WO2017038413A1 - Procédé de fabrication d'un matériau composite et matériau composite - Google Patents

Procédé de fabrication d'un matériau composite et matériau composite Download PDF

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Publication number
WO2017038413A1
WO2017038413A1 PCT/JP2016/073508 JP2016073508W WO2017038413A1 WO 2017038413 A1 WO2017038413 A1 WO 2017038413A1 JP 2016073508 W JP2016073508 W JP 2016073508W WO 2017038413 A1 WO2017038413 A1 WO 2017038413A1
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Prior art keywords
composite material
fibrous carbon
dispersion
carbon nanostructure
plating
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PCT/JP2016/073508
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English (en)
Japanese (ja)
Inventor
新井　進
貢 上島
有信 堅田
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日本ゼオン株式会社
国立大学法人信州大学
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Application filed by 日本ゼオン株式会社, 国立大学法人信州大学 filed Critical 日本ゼオン株式会社
Priority to JP2017537702A priority Critical patent/JP7023112B2/ja
Priority to CN201680047089.4A priority patent/CN107923059A/zh
Publication of WO2017038413A1 publication Critical patent/WO2017038413A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the present invention relates to a method for producing a composite material and a composite material, and more particularly to a method for producing a composite material containing a metal and a fibrous carbon nanostructure, and a composite material obtained by the production method.
  • CNT carbon nanotubes
  • the metal and the fibrous carbon nanostructure have a large difference in specific gravity between the materials, and thus there is a problem in that the composite material is very difficult to prepare. Therefore, as a method for solving the above problem, for example, a technique has been proposed in which metal and CNT are combined well by mixing CNT into a plating solution and forming a plating film with the plating solution. (See Patent Document 1).
  • the fibrous carbon nanostructure is used in the plating solution. It is necessary to satisfactorily disperse the structure and suppress the formation of aggregates of fibrous carbon nanostructures in the obtained composite material.
  • an object of the present invention is to provide a method for producing a composite material having excellent physical properties by favorably compounding a metal and a fibrous carbon nanostructure. Moreover, an object of this invention is to provide the composite material manufactured using the said manufacturing method.
  • the present inventors have intensively studied to achieve the above object. And the present inventors surprisingly made metal and fibrous carbon nanostructures by immersing a carbon film formed by assembling fibrous carbon nanostructures into a film and immersing them in a plating solution. The present inventors have found that a composite material in which the body is well composited can be obtained, and the present invention has been completed.
  • the present invention aims to advantageously solve the above-described problems, and the method for producing a composite material of the present invention comprises plating a carbon film containing fibrous carbon nanostructures using a plating solution.
  • the method includes a step of performing processing. In this way, when a carbon film containing fibrous carbon nanostructures is plated, a metal is deposited inside the carbon film to produce a composite material in which the metal and fibrous carbon nanostructures are well compounded. be able to.
  • Such a composite material is excellent in physical properties such as conductivity and thermal conductivity.
  • the manufacturing method of the composite material of the present invention is a step of preparing the carbon film by removing the solvent from the dispersion containing the fibrous carbon nanostructure and the solvent prior to the step of performing the plating treatment. It is preferable to contain.
  • a carbon film obtained by removing a solvent from a dispersion liquid in which fibrous carbon nanostructures are dispersed in a solvent tends to have a low density. Therefore, the plating solution easily penetrates into the carbon film in the plating process, and the metal is easily deposited inside the carbon film. Therefore, the metal and the fibrous carbon nanostructure can be more favorably combined, and the physical properties of the composite material can be further improved.
  • the density of the carbon film is 0.01 g / cm 3 or more 1.8 g / cm 3 or less. If a carbon film having a density within the above-described range is used, the metal and the fibrous carbon nanostructure can be more satisfactorily combined while ensuring the strength of the obtained composite material.
  • the said plating solution contains a nonionic surfactant.
  • a plating solution containing a nonionic surfactant easily penetrates into the carbon film and facilitates deposition of metal inside the carbon film. Therefore, the metal and the fibrous carbon nanostructure can be more satisfactorily combined, and the physical properties of the composite material can be further enhanced.
  • the nonionic surfactant is preferably a polyether surfactant. If a plating solution containing a polyether-based surfactant is used, the metal and the fibrous carbon nanostructure can be combined more satisfactorily.
  • the said fibrous carbon nanostructure contains a carbon nanotube. If a fibrous carbon nanostructure containing carbon nanotubes is used, the physical properties of the composite material can be further enhanced. In addition, it is preferable that the specific surface area of the fibrous carbon nanostructure containing the said carbon nanotube is 600 m ⁇ 2 > / g or more. If a fibrous carbon nanostructure having a specific surface area of 600 m 2 / g or more is used, the physical properties of the composite material can be further enhanced.
