia), petal type (several graphene sheet structures), etc. This will be explained in detail.
- the fibrous carbon nanohorn aggregate 11 does not aggregate because of the spherical carbon nanohorn aggregate 12, and is dispersed in the base material 13. In addition, since the target using the catalyst metal is produced by evaporation, the catalyst metal exists inside the fibrous carbon nanohorn aggregate 11.
- the spherical carbon nanohorn aggregates 12 are dispersed in the base material 13.
- the spherical carbon nanohorn aggregate 12 is formed by agglomerating a plurality of single-walled carbon nanohorns into a spherical shape.
- Each single-walled carbon nanohorn constituting the spherical carbon nanohorn aggregate 12 is the same as the single-walled carbon nanohorn constituting the fibrous carbon nanohorn aggregate 11.
- the spherical carbon nanohorn aggregate 12 is highly dispersed in the base material 13 and adsorbed on the fibrous carbon nanohorn aggregate 11 having a large aspect ratio. For this reason, the electron conductive path of the nanocarbon composite material 100 increases.
- the catalytic metal is mainly present inside the spherical carbon nanohorn aggregate 12.
- fibrous carbon nanohorn aggregates 11 and spherical carbon nanohorn aggregates 12 are dispersed in the base material 13.
- the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 are highly dispersible, the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 are contained in the base material 13 without a dispersant. It can also be distributed.
- the base material 13 is made of any one or a plurality of metals, oxides, conductive polymer compounds, resins, and elastomers, for example.
- the single-walled carbon nanohorns of the fibrous carbon nanohorn aggregates 11 and the spherical carbon nanohorn aggregates 12 are both pointed outward.
- the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 have many contact points with each other, the adhesion is increased, and the resistance to the structural change and the durability are increased.
- the fibrous and spherical products in the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 are generated at the same time and mixed and exist. For this reason, it becomes a structure where a fibrous product does not aggregate easily.
- the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 are separated separately using a centrifugal separation method, filtration with a filter, a difference in sedimentation speed after being dispersed in a solvent, gel permeation chromatography, or the like. You can also However, in order to maintain the high dispersibility of the fibrous carbon nanohorn aggregate 11, it is preferable to use it as it is without separation.
- the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 may be simply referred to as a carbon nanohorn aggregate.
- Each single-layer carbon nanohorn of the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 was produced by the present inventor and had a diameter of approximately 1 nm to 5 nm and a length of 30 nm to 100 nm. .
- the fibrous carbon nanohorn aggregate 11 can have a diameter of about 30 nm to 200 nm and a length of about 1 ⁇ m to 100 ⁇ m.
- the spherical carbon nanohorn aggregate 12 has a diameter of about 30 nm to 200 nm and a substantially uniform size.
- the carbon nanohorn aggregate is formed of a seed type, a bud type, a dahlia type, a petal-dahlia type, a petal type alone or in combination.
- the seed mold is a shape with little or no angular protrusions on the spherical surface.
- the bud type is a shape in which some angular protrusions are seen on the spherical surface.
- the dahlia type is a shape in which a lot of angular protrusions are seen on a spherical surface.
- the petal type is a shape in which petal-like protrusions are seen on a spherical surface.
- the petal-dahlia type is an intermediate structure between the dahlia type and the petal type.
- the fibrous carbon nanohorn aggregate 11 is generated in a state of being mixed with the spherical carbon nanohorn aggregate 12.
- the form (particle size and the like) of the spherical carbon nanohorn aggregate 12 can be adjusted depending on the production conditions, and in particular, is changed depending on the laser output, the type of gas, and the flow rate.
- Fine holes can be formed in the fibrous carbon nanohorn aggregate 11 or the spherical carbon nanohorn aggregate 12 (opening) by oxidation treatment.
- oxidation treatment By performing the oxidation treatment, defective portions such as five-membered rings and seven-membered rings are oxidized. As a result, a part having a five-membered ring or a seven-membered ring such as a side surface or a tip is opened.
- surface functional groups containing oxygen are formed in the pores.
- a gas phase process and a liquid phase process can be used for the oxidation treatment.
