JP2012101140A

JP2012101140A - Powder solubilization method and powder solubilization apparatus

Info

Publication number: JP2012101140A
Application number: JP2010249018A
Authority: JP
Inventors: Yoshimi Nishimura; 芳実西村; Shigeji Hishida; 茂二菱田; Mitsuhiro Toyama; 光宏陶山; Osamu Takai; 治高井; Nagahiro Saito; 永宏斎藤; Junko Hieda; 純子稗田; Chiaki Terajima; 千晶寺島
Original assignee: KURITA SEISAKUSHO KK; Nagoya University NUC; Kurita Seisakusho Corp
Current assignee: KURITA SEISAKUSHO KK; Nagoya University NUC; Kurita Seisakusho Corp
Priority date: 2010-11-05
Filing date: 2010-11-05
Publication date: 2012-05-31

Abstract

PROBLEM TO BE SOLVED: To provide a powder solubilization method in which surface modification treatment of slightly soluble powder such as a CNM is accelerated, and thereby which can perform a lot of surface modification treatment by low cost, and to provide a powder solubilization apparatus which can perform powder solubilization treatment based on the powder solubilization method.SOLUTION: A termination part 5 of a stirring member 4 is made a counter electrode of an electrode 14 in liquid, and a synthetic voltage V of a high voltage high frequency pulse generator 17 is impressed between both electrodes. A CNT at a vicinity of a water surface 32 or a CNT 11 which floats on a water surface 32 serves as a powder electrode by impression of the synthetic voltage V, and makes a plasma discharge 27 in liquid generate with the electrode 14 in liquid. A circumference of the electrode 14 in liquid reaches a boiling status by the plasma discharge 27 in liquid, an active water steam 28 containing radicals such as Hand OHarises. The floating CNT powder is made hydrophilic in such that a hydration layer is formed at a CNT circumference by contacting with the active water steam 28 and the plasma in liquid.

Description

本発明は、カーボンナノボール（ｃａｒｂｏｎｎａｎｏｂａｌｌ：ＣＮＢ）、カーボンナノチューブ（ｃａｒｂｏｎｎａｎｏｔｕｂｅ：ＣＮＴ）、フラーレン、ダイヤモンドライクカーボン（ｄｉａｍｏｎｄ−ｌｉｋｅｃａｒｂｏｎ：ＤＬＣ）、ナノダイヤパウダー等の難溶解性粉体を水やアルコール等の溶媒に溶解させる粉体可溶化方法及びその粉体可溶化方法に基づいて前記難溶解性粉体の可溶化処理を行う粉体可溶化装置に関する。 In the present invention, a hardly soluble powder such as carbon nanoball (CNB), carbon nanotube (CNT), fullerene, diamond-like carbon (DLC), nanodiameter powder or the like is used as water or alcohol. The present invention relates to a powder solubilization method for dissolving in a solvent and a powder solubilization apparatus for performing the solubilization treatment of the hardly soluble powder based on the powder solubilization method.

ＣＮＢ、ＣＮＴ、フラーレン、ＤＬＣ等のカーボンナノ材料（ｃａｒｂｏｎｎａｎｏｍａｔｅｒｉａｌｓ：ＣＮＭ）は、電子材料、医薬品、化粧品、潤滑剤など多岐に亘る応用が可能な優れた特性を有しているため、新規な機能素材として次世代への期待が高まっており、急速な開発が進められている。 Carbon nanomaterials (CNM) such as CNB, CNT, fullerene, and DLC have excellent characteristics that can be applied in a wide range of applications such as electronic materials, pharmaceuticals, cosmetics, and lubricants. Expectations for the next generation are increasing as materials, and rapid development is underway.

例えば、ＣＮＴはアルミニウムの半分という軽量性、鋼鉄の数十倍の強度、更にいくら曲げても折れないしなやかな弾力性からなる優れた材料特性を具備している。しかも、ＣＮＴは構造によって電気伝導率が変わることから、シリコン以後の半導体の素材として期待されているほか、内部に筒状の中空空間を有しているため、種々の分子を内包させることが可能であり、例えば燃料電池の電極等としての利用の可能性が秘められている。ＣＮＴとしては、単層カーボンナノボール（ｓｉｎｇｌｅｗａｌｌｃａｒｂｏｎｎａｎｏｔｕｂｅ：ＳＷＣＮＴ）と多層カーボンナノボール（ｍｕｌｔｉｗａｌｌｃａｒｂｏｎｎａｎｏｔｕｂｅ：ＭＷＣＮＴ）が見出されている。 For example, CNTs have excellent material properties such as lightness that is half that of aluminum, strength several tens of times that of steel, and supple elasticity that does not break even when bent. In addition, CNTs are expected to be used as semiconductor materials after silicon because their electrical conductivity changes depending on the structure, and because they have a cylindrical hollow space inside, they can contain various molecules. For example, the possibility of use as an electrode of a fuel cell is hidden. As CNTs, single-walled carbon nanoballs (SWCNT) and multi-walled carbon nanoballs (MWCNT) have been found.