  • the present invention aims to advantageously solve the above-mentioned problems, and the composite material of the present invention is characterized by being manufactured using any one of the above-described composite material manufacturing methods. If any one of the composite material manufacturing methods described above is used, a composite material having excellent physical properties can be obtained.
  • a metal and a fibrous carbon nanostructure can be favorably compounded to produce a composite material having excellent physical properties.
  • a composite material having excellent physical properties can be obtained.
  • Example 2 is a cross-sectional photograph of the composite material of Example 1 taken with a field emission scanning electron microscope. It is a cross-sectional photograph of the composite material of Example 2 photographed with a field emission scanning electron microscope.
  • the method for producing a composite material of the present invention can be used when producing a composite material in which a metal and a fibrous carbon nanostructure are combined.
  • the composite material of this invention manufactured using the manufacturing method of the composite material of this invention is excellent in physical properties, such as electroconductivity and heat conductivity.
  • the manufacturing method of the composite material of this invention includes the process (plating process process) which performs a plating process using the plating solution on the carbon film containing a fibrous carbon nanostructure. And in the manufacturing method of the composite material of this invention, a metal and fibrous carbon nanostructure are compounded favorably by depositing the metal derived from a plating solution inside a carbon film, and excellent electrical conductivity, thermal conductivity, etc. A composite material exhibiting the physical properties of can be obtained.
  • the carbon film is composed of an aggregate of fibrous carbon nanostructures obtained by assembling a plurality of fibrous carbon nanostructures into a film shape.
  • the process of obtaining a carbon film by assembling a plurality of fibrous carbon nanostructures into a film form is not particularly limited.
  • the following processes (1) Step of forming a film by removing a solvent from a dispersion containing a plurality of fibrous carbon nanostructures and a solvent (2) Fibrous carbon obtained by growing in a substantially vertical direction on a substrate A step of forming a film by allowing the aggregate of nanostructures to fall on a substrate and then compressing as necessary is mentioned.
  • the step (1) is preferable.
  • the carbon film obtained through the step (1) tends to have a low density, and the plating solution easily permeates in the plating process. Therefore, the metal deposition inside the carbon film is facilitated, the metal and the fibrous carbon nanostructure are more complexed, and the physical properties of the composite material can be further improved.
  • the carbon film preparation step will be described in detail by taking the step (1) as an example.
  • the dispersion used for the preparation of the carbon film is not particularly limited, and a dispersion obtained by dispersing an aggregate of fibrous carbon nanostructures in a solvent using a known dispersion treatment method can be used.
  • a dispersion containing a fibrous carbon nanostructure and a solvent and optionally further containing an additive for dispersion such as a dispersant can be used.
  • the fibrous carbon nanostructure is not particularly limited, and for example, a fibrous carbon nanostructure having an aspect ratio exceeding 10 can be used.
  • a fibrous carbon nanostructure carbon nanotubes, vapor-grown carbon fibers, carbon fibers obtained by carbonizing organic fibers, and cut products thereof can be used. These may be used individually by 1 type and may use 2 or more types together.
  • the “aspect ratio” can be obtained by measuring the diameter (outer diameter) and length of 100 fibrous carbon nanostructures randomly selected using a transmission electron microscope.
  • the fibrous carbon nanostructure it is more preferable to use a fibrous carbon nanostructure including carbon nanotubes. This is because the physical properties of the composite material can be further improved by using a fibrous carbon nanostructure containing carbon nanotubes.
  • the fibrous carbon nanostructure containing CNT may be composed of only CNT, or may be a mixture of CNT and fibrous carbon nanostructure other than CNT.
  • the CNT in the fibrous carbon nanostructure is not particularly limited, and single-walled carbon nanotubes and / or multi-walled carbon nanotubes can be used. Preferably, it is a single-walled carbon nanotube. This is because the use of single-walled carbon nanotubes can further improve the physical properties of the composite material as compared to the case of using multi-walled carbon nanotubes.
  • the average diameter (Av) of the fibrous carbon nanostructure containing CNTs is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 15 nm or less, and preferably 10 nm or less. It is more preferable. If the average diameter (Av) of the fibrous carbon nanostructure is 0.5 nm or more, a sufficient space for the metal to deposit between the plurality of fibrous carbon nanostructures in the carbon film is ensured. A composite material in which the fibrous carbon nanostructures are better composited can be obtained. Moreover, if the average diameter (Av) of the fibrous carbon nanostructure is 15 nm or less, the physical properties of the composite material can be further improved.