- air, oxygen, or carbon monoxide can be used as the atmospheric gas, and air is suitable from the viewpoint of cost.
- the temperature during the oxidation treatment can be in the range of 300 to 650 ° C., and 400 to 550 ° C. is more suitable.
- the oxidation treatment is performed at 300 ° C. or higher, there is no concern that carbon hardly burns and cannot be opened. Further, when the oxidation treatment is performed at 650 ° C. or lower, it is possible to suppress the entire carbon nanohorn aggregate from burning.
- it can be oxidized with nitric acid, sulfuric acid, hydrogen peroxide, or the like.
- nitric acid can be used in a temperature range from room temperature to 120 ° C. When the temperature during the oxidation treatment is 120 ° C.
- the fibrous carbon nanohorn aggregate 11 or the spherical carbon nanohorn aggregate 12 is not oxidized more than necessary.
- hydrogen peroxide can be used in the temperature range of room temperature to 100 ° C. More preferably, hydrogen peroxide is used in a temperature range of 40 ° C. or higher and 100 ° C. or lower.
- the oxidizing power of hydrogen peroxide efficiently acts on the fibrous carbon nanohorn aggregates 11 or the spherical carbon nanohorn aggregates 12 and can efficiently form openings. In the case of a liquid phase process, it is more effective to use light irradiation together.
- the catalyst (metal) contained in the production of the fibrous carbon nanohorn aggregate 11 or the spherical carbon nanohorn aggregate 12 is dissolved in nitric acid, sulfuric acid, and hydrochloric acid, it can be removed. From the viewpoint of ease of use, hydrochloric acid is suitable.
- the temperature at which the catalyst is dissolved can be appropriately selected. However, in order to sufficiently remove the catalyst, it is desirable to heat the fibrous carbon nanohorn aggregates 11 or the spherical carbon nanohorn aggregates 12 to 70 ° C. or higher to perform the oxidation treatment.
- a catalyst may be covered with a carbon film at the time of carbon nanohorn aggregate
- the obtained fibrous carbon nanohorn aggregate 11 or spherical carbon nanohorn aggregate 12 can be improved in crystallinity by heat treatment in an inert gas, hydrogen, or vacuum.
- a heat treatment temperature of 800 to 2000 ° C. can be used, but 1000 to 1500 ° C. is more preferable.
- the surface functional group formed by the oxidation treatment that forms the pores can also be removed by this heat treatment.
- the heat treatment temperature 150 to 2000 ° C. can be used.
- the heat treatment temperature is desirably 150 ° C. to 600 ° C.
- the removal of the C ⁇ O bond in the carbonyl group or the like as the surface functional group is preferably a heat treatment at 600 ° C. or higher.
- the surface functional group can be removed by reduction.
- the reduction can be performed in a gas atmosphere such as hydrogen or in a liquid atmosphere such as hydrazine.
- the blending amounts of the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 dispersed in the base material 13 are in terms of durability and conductivity. From 0.001 mass% to 60 mass%, more preferably from 0.05 mass% to 50 mass%. Moreover, the ratio of the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn 12 can be adjusted as appropriate. The proportion of the fibrous carbon nanohorn aggregate 11 is preferably 5% by mass or more and 80% or less, and more preferably 10% by mass or more and 70% by mass or less.
- the base material 13 is made of any one or a plurality of metals, oxides, conductive polymer compounds, resins, and elastomers, for example.
- the material of the base material 13 can be selected for convenience in accordance with physical properties required for the nanocarbon composite material 100, such as conductivity, durability, elastic modulus, mechanical strength, electromagnetic shielding, and flame retardancy.
- the base material 13 to be used is a metal
- a metal from the viewpoints of conductivity, durability, corrosion resistance, and thermal conductivity
- gold (Au) gold
- silver (Ag) platinum
- Pt platinum
- Base metal 13 is made of noble metal such as palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os), copper (Cu), aluminum (Al), tin (Sn), etc.
- noble metal such as palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os), copper (Cu), aluminum (Al), tin (Sn), etc.