ＣＮＭの応用として、例えば、樹脂やフィルムにＣＮＭを混練することにより機械的強度や耐摩耗性等を向上させ高機能化を図ることができる。ＣＮＭを混練するには、ＣＮＭと樹脂成分を相互に強固に化学的結合をさせるため、ＣＮＭに親水性の表面修飾を行う必要がある。例えば、ＣＮＴの表面を水酸基で修飾することにより、ＣＮＴの周りに水和層が形成されて水溶化され、この修飾ＣＮＴを樹脂に分散させることにより、上記高機能化されたＣＮＴ含有樹脂を生成することができる。 As an application of CNM, for example, by kneading CNM with a resin or a film, mechanical strength, wear resistance, etc. can be improved and higher functionality can be achieved. In order to knead CNM, it is necessary to perform hydrophilic surface modification on CNM in order to cause CNM and the resin component to chemically bond to each other firmly. For example, by modifying the surface of the CNT with a hydroxyl group, a hydrated layer is formed around the CNT to make it water-soluble, and the modified CNT is dispersed in the resin to produce the above highly functional CNT-containing resin. can do.

特開２００８−１３８１０号公報（特許文献１）には、貯留部に貯留している金属塩の溶液に配置した一対の液中電極間に液中プラズマを生じさせることにより、溶媒を構成する元素や化合物のラジカルや電子を生じさせ、この生じた元素や化合物のラジカルや電子によって溶液中の金属イオンを還元することにより金属塩を構成する金属のナノ粒子を生成するナノテクノロジーが開示されている。 Japanese Patent Laid-Open No. 2008-13810 (Patent Document 1) discloses an element that constitutes a solvent by generating in-liquid plasma between a pair of in-liquid electrodes arranged in a solution of a metal salt stored in a storage part. Nanotechnology that generates metal nanoparticles that constitute metal salts by generating radicals and electrons of compounds and compounds, and reducing metal ions in solution by the radicals and electrons of the generated elements and compounds is disclosed. .

特開２００８−１３８１０号公報JP 2008-13810 A

ＣＮＭは一般的に水やアルコール等の有機溶媒に溶けにくい難溶解性を有している。このため、従来、難溶解性粉体であるＣＮＭに親水性の表面修飾を施すには、例えばＣＮＴの表面に酸処理等の化学的処理を行なって表面改質を行ったり、界面活性剤をＣＮＴの表面に物理的吸着を行ったりしている。しかしながら、これらの化学的処理あるいは物理的吸着処理では、表面修飾処理に時間を要するため、事業化に向けての高速化及び大量処理を妨げる問題があった。また、化学的処理に用いる酸等によりＣＮＭ構造に影響を与えるおそれがあり、界面活性剤による表面修飾処理の場合には物理的吸着の処理制御に困難を伴う。更に、特許文献１に開示されたナノテクノロジーを用いれば、液中プラズマによりＣＮＴ等への表面修飾処理時間を短縮できるが、難溶解性のＣＮＴを液中電極間に導く技術を必要とし、実現困難となっていた。 CNM is generally difficult to dissolve in organic solvents such as water and alcohol. For this reason, in order to apply hydrophilic surface modification to CNM, which is a hardly soluble powder, for example, the surface of CNTs is subjected to chemical treatment such as acid treatment to modify the surface, or a surfactant is used. Physical adsorption is performed on the surface of the CNT. However, in these chemical treatments or physical adsorption treatments, the surface modification treatment takes time, and thus there has been a problem that hinders speeding up and commercialization for commercialization. In addition, there is a possibility that the CNM structure may be affected by an acid or the like used for chemical treatment. In the case of surface modification treatment with a surfactant, it is difficult to control physical adsorption treatment. Furthermore, if the nanotechnology disclosed in Patent Document 1 is used, the surface modification processing time for CNTs and the like can be shortened by in-liquid plasma, but this requires a technique for introducing hardly soluble CNTs between the electrodes in the liquid. It was difficult.