  • the “average diameter (Av) of fibrous carbon nanostructures” is obtained by measuring the diameter (outer diameter) of 100 fibrous carbon nanostructures selected at random using a transmission electron microscope. Can do. And the average diameter (Av) of the fibrous carbon nanostructure containing CNT may be adjusted by changing the manufacturing method and manufacturing conditions of the fibrous carbon nanostructure containing CNT, or obtained by a different manufacturing method. You may adjust by combining multiple types of fibrous carbon nanostructure containing the produced CNT.
  • the BET specific surface area of the fibrous carbon nanostructure containing CNTs is preferably 600 m 2 / g or more, more preferably 800 m 2 / g or more, and preferably 2500 m 2 / g or less. More preferably, it is 1200 m 2 / g or less. If the BET specific surface area of the fibrous carbon nanostructure containing CNTs is 600 m 2 / g or more, the physical properties of the composite material can be further improved.
  • the BET specific surface area of the fibrous carbon nanostructure containing CNTs is 2500 m 2 / g or less, excessive crowding of the fibrous carbon nanostructure in the carbon film and the composite material is suppressed, and the metal And the fibrous carbon nanostructure can be combined more satisfactorily.
  • the “BET specific surface area” refers to a nitrogen adsorption specific surface area measured using the BET method.
  • the fibrous carbon nanostructure containing CNT is an aggregate oriented in a direction substantially perpendicular to the base material on a base material having a catalyst layer for carbon nanotube growth on the surface according to the super growth method described later.
  • the mass density of the fibrous carbon nanostructure as the aggregate is preferably 0.002 g / cm 3 or more and 0.2 g / cm 3 or less. If the mass density is 0.2 g / cm 3 or less, the bonding between the fibrous carbon nanostructures becomes weak, so that the fibrous carbon nanostructures can be uniformly dispersed. Further, if the mass density is 0.002 g / cm 3 or more, the integrity of the fibrous carbon nanostructure can be improved, and the handling can be facilitated because it can be prevented from being broken.
  • the fibrous carbon nanostructure containing CNTs has a shape in which the t-plot obtained from the adsorption isotherm is convex upward.
  • the opening process of CNT is not performed and the t-plot shows a convex shape upward.
  • the “t-plot” is obtained by converting the relative pressure into the average thickness t (nm) of the nitrogen gas adsorption layer in the adsorption isotherm of the fibrous carbon nanostructure measured by the nitrogen gas adsorption method. Can do.
  • the average thickness t of the nitrogen gas adsorption layer is plotted against the relative pressure P / P0, and the average thickness t of the nitrogen gas adsorption layer corresponding to the relative pressure is obtained from the known standard isotherm to perform the above conversion.
  • a t-plot of the fibrous carbon nanostructure containing CNT is obtained (de-boer et al. T-plot method).
  • the growth of the nitrogen gas adsorption layer is classified into the following processes (1) to (3). Then, the inclination of the t-plot is changed by the following processes (1) to (3).
  • the t-plot showing an upwardly convex shape is located on a straight line passing through the origin in a region where the average thickness t of the nitrogen gas adsorption layer is small, whereas when t becomes large, the plot becomes the straight line. The position will be shifted downward.
  • the fibrous carbon nanostructure having such a t-plot shape has a large ratio of the internal specific surface area to the total specific surface area of the fibrous carbon nanostructure, and there are many carbon nanostructures constituting the fibrous carbon nanostructure. It is shown that the opening is formed.
  • the inflection point of the t-plot of the fibrous carbon nanostructure containing CNT is preferably in a range satisfying 0.2 ⁇ t (nm) ⁇ 1.5, and 0.45 ⁇ t (nm) ⁇ More preferably, it is in the range of 1.5, and more preferably in the range of 0.55 ⁇ t (nm) ⁇ 1.0.
  • the “position of the bending point” is an intersection of the approximate line A in the process (1) described above and the approximate line B in the process (3) described above.
  • the fibrous carbon nanostructure containing CNTs preferably has a ratio (S2 / S1) of the internal specific surface area S2 to the total specific surface area S1 obtained from the t-plot of 0.05 or more and 0.30 or less.
  • the total specific surface area S1 and the internal specific surface area S2 of the fibrous carbon nanostructure containing CNTs are not particularly limited, but individually, S1 is preferably 600 m 2 / g or more and 1400 m 2 / g or less. 800 m 2 / g or more and 1200 m 2 / g or less is more preferable.