- an alloy composition such as Sn—Ag, Sn—Cu, Sn—Ag—Cu, Sn—Pb, or Al—Si may be used for the base material 13. it can.
- the base material 13 is an oxide
- it can be selected as appropriate.
- Zr oxide, Al oxide, Ti oxide, V oxide, ITO (Indium Tin Oxide), etc. are used for the base material 13. It is preferable.
- the base material 13 to be used is a conductive polymer compound, for example, polythiophene, polyacetylene, polyaniline, or polypyrrole can be used for the base material 13.
- the base material 13 used is an elastomer, for example, a kind selected from nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene, urethane rubber, acrylic rubber, fluorine rubber, styrene-butadiene rubber, and silicon rubber
- a kind selected from nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene, urethane rubber, acrylic rubber, fluorine rubber, styrene-butadiene rubber, and silicon rubber The above can be used for the base material 13.
- the base material 13 to be used is a resin
- a resin for example, epoxy resin, polystyrene resin, silicone resin, acrylic resin, chloroprene resin, polysulfide resin, polyurethane resin, polyisobutyl resin
- resins fluorosilicone resins, polycarbonate resins, polyester resins, polyethylene resins, and polyamide resins
- FIG. 2 is a diagram showing a manufacturing flow of the nanocarbon composite material 100.
- an atmosphere setting step (S1) the inside of the container in which the catalyst-containing carbon target is arranged is placed in an inert gas, nitrogen gas, hydrogen, carbon monoxide gas, or a mixed atmosphere.
- the catalyst-containing carbon target is evaporated by laser ablation while rotating the catalyst-containing carbon target.
- Fibrous carbon nanohorn aggregates 11 and spherical carbon nanohorn aggregates 12 can be obtained in the process in which the evaporated carbon and the catalyst cool down.
- the target is irradiated with a laser in pulses or continuously. And when irradiation intensity becomes more than a threshold value, a target will convert energy. As a result, a plume is generated, and the product is mainly deposited on a substrate provided downstream of the target.
- the product may be generated in a space in the apparatus and recovered in a recovery chamber.
- a CO 2 laser For the laser ablation, a CO 2 laser, a YAG (Yttrium Aluminum Garnet) laser, or an excimer laser can be used. It is most appropriate to use a CO 2 laser that can easily increase the output.
- the CO 2 laser can be used at an output of 1 kW / cm 2 to 1000 kW / cm 2 , and laser ablation can be performed by continuous irradiation and pulse irradiation.
- ⁇ Continuous irradiation is preferable for the generation of carbon nanohorn aggregates.
- Laser light is condensed and irradiated by a ZnSe lens or the like.
- assembly 12 can be continuously synthesize
- the target rotation speed can be arbitrarily set, but 0.1 to 6 rpm is particularly preferable. On the other hand, if the target rotation speed is slower than 0.1 rpm, the target is easily graphitized, which is not preferable. Moreover, if the target rotation speed is faster than 6 rpm, amorphous carbon increases, which is not preferable.
- the laser output is preferably 15 kW / cm 2 or more, and 30 to 300 kW / cm 2 is most effective.
- the target does not evaporate and it is difficult to synthesize the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12.
- the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 can be synthesized, but this is not appropriate because the ratio of amorphous carbon increases.
- the pressure in the chamber can be used at 13332.2 hPa (10000 Torr) or less. However, the closer the pressure is to vacuum, the easier it is to produce carbon nanotubes, and the carbon nanohorn aggregates cannot be obtained.
- the irradiation area can also be controlled by the laser output and the degree of light condensing by the lens.
- the irradiation area can be 0.01 cm 2 to 1 cm 2 .
- the concentration of the catalyst can be appropriately selected, but is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass with respect to carbon. If the concentration of the catalyst is less than 0.1% by mass, only spherical shapes can be obtained, which is not desirable. Moreover, since the target cost will increase when the concentration of the catalyst exceeds 10% by mass, it is not preferable.
- a part of the carbon skeleton of the fibrous carbon nanohorn and the carbon nanohorn aggregate may be substituted with a catalytic metal element or the like.
- the temperature inside the container can be set arbitrarily.