従って、本発明の目的は、ＣＮＭ等の難溶解性粉体の表面修飾処理を高速化して、大量の表面修飾処理を低コストで行うことのできる粉体可溶化方法及びその粉体可溶化方法に基づき粉体可溶化処理を行える粉体可溶化装置を提供することである。 Accordingly, an object of the present invention is to provide a powder solubilization method and a powder solubilization method capable of performing a large amount of surface modification treatment at a low cost by speeding up the surface modification treatment of a hardly soluble powder such as CNM. It is providing the powder solubilization apparatus which can perform a powder solubilization process based on this.

本発明者は、液中プラズマを用いてＣＮＭ表面を高速且つ大量に修飾処理する方法を鋭意研究した結果、液面に接したＣＮＭ自体を片方のプラズマ電極として用い、液中に配した液中電極との間で液中プラズマ放電を行うことにより、難溶解性粉体の高速且つ大量の表面修飾処理が可能となる知見を得るに至った。 As a result of earnest research on a method for modifying a CNM surface at a high speed and in a large amount by using in-liquid plasma, the present inventor used CNM itself in contact with the liquid surface as one plasma electrode, and in the liquid arranged in the liquid By conducting in-liquid plasma discharge with the electrode, the inventors have come to the knowledge that high-speed and large-scale surface modification treatment of hardly soluble powders is possible.

本発明は上記課題を解決するため、上記知見に基づきになされたものであり、本発明の第１の形態は、溶媒を収容した溶媒槽の液中に少なくとも１つの液中電極を配置し、前記溶媒槽内の前記溶媒の液面に難溶解性粉体を供給し、前記難溶解性粉体により構成された粉体電極と前記液中電極との電極間に高電圧高周波パルスを印加して高電圧放電による液中プラズマを発生させ、前記難溶解性粉体を前記液中に溶解させる粉体可溶化方法である。 In order to solve the above problems, the present invention has been made based on the above knowledge, and the first aspect of the present invention is that at least one submerged electrode is disposed in a liquid in a solvent tank containing a solvent, A hardly soluble powder is supplied to the liquid surface of the solvent in the solvent tank, and a high-voltage high-frequency pulse is applied between the powder electrode composed of the hardly soluble powder and the electrode in the liquid. This is a powder solubilization method in which plasma in liquid by high voltage discharge is generated and the hardly soluble powder is dissolved in the liquid.

本発明の第２の形態は、第１の形態において、前記難溶解性粉体が非導電性物質からなり、前記液中電極に対して前記溶媒の液面を介して対向電極を配置し、前記対向電極と前記液面間に前記難溶解性粉体を供給し、前記液中電極と前記対向電極との電極間に前記高電圧高周波パルスを印加したとき、前記対向電極と前記液面間に介在する前記難溶解性粉体により形成される誘電体層により前記粉体電極を構成して、前記高電圧放電による液中プラズマを発生させる粉体可溶化方法である。 According to a second aspect of the present invention, in the first aspect, the hardly soluble powder is made of a non-conductive substance, and a counter electrode is disposed through the liquid level of the solvent with respect to the liquid electrode. When the hardly soluble powder is supplied between the counter electrode and the liquid surface, and the high-voltage high-frequency pulse is applied between the electrode in the liquid and the counter electrode, the gap between the counter electrode and the liquid surface In the powder solubilization method, the powder electrode is constituted by a dielectric layer formed of the hardly soluble powder interposed in the substrate, and plasma in liquid by the high voltage discharge is generated.

本発明の第３の形態は、第２の形態において、前記難溶解性粉体を撹拌する撹拌部材を前記溶媒槽の液面近傍に配置し、前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加し、前記撹拌部材により撹拌しながら前記難溶解性粉体を前記液面側に供給する粉体可溶化方法である。 According to a third aspect of the present invention, in the second aspect, the stirring member for stirring the hardly soluble powder is disposed near the liquid surface of the solvent tank, and the terminal portion of the stirring member is used as the counter electrode. This is a powder solubilization method in which a high-voltage high-frequency pulse is applied and the hardly soluble powder is supplied to the liquid surface side while being stirred by the stirring member.

本発明の第４の形態は、第１、第２又は第３の形態において、前記難溶解性粉体が、カーボンナノボール（ＣＮＢ）、単層又は多層のカーボンナノチューブ（