  • S2 is preferably 30 m 2 / g or more and 540 m 2 / g or less.
  • the total specific surface area S1 and the internal specific surface area S2 of the fibrous carbon nanostructure containing CNT can be determined from the t-plot. Specifically, first, the total specific surface area S1 can be obtained from the slope of the approximate line in the process (1), and the external specific surface area S3 can be obtained from the slope of the approximate line in the process (3). Then, the internal specific surface area S2 can be calculated by subtracting the external specific surface area S3 from the total specific surface area S1.
  • the fibrous carbon nanostructure containing CNTs having the above-described properties is obtained by, for example, supplying a raw material compound and a carrier gas onto a substrate having a catalyst layer for producing carbon nanotubes on the surface,
  • a method supergrowth method; which dramatically improves the catalytic activity of the catalyst layer by allowing a small amount of an oxidizing agent (catalyst activation material) to be present in the system.
  • an oxidizing agent catalyst activation material
  • the fibrous carbon nanostructure containing CNT manufactured by the super growth method may be comprised only from SGCNT, and may be comprised from SGCNT and a non-cylindrical carbon nanostructure.
  • the fibrous carbon nanostructure containing CNT includes a single-layer or multi-layered flat cylindrical carbon nanostructure (hereinafter referred to as “ It may be referred to as “graphene nanotape (GNT)”.
  • GNT is presumed to be a substance in which a tape-like portion in which inner walls are close to each other or bonded is formed over the entire length from the synthesis, and a carbon six-membered ring network is formed in a flat cylindrical shape.
  • the And the shape of GNT is a flat cylindrical shape, and the presence of a tape-like part in which the inner walls are close to each other or bonded is present in GNT.
  • GNT and fullerene (C60) are sealed in a quartz tube.
  • fullerene insertion GNT obtained by heat treatment (fullerene insertion treatment) under reduced pressure is observed with a transmission electron microscope, it is confirmed that there is a portion (tape-like portion) in which fullerene is not inserted in the GNT. Can do.
  • the shape of GNT is a shape which has a tape-shaped part in the center part of the width direction, and the shape of the cross section orthogonal to the extending direction (axial direction) is the cross-sectional length in the vicinity of both ends in the cross-sectional longitudinal direction. It is more preferable that the maximum dimension in the direction orthogonal to the direction is larger than the maximum dimension in the direction orthogonal to the longitudinal direction of the cross section in the vicinity of the central portion in the longitudinal direction of the cross section. preferable.
  • “near the central portion in the longitudinal direction of the cross section” means the longitudinal width of the cross section from the longitudinal center line of the cross section (a straight line passing through the longitudinal center of the cross section and perpendicular to the longitudinal direction line).
  • the “near the end in the longitudinal direction of the cross section” means the area outside the longitudinal direction of “near the center in the longitudinal direction of the cross section”.
  • a carbon nanostructure containing GNT as a non-cylindrical carbon nanostructure is a base material having a catalyst layer on the surface when a CNT is synthesized by a super-growth method using a base material having a catalyst layer on the surface.
  • Catalyst base material can be obtained by a predetermined method.
  • the carbon nanostructure containing GNT is obtained by applying a coating liquid A containing an aluminum compound on a substrate, drying the applied coating liquid A, and then forming an aluminum thin film (catalyst supporting layer) on the substrate.
  • the coating liquid B containing the iron compound is applied, and the applied coating liquid B is dried at a temperature of 50 ° C. or less to form the iron thin film (catalyst layer) on the aluminum thin film. It can be obtained by synthesizing CNTs by the super-growth method using the catalyst substrate obtained by forming.
  • the solvent of the dispersion is not particularly limited.
  • Amides polar organic solvents such as ethers, N, N-dimethylformamide, N-methylpyrrolidone, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, orthodichlorobenzene, paradichlorobenzene And the like. These may be used alone or in combination of two or more.
  • the additive for dispersion that is arbitrarily blended in the dispersion is not particularly limited, and examples thereof include additives generally used for preparing dispersions such as dispersants.
  • the dispersant It is preferable that the amount of the additive for dispersion such as is small.
  • the dispersant used for preparing the dispersion is not particularly limited as long as it can disperse the fibrous carbon nanostructure and can be dissolved in the solvent described above. Natural polymers can be used.
  • examples of the surfactant include sodium dodecylsulfonate, sodium deoxycholate, sodium cholate, sodium dodecylbenzenesulfonate, and the like.