- the temperature in the container is preferably set to 0 to 100 ° C. Even more preferably, setting the temperature in the container to room temperature is suitable for mass synthesis and cost reduction.
- nitrogen gas, inert gas, hydrogen, carbon monoxide, or the like is introduced alone or in a mixed manner to achieve the above atmosphere. These gases circulate in the container. Therefore, the generated substance can be recovered by this gas flow.
- nitrogen gas is used as the atmosphere, part of the carbon skeleton of the fibrous carbon nanohorn and the carbon nanohorn aggregate may be substituted with a nitrogen atom or the like.
- it may be a closed atmosphere with the introduced gas.
- An arbitrary amount of the atmospheric gas flow rate can be used, but a range of 0.5 L / min to 100 L / min is preferable as the atmospheric gas flow rate.
- the gas flow rate control step (S3) the gas flow rate is controlled to be constant in the process of evaporating the catalyst-containing carbon target. That is, in the process of evaporating the target, the gas flow rate is controlled to be constant.
- the gas flow rate can be kept constant by combining the supply gas flow rate and the exhaust gas flow rate.
- the gas flow rate control step (S3) is performed near normal pressure, the gas flow rate can be controlled to be constant by extruding and exhausting the gas in the container with the supply gas.
- a carbon nanohorn aggregate obtained through a process including an atmosphere setting step (S1), an evaporation step (S2) and a gas flow rate control step (S3) is mixed with the base material.
- assembly in this mixing process (S4) should just contain the fibrous carbon nanohorn aggregate
- the manufacturing method of the nanocarbon composite material 100 has been described above.
- Example 1 A carbon target containing 1% by mass of iron in a nitrogen atmosphere was subjected to CO 2 laser ablation to prepare a fibrous carbon nanohorn aggregate 11 and a spherical carbon nanohorn aggregate 12 as Sample 1.
- FIG. 3 is a scanning electron micrograph of the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 produced according to the present invention, and is a scanning electron micrograph of Sample 1.
- the fibrous substance has a diameter of about 30 to 100 nm and a length of several ⁇ m to several tens of ⁇ m. Most of the spherical substances have a substantially uniform size in a diameter range of about 30 to 200 nm.
- FIG. 4 is a transmission electron micrograph of the fibrous carbon nanohorn aggregate 11 produced according to the present invention.
- FIG. 5 is a transmission electron micrograph of the spherical carbon nanohorn assembly 12 produced according to the present invention. That is, FIG. 4 and FIG. 5 are transmission electron micrographs of the product contained in Sample 1.
- Example 3 Sample 1 prepared in Example 1 was adjusted to 10% of the total in polycarbonate resin, and this was used as composite material 1A. Bisphenol A type polycarbonate was used as the polycarbonate resin.
- composite material 2A a composite material of fibrous carbon nanohorn aggregates 11
- composite material 3A a composite material of only spherical carbon nanohorn aggregates 12
- composite material 4A A composite material was prepared.
- FIG. 6 is a diagram showing the conductivity and tensile strength of the nanocarbon composite material (composite material 1A) and the comparative example (composite material 2A, composite material 3A, composite material 4A) in the embodiment of the present invention.
- the conductivity is indicated by resistivity, and the smaller the value ( ⁇ ⁇ cm), the better.
- the conductivity and tensile strength of the composite material 1A are comprehensively superior to the composite materials 2A, 3A, and 4A. That is, by using both the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12, it can be seen that the conductivity and tensile strength are greatly improved as compared with carbon black or the like that has been generally used. It was.
- the fibrous structure (composite material 2A) and the spherical structure (composite material 3A) were both superior in both conductivity and tensile strength as compared with the carbon black structure (composite material 4A).
- Example 4 Sample 1 prepared in Example 1 was ultrasonically dispersed in methyl isobutyl ketone (MIBK) and mixed with a fluororubber solution and dried to obtain a composite material (referred to as composite material 1B).
- MIBK methyl isobutyl ketone
- composite material 2B a composite material including only fibrous carbon nanohorn aggregates 11
- composite material 3B a composite material including only spherical carbon nanohorn aggregates 12
- composite material 4B a composite material including only carbon black.
- FIG. 7 is a diagram showing the electrical conductivity and tensile strength of the nanocarbon composite material (composite material 1B) and comparative examples (composite material 2B, composite material 3B, composite material 4B) in the embodiment of the present invention.
- the conductivity and tensile strength of the composite material 1B are comprehensively superior to the composite materials 2B, 3B, and 4B. That is, by using both the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12, it can be seen that the conductivity and tensile strength are greatly improved as compared with carbon black or the like that has been generally used. It was. Further, both the fibrous structure (composite material 2B) and the spherical structure (composite material 3B) were superior in both conductivity and tensile strength compared to the carbon black structure (composite material 4B).
- the fibrous structure (composite material 2B) was superior in properties, particularly in terms of tensile strength, compared to the spherical structure (composite material 3B).
- Example 5 Sample 1 prepared in Example 1 and conductive particles that are silver particles were mixed by a three-roll mill to prepare a conductive paste (referred to as paste 1C). At this time, the silver particles were adjusted to 95%, the epoxy resin to 4%, and the sample 1 to 1%. After the paste 1C was cured at 150 ° C., the conductivity was evaluated.
- paste 2C a paste of fibrous carbon nanohorn aggregates 11
- paste 3C a paste of only spherical carbon nanohorn aggregates 12
- paste 4C carbon black only A paste
- FIG. 8 is a diagram showing the electrical conductivity of the electrical paste made of the nanocarbon composite material (sample 1) and the comparative examples (paste 2C, paste 3C, paste 4C) in the embodiment of the present invention. Further, although not shown in FIG. 8, a silver paste containing no carbon material was also produced. The conductivity of this silver paste was 9.0 ⁇ 10 ⁇ 5 ⁇ ⁇ cm.
- the conductivity of the paste 1C is comprehensively superior to the pastes 2C, 3C, and 4C. That is, it has been found that the use of both the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 significantly improves the conductivity compared to carbon black or the like that has been generally used. Further, both the fibrous structure (paste 2C) and the spherical structure (paste 3C) were superior in conductivity compared to the carbon black structure (paste 4C).
- Sample 1 produced in Example 1 was mixed with Al powder as a base material so as to be 20% of the whole. The obtained sample was sintered under the condition at 560 ° C. to produce a composite material 1D. At that time, the pressure was increased at 30 MPa.
- composite material 2D a composite material only of fibrous carbon nanohorn aggregates 11
- composite material 3D a composite material only of spherical carbon nanohorn aggregates 12
- composite material 4D A composite material only of carbon black
- FIG. 9 is a diagram showing the thermal conductivity of the nanocarbon composite material (composite material 1D) and the comparative example (composite material 2D, composite material 3D, composite material 4D) in the embodiment of the present invention.
- the thermal conductivity of the sintered body of simple aluminum produced under the same conditions was 200 W / mK. Therefore, all of the composite materials 1D to 4D have improved thermal conductivity as compared with the sintered body of aluminum alone.
- the thermal conductivity of the composite material 1D is superior to the composite materials 2D, 3D, and 4D. That is, it has been found that the use of both the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 greatly improves the thermal conductivity compared to carbon black or the like that has been generally used. Further, both the fibrous structure (composite material 2D) and the spherical structure (composite material 3D) were superior in thermal conductivity compared to the carbon black structure (composite material 4D). Furthermore, the fibrous structure (composite material 2D) was superior in thermal conductivity to the spherical structure (composite material 3D).
- Example 7 A fibrous carbon nanohorn aggregate and a spherical carbon nanohorn aggregate were prepared in the same manner as Sample 1 of Example 1 except that a carbon target containing 5 mass% of iron was used. When the obtained product was observed by TEM (Transmission Electron Microscope) and SEM (Scanning Electron Microscope), it was confirmed that both fibrous carbon nanohorn aggregates and spherical carbon nanohorn aggregates were produced. Both carbon nanohorn aggregates included seed type, bud type, dahlia type, and petal-dahlia type. The ratio between the fibrous structure and the spherical structure was slightly higher than that of the sample 1 of Example 1.