  • examples of the synthetic polymer include polyether diol, polyester diol, polycarbonate diol, polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, acetal group-modified polyvinyl alcohol, butyral group-modified polyvinyl alcohol, and silanol group-modified.
  • Polyvinyl alcohol ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer resin, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acrylic resin, epoxy resin, modified epoxy resin, phenoxy resin, modified phenoxy system Resin, phenoxy ether resin, phenoxy ester resin, fluorine resin, melamine resin, alkyd resin, phenol resin, Polyacrylamide, polyacrylic acid, polystyrene sulfonic acid, polyethylene glycol, and polyvinylpyrrolidone.
  • examples of natural polymers include polysaccharides such as starch, pullulan, dextran, dextrin, guar gum, xanthan gum, amylose, amylopectin, alginic acid, gum arabic, carrageenan, chondroitin sulfate, hyaluronic acid, curdlan, chitin, chitosan, Examples thereof include cellulose and salts or derivatives thereof. And these dispersing agents can be used 1 type or in mixture of 2 or more types.
  • the aggregate of 1 mm or more is not visually confirmed in the dispersion liquid.
  • the fibrous carbon nanostructures in the dispersion are dispersed at a level at which the median diameter (average particle diameter) measured by a particle size distribution meter is 150 ⁇ m or less. If the fibrous carbon nanostructure is well dispersed in the dispersion, the density unevenness of the carbon film obtained by removing the solvent is suppressed. In addition, the plating solution easily penetrates uniformly into the carbon film with less density unevenness, and the metal and the fibrous carbon nanostructure can be combined more satisfactorily. As a result, the physical properties of the composite material are further improved.
  • the solid content concentration of the dispersion is preferably 0.001% by mass or more and 20% by mass or less, although it depends on the type of the fibrous carbon nanostructure.
  • the solid content concentration is less than 0.001% by mass, the amount of the carbon film obtained by removing the solvent decreases, and the production efficiency may not be sufficiently increased.
  • solid content concentration exceeds 20 mass%, while there exists a possibility that the dispersibility of the fibrous carbon nanostructure in a dispersion liquid may fall, the viscosity of a dispersion liquid will increase and fluidity
  • the dispersion As the dispersion, a commercially available dispersion obtained by dispersing an aggregate of fibrous carbon nanostructures in a solvent may be used. However, the dispersion was prepared by performing the dispersion preparation step before the carbon film preparation step. It is preferable to use a dispersion. Among them, from the viewpoint of using a dispersion in which fibrous carbon nanostructures are well dispersed in a solvent and obtaining a composite material having excellent physical properties by suppressing unevenness in the density of the carbon film, the dispersion may be used in the solvent. It is more preferable to use a dispersion obtained by subjecting a coarse dispersion formed by adding fibrous carbon nanostructures to a dispersion treatment that provides a cavitation effect or a crushing effect.
  • a coarse dispersion obtained by adding the above-described fibrous carbon nanostructure and any additive for dispersion to the solvent described above is a dispersion capable of obtaining a cavitation effect described in detail below. It is preferable to use a dispersion obtained by subjecting to a dispersion treatment capable of obtaining a treatment or crushing effect.
  • the dispersion treatment that provides a cavitation effect is a dispersion method that uses a shock wave that is generated when a vacuum bubble generated in water bursts when high energy is applied to a liquid.
  • the fibrous carbon nanostructure can be favorably dispersed.
  • dispersion treatment that provides a cavitation effect
  • dispersion treatment using ultrasonic waves dispersion treatment using a jet mill
  • dispersion treatment using high shear stirring Only one of these distributed processes may be performed, or a plurality of distributed processes may be combined. More specifically, for example, an ultrasonic homogenizer, a jet mill, and a high shear stirring device are preferably used. These devices may be conventionally known devices.
  • the coarse dispersion may be irradiated with ultrasonic waves using the ultrasonic homogenizer.
  • the irradiation time may be appropriately set depending on the amount of the fibrous carbon nanostructure and the like, for example, preferably 3 minutes or more, more preferably 30 minutes or more, and preferably 5 hours or less, more preferably 2 hours or less.
  • the output is preferably 20 W or more and 500 W or less, more preferably 100 W or more and 500 W or less, and the temperature is preferably 15 ° C. or more and 50 ° C. or less.
  • the number of treatments may be appropriately set depending on the amount of the fibrous carbon nanostructure and the like, for example, preferably 2 times or more, preferably 100 times or less, and more preferably 50 times or less.
  • the pressure is preferably 20 MPa or more and 250 MPa or less
  • the temperature is preferably 15 ° C. or more and 50 ° C. or less.