- Example 8 Under a nitrogen atmosphere, a carbon target containing 5% by mass of iron was subjected to CO 2 laser ablation to produce a fibrous carbon nanohorn aggregate and a spherical carbon nanohorn aggregate. At this time, the target was rotated at 2 rpm. The energy density of the CO 2 laser was continuously irradiated at 150 kW / cm 2 , and the chamber temperature was room temperature. In the chamber, the gas flow rate was adjusted to 10 L / min. The pressure was controlled at 933.254 to 1266.559 hPa (700 to 950 Torr). When the obtained product was subjected to TEM observation and SEM observation, it was confirmed that both fibrous carbon nanohorn aggregates and spherical carbon nanohorn aggregates were produced.
- Both carbon nanohorn aggregates included seed type, bud type, dahlia type, and petal-dahlia type, but there were more dahlia type and petal-dahlia type than others. Further, the ratio between the fibrous structure and the spherical structure was slightly higher than that of the sample 1 of Example 1.
- the nanocarbon composite material 100 is formed by dispersing the fibrous carbon nanohorn aggregate 11 in which a plurality of single-walled carbon nanohorns are connected in a fibrous form in the base material 13. .
- each of the plurality of single-walled carbon nanohorns is connected in a one-dimensional direction in a fibrous manner with the tips gathering radially outward.
- the fibrous carbon nanohorn aggregate 11 forms a better conductive path than the conventional spherical carbon nanohorn aggregate, and has excellent conductivity.
- the fibrous carbon nanohorn aggregate 11 has a higher dispersibility than a carbon material having a normal needle-like structure. For this reason, when the fibrous carbon nanohorn aggregate 11 is dispersed (highly dispersed) in the base material 13 at a high ratio, a nanocarbon composite material excellent in imparting conductivity can be provided.
- the thermal conductivity is also improved by dispersing the fibrous carbon nanohorn in the base material and forming a conductive path. Moreover, since it has many contacts when fibrous carbon nanohorn aggregates adsorb
- the spherical single-layer carbon nanohorn aggregate 12 is further dispersed in the base material 13.
- the spherical carbon nanohorn aggregate 12 is highly dispersed in the base material 13 and is uniformly mixed with the fibrous carbon nanohorn aggregate 11 and the base material 13 having a large aspect ratio to prevent re-aggregation. Moreover, the spherical carbon nanohorn 12 and the fibrous carbon nanohorn 11 having high dispersibility do not aggregate in the base material and are adsorbed to each other. For this reason, the electron conductive path of the nanocarbon composite material 100 increases. Thereby, the nanocarbon composite material excellent in conductivity imparting can be obtained. In addition, each single-layer carbon nanohorn aggregate 11 of the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 is pointed outward.
- the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 have many contact points with each other and have high adhesion. By this effect, good electrical conductivity, thermal conductivity, resistance to structural changes, and durability are increased. For this reason, in addition to imparting conductivity, a nanocarbon composite material excellent in imparting thermal conductivity and mechanical strength can be obtained.
- the base material 13 is made of any one or more of metals, oxides, conductive polymer compounds, resins, and elastomers.
- the fibrous carbon nanohorn aggregate 11 and the spherical carbon nanohorn aggregate 12 having high dispersibility have high affinity with the base material 13 and can be combined. Therefore, the material of the base material 13 can be selected for convenience in accordance with physical properties required for the nanocarbon composite material 100 such as conductivity, durability, elastic modulus, mechanical strength, electromagnetic shielding, and flame retardancy. .
- the fibrous carbon nanohorn aggregate 11 has a diameter of 30 nm to 200 nm and a length of 1 ⁇ m to 100 ⁇ m.
- the single-walled carbon nanohorn has a diameter of 1 nm to 5 nm, a length of 30 nm to 100 nm, and a tip having a horn shape.
- the fibrous carbon nanohorn aggregate 11 includes at least one carbon nanohorn aggregate of a seed type, a bud type, a dahlia type, a petal dahlia type, and a petal type. Contains structure.