  • stirring and shearing may be applied to the coarse dispersion with a high shear stirring device.
  • the operation time time during which the machine is rotating
  • the peripheral speed is preferably 5 m / second or more and 50 m / second or less
  • the temperature is preferably 15 ° C. or more and 50 ° C. or less.
  • the dispersion treatment for obtaining the above-described cavitation effect it is more preferable to perform the dispersion treatment for obtaining the above-described cavitation effect at a temperature of 50 ° C. or lower. This is because a change in concentration due to the volatilization of the solvent is suppressed.
  • the dispersion treatment that provides the crushing effect can uniformly disperse the fibrous carbon nanostructures in the solvent, as well as the fibrous carbon due to the shock wave when the bubbles disappear, compared to the dispersion treatment that provides the cavitation effect described above. This is advantageous in that damage to the nanostructure can be suppressed.
  • the fibrous carbon nanostructure can be uniformly dispersed in the solvent while suppressing the generation of bubbles.
  • the back pressure applied to the coarse dispersion may be reduced to atmospheric pressure all at once, but is preferably reduced in multiple stages.
  • a dispersion system having a disperser having the following structure may be used.
  • the disperser has a disperser orifice having an inner diameter d1, a dispersion space having an inner diameter d2, and a terminal portion having an inner diameter d3 from the inflow side to the outflow side of the coarse dispersion liquid (where d2>d3> d1)).
  • the inflowing high-pressure for example, 10 to 400 MPa, preferably 50 to 250 MPa
  • coarse dispersion passes through the disperser orifice and becomes a high flow rate fluid with a decrease in pressure.
  • the high-velocity coarse dispersion liquid flowing into the dispersion space flows at high speed in the dispersion space and receives a shearing force at that time.
  • the flow rate of the coarse dispersion decreases, and the fibrous carbon nanostructure is well dispersed.
  • a fluid having a pressure (back pressure) lower than the pressure of the inflowing coarse dispersion liquid flows out from the terminal portion as the dispersion liquid of the fibrous carbon nanostructure.
  • the back pressure of the coarse dispersion can be applied to the coarse dispersion by applying a load to the flow of the coarse dispersion.
  • a rough pressure can be obtained by disposing a multistage step-down device downstream of the disperser.
  • a desired back pressure can be applied to the dispersion. Then, by reducing the back pressure of the coarse dispersion in multiple stages using a multistage pressure reducer, bubbles are generated in the dispersion when the dispersion of the fibrous carbon nanostructure is finally released to atmospheric pressure. Can be suppressed.
  • the disperser may include a heat exchanger for cooling the coarse dispersion and a cooling liquid supply mechanism. This is because the generation of bubbles in the coarse dispersion can be further suppressed by cooling the coarse dispersion that has been heated to a high temperature by applying a shearing force with the disperser. In addition, it can suppress that a bubble generate
  • the occurrence of cavitation can be suppressed, so damage to the fibrous carbon nanostructure caused by cavitation that is sometimes a concern, especially when the bubbles disappear. Damage to the fibrous carbon nanostructure due to the shock wave can be suppressed.
  • distribution process from which a crushing effect is acquired can be implemented by controlling a dispersion
  • the method for removing the solvent from the dispersion is not particularly limited, and a known solvent removing method such as drying or filtration can be used. Among these, from the viewpoint of efficiently removing the solvent, it is preferable to use reduced-pressure drying, vacuum drying or filtration as the solvent removal method. Furthermore, from the viewpoint of removing the solvent easily and quickly, the solvent removal method is preferably filtration, and more preferably vacuum filtration. If the solvent is removed quickly and efficiently, the once-dispersed fibrous carbon nanostructures can be prevented from aggregating again, and density unevenness of the resulting carbon film can be suppressed. Here, it is not necessary to completely remove the solvent in the dispersion liquid. If the fibrous carbon nanostructure remaining after the removal of the solvent can be handled as an aggregate (carbon film), some solvent remains. There is no problem even if you do.
  • the thickness of the obtained carbon film is preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, more preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less. Preferably, it is 60 micrometers or less.
  • the thickness of the carbon film is 2 ⁇ m or more, the strength of the resulting composite can be ensured.
  • the thickness of the carbon film is 200 ⁇ m or less, the plating solution can easily penetrate to the central portion in the thickness direction of the carbon film, and a composite material in which the metal and the fibrous carbon nanostructure are more preferably combined can be obtained. it can.