- the spherical carbon nanohorn aggregate 12 has a carbon nanohorn aggregate structure of at least one of a seed type, a bud type, a dahlia type, a petal dahlia type, and a petal type. Contains.
- a catalytic metal is incorporated into the fibrous carbon nanohorn aggregate 11.
- the catalytic metal is mainly taken into the spherical carbon nanohorn aggregate 12.
- the method for manufacturing the nanocarbon composite material 100 in the embodiment of the present invention includes an atmosphere setting step, an evaporation step, a gas flow rate control step, and a mixing step.
- the atmosphere setting step the inside of the container in which the catalyst-containing carbon target is arranged is placed in an inert gas, nitrogen gas, or mixed atmosphere.
- the evaporation step the catalyst-containing carbon target is evaporated by laser ablation while rotating the catalyst-containing carbon target.
- the gas flow rate control step the gas flow rate is controlled to be constant in the process of evaporating the catalyst-containing carbon target.
- fibrous carbon nanohorn aggregates 11 obtained by processing including an atmosphere setting step, an evaporation step, and a gas flow rate control step are mixed with base material 13.
- the fibrous carbon nanohorn aggregate 11 a plurality of single-layer carbon nanohorns are aggregated in a fibrous form.
- the manufacturing method of the nanocarbon composite material 100 in the manufacturing method of the nanocarbon composite material 100 according to the embodiment of the present invention, in the mixing process, in addition to the fibrous carbon nanohorn aggregate 11, a process including an atmosphere setting process, an evaporation process, and a gas flow rate control process is performed simultaneously.
- the obtained spherical single-layer carbon nanohorn aggregate 12 is mixed with the base material 13. Even with such a method of manufacturing the nanocarbon composite material 100, the same effects as those of the nanocarbon composite material 100 described above can be achieved.
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Abstract
Description
本発明者は、高導電性を発現するカーボンナノホーン集合体について鋭意検討した結果、導電性付与に優れた繊維状のカーボンナノホーン集合体を見出した(特願2015-52185)。
(実施例1)
窒素雰囲気下で、鉄を1質量%含有した炭素ターゲットをCO2レーザーアブレーションすることにより、繊維状カーボンナノホーン集合体11と球状カーボンナノホーン集合体12をサンプル1として作製した。
(実施例2)
図3は、本発明によって作製された繊維状カーボンナノホーン集合体11および球状カーボンナノホーン集合体12の走査型電子顕微鏡写真であって、サンプル1の走査型電子顕微鏡写真である。
(実施例3)
実施例1で作製されたサンプル1をポリカーボネート樹脂中に全体の10%になるように調整し、これを複合材1Aとした。ポリカーボネート樹脂には、ビスフェノールA型のポリカーボネートを用いた。
(実施例4)
実施例1で作製されたサンプル1をメチルイソブチルケトン(MIBK:(methyl isobutyl ketone)に超音波分散させ、フッ素ゴム溶液に混ぜ乾燥することで複合材料を得た(複合材1Bとする)。
(実施例5)
実施例1で作製されたサンプル1と、銀粒子である導電性粒子を三本ロールミルで混合し、導電性ペーストを作製した(ペースト1Cとする)。この時、銀粒子が95%、エポシキ樹脂が4%、サンプル1が1%になるように調整した。ペースト1Cを150℃で硬化させた後、導電性を評価した。
(実施例6)
実施例1で作製されたサンプル1を、全体の20%になるように母材であるAl粉末を混合した。得られた試料を560℃での条件下で焼結することで、複合材1Dを作製した。その際、圧力は30MPaで加圧した。
鉄を5質量%含有した炭素ターゲットを使用する以外は実施例1のサンプル1と同様にして、繊維状カーボンナノホーン集合体と球状カーボンナノホーン集合体を作製した。得られた生成物を、TEM(Transmission Electron Microscope)観察およびSEM(Scanning Electron Microscope)観察を行ったところ、繊維状カーボンナノホーン集合体と球状カーボンナノホーン集合体が両方作製されたことが確認できた。どちらのカーボンナノホーン集合体も種型、つぼみ型、ダリア型、ペタル-ダリア型が含まれていた。また繊維状構造と球状構造の比率は、実施例1のサンプル1より、僅かに多かった。
(実施例8)
窒素雰囲気下で、鉄を5質量%含有した炭素ターゲットをCO2レーザーアブレーションすることで、繊維状カーボンナノホーン集合体と球状カーボンナノホーン集合体を作製した。この時、ターゲットは2rpmで回転させた。CO2レーザーのエネルギー密度は、150kW/cm2で連続的に照射し、チャンバー温度は室温であった。チャンバー内は、ガス流量を10L/minになるように調整した。圧力は933.254~1266.559hPa(700~950Torr)に制御した。得られた生成物を、TEM観察およびSEM観察を行ったところ、繊維状カーボンナノホーン集合体と球状カーボンナノホーン集合体が両方作製されたことが確認できた。どちらのカーボンナノホーン集合体も種型、つぼみ型、ダリア型、ペタル-ダリア型が含まれていたが、ダリア型とペタル-ダリア型が他と比して多かった。また繊維状構造と球状構造の比率は、実施例1のサンプル1より僅かに多かった。
12 球状カーボンナノホーン集合体
13 母材
100 ナノ炭素複合材料
Claims (10)
- 複数の単層カーボンナノホーン集合体が繊維状に繋がっている繊維状カーボンナノホーン集合体が母材中に分散して形成されるナノ炭素複合材料。
- 前記繊維状カーボンナノホーン集合体に加えて、球状単層カーボンナノホーン集合体がさらに前記母材中に分散して形成されている請求項1に記載のナノ炭素複合材料。
- 前記母材は、金属、酸化物、導電性高分子化合物、樹脂、エラストマーのうち、いずれか1つまたは複数からなる請求項1または2に記載のナノ炭素複合材料。
- 前記繊維状カーボンナノホーン集合体は、直径が30nm~200nm、長さが1μm~100μmである請求項1~3のいずれか1項に記載のナノ炭素複合材料。
- 前記単層カーボンナノホーンは、直径が1nm~5nm、長さが30nm~100nmであり、先端がホーン状である請求項1~4のいずれか1項に記載のナノ炭素複合材料。
- 前記繊維状カーボンナノホーン集合体は、種型、つぼみ型、ダリア型、ペタルダリア型、ペタル型のうちの少なくとも1種類のカーボンナノホーン集合体が繊維状に繋がったものである請求項1~5のいずれか1項に記載のナノ炭素複合材料。
- 前記球状カーボンナノホーン集合体は、種型、つぼみ型、ダリア型、ペタルダリア型、ペタル型のうちの少なくとも1種類のカーボンナノホーン集合体を含有している請求項2~6のいずれか1項に記載のナノ炭素複合材料。
- 前記繊維状カーボンナノホーン集合体または前記球状カーボンナノホーン集合体の内部に触媒金属が取込まれている請求項1~7のいずれか1項に記載のナノ炭素複合材料。
- 触媒含有炭素ターゲットを配置した容器内を、不活性ガス、窒素ガス、または、混合雰囲気下にする雰囲気設定工程と、
前記触媒含有炭素ターゲットを回転させながらレーザーアブレーションにより、前記触媒含有炭素ターゲットを蒸発させる蒸発工程と、
前記触媒含有炭素ターゲットが蒸発する過程で、ガス流量を一定に制御するガス流量制御工程と、
前記雰囲気設定工程、前記蒸発工程および前記ガス流量制御工程を含む処理により得られる、複数の単層カーボンナノホーンが繊維状に繋がっている繊維状カーボンナノホーン集合体を、母材に混合する混合工程とを含むナノ炭素複合材料の製造方法。 - 前記混合工程では、前記繊維状カーボンナノホーン集合体に加えて、前記雰囲気設定工程、前記蒸発工程および前記ガス流量制御工程を含む処理により得られる球状単層カーボンナノホーン集合体を母材に混合する請求項9に記載のナノ炭素複合材料の製造方法。
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US20180162735A1 (en) | 2018-06-14 |
US10703633B2 (en) | 2020-07-07 |
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JPWO2016208170A1 (ja) | 2018-05-24 |
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