  • the density of the carbon film is preferably 0.01 g / cm 3 or more, more preferably 0.1 g / cm 3 or more, still more preferably 0.5 g / cm 3 or more, 1.8 g / cm 3 or less, more preferably 1.5 g / cm 3 or less, and still more preferably 1.2 g / cm 3 or less. If the density of the carbon film is 0.01 g / cm 3 or more, the strength of the resulting composite can be ensured. On the other hand, if the density of the carbon film is 1.8 g / cm 3 or less, the plating solution can easily penetrate into the central portion of the carbon film in the thickness direction, and the composite in which the metal and the fibrous carbon nanostructure are more effectively combined. Material can be obtained.
  • the “density of the carbon film” can be obtained by measuring the mass, area and thickness of the carbon film and dividing the mass of the carbon film by the volume.
  • a composite material can be obtained by subjecting the above-described carbon film to electrolytic plating treatment or electroless plating treatment, preferably electrolytic plating treatment, using a plating solution.
  • the plating solution used for the plating treatment contains at least metal ions that can be plated, and optionally further contains an additive for the plating solution (nonionic surfactant and other additives generally added to the plating solution).
  • the metal ions that can be plated are not particularly limited, and examples include metal ions that can be plated, such as ions of copper, nickel, tin, platinum, chromium, and zinc. Among these, copper ions are preferred as metal ions that can be plated. Copper is excellent in electrical conductivity, thermal conductivity, and the like, and if it is combined with a fibrous carbon nanostructure, a composite material having excellent performance (for example, electrical conductivity and thermal conductivity) can be obtained. Because.
  • the metal ions that can be plated are not particularly limited and can be introduced into the plating solution by dissolving a known metal compound such as copper sulfate pentahydrate or nickel sulfate hexahydrate. . Further, the concentration of metal ions that can be plated in the plating solution is not particularly limited.
  • the plating solution preferably contains a nonionic surfactant.
  • the plating solution containing the nonionic surfactant is presumed to be because the nonionic surfactant has excellent affinity with the fibrous carbon nanostructure, but can easily penetrate into the carbon film. Therefore, if a plating solution containing a nonionic surfactant is used, the metal and the fibrous carbon nanostructure can be more satisfactorily combined, and the physical properties of the composite material can be further enhanced.
  • nonionic surfactants examples include polyether surfactants, alkylphenol surfactants, polyester surfactants, sorbitan ester ether surfactants, alkylamine surfactants, and the like.
  • polyether surfactants are preferred from the viewpoint of further improving the physical properties of the composite material.
  • Polyether-based surfactants include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene dodecyl ether, polyoxyethylene nonylphenyl ether , Polyoxyethylene octyl phenyl ether, and polyoxyethylene / polyoxypropylene block copolymer.
  • polyethylene glycol is particularly preferable.
  • a nonionic surfactant may be used individually by 1 type and may use 2 or more types together.
  • the weight average molecular weight of the nonionic surfactant is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, and preferably 20000 or less. It is more preferably 10,000 or less, further preferably 5000 or less, and particularly preferably 4000 or less. When the weight-average molecular weight of the nonionic surfactant is within the above range, the metal and the fibrous carbon nanostructure can be combined more satisfactorily, and the physical properties of the composite material can be further improved.
  • the weight average molecular weight (Mw) of a nonionic surfactant can be calculated
  • the concentration of the nonionic surfactant in the plating solution is not particularly limited, but is preferably 5 ppm by mass or more, more preferably 10 ppm by mass or more, and further preferably 50 ppm by mass or more, Moreover, it is preferable that it is 500 mass ppm or less, It is more preferable that it is 300 mass ppm or less, It is still more preferable that it is 200 mass ppm or less. If the concentration of the nonionic surfactant is within the above-described range, the metal and the fibrous carbon nanostructure can be combined more satisfactorily, and the physical properties of the composite material can be further enhanced.
  • the plating solution may contain known additives for a plating solution such as a brightener in addition to the above-described components within a range not impairing the effects of the present invention.
  • the plating solution can be prepared by dissolving or dispersing the above-described components in a known solvent such as water.
  • the method for plating the carbon film is not particularly limited as long as the metal ion-derived metal in the plating solution can be deposited inside the carbon film.
  • a carbon film may be used as the cathode, or a laminate formed by adhering a carbon film to the substrate surface via a carbon tape or the like may be used. From the viewpoint of facilitating the penetration of the plating solution into the carbon film and efficiently producing a composite material in which the metal and the fibrous carbon nanostructure are combined, it is possible to use a cathode made of only the carbon film. preferable.
  • the metal ion-derived metal in the plating solution is deposited from both sides of the carbon film to the inside of the carbon film.
  • electrolytic plating there is no limitation to direct current plating, and current reversal plating and pulse plating can also be employed.
  • the plating treatment is not limited to electrolytic plating, and electroless plating can also be employed.
  • the plating solution may be stirred, for example, with a stirrer or the like.
  • a waiting time from when the carbon film is immersed in the plating solution to when the plating treatment is started (for example, in the case of electrolytic plating treatment, energization is started) (wait time before plating treatment) ) Is preferably provided.
  • the waiting time before the plating treatment is preferably 5 minutes or more, more preferably 10 minutes or more. If the waiting time before the plating treatment is 5 minutes or more, the penetration of the plating solution can be promoted to the inside of the carbon film.
  • the upper limit of the waiting time before the plating process is not particularly limited, but is usually 60 minutes or less.
  • the amount of energization is preferably 40C or more, more preferably 50C or more. If the energization amount is 40C or more, the plating process can be sufficiently performed to the inside of the carbon film.
  • composite material (Composite material) And the composite material manufactured using the manufacturing method mentioned above shows the outstanding electroconductivity and heat conductivity, since the metal and the fibrous carbon nanostructure have compounded favorably.
  • Such a composite material is expected to have a wide range of applications in, for example, electronics-related fields.
  • a cross-sectional sample of a sheet-like composite material was prepared using a cross-section polisher (registered trademark).
  • the composite state of copper and fibrous carbon nanostructures in the obtained cross-sectional sample was observed at a magnification of 400 times using a field emission scanning electron microscope (FE-SEM).
  • Example 1 ⁇ Synthesis of fibrous carbon nanostructure containing single-walled CNT>
  • a fibrous carbon nanostructure containing single-walled CNTs used in the examples was prepared by the super-growth method (hereinafter referred to as “fibrous carbon nanostructure A”) as described in International Publication No. 2006/011655.
  • the thickness of the iron catalyst thin film layer of the metal catalyst was 2 nm.
  • the obtained fibrous carbon nanostructure A had a BET specific surface area of 1050 m 2 / g (unopened state) and an average diameter (Av) of 3.3 nm.
  • the fibrous carbon nanostructure A was measured with a Raman spectrophotometer, a spectrum of a radial breathing mode (RBM) in a low wavenumber region of 100 to 300 cm ⁇ 1 characteristic for single-walled CNTs was observed. Further, the t-plot in the unopened state shows an upwardly convex shape, the inflection point is in the range of 0.55 ⁇ t (nm) ⁇ 1.0, and the total specific surface area S1 and the internal specific surface area S2 The ratio satisfied 0.05 ⁇ S2 / S1 ⁇ 0.30.
  • RBM radial breathing mode
  • the median diameter (average particle diameter) of the fibrous carbon nanostructure A in the dispersion A was 24.1 ⁇ m.
  • the obtained dispersion A was filtered under reduced pressure using Kiriyama filter paper (No. 5A) to obtain a carbon film A having a thickness of 40 ⁇ m and a density of 0.85 g / cm 3 .
  • ⁇ Preparation of composite material> Using the carbon film A described above as the cathode and the phosphorus-containing copper plate as the anode, composite material A was obtained by performing electrolytic plating in a copper plating bath under the following conditions.
  • Example 2 ⁇ Preparation of carbon film> A carbon film B was prepared in the same manner as the carbon film A except that the thickness was 40 ⁇ m and the density was 1.30 g / cm 3 .
  • a carbon tape was affixed on a pure copper plate (substrate) that had been degreased and acid cleaned.
  • a cathode was obtained by further bonding the above-described carbon film B on the carbon tape. Using this cathode and a copper plate as the anode, a composite material B was obtained by performing electrolytic plating under the following conditions in a copper plating bath.
  • a metal and a fibrous carbon nanostructure can be favorably compounded to produce a composite material having excellent physical properties.
  • a composite material having excellent physical properties can be obtained.

Abstract

Un objet de la présente invention est de fournir un procédé de fabrication d'un matériau composite, ledit procédé permettant à un métal et à une nanostructure de carbone fibreuse d'être suffisamment combinés pour produire un matériau composite présentant des propriétés physiques supérieures. Ce procédé de fabrication d'un matériau composite est caractérisé par le fait qu'il comprend une étape dans laquelle un film de carbone contenant ladite nanostructure de carbone fibreuse est soumis à un processus de placage à l'aide d'un fluide de placage.
PCT/JP2016/073508 2015-08-28 2016-08-03 Procédé de fabrication d'un matériau composite et matériau composite WO2017038413A1 (fr)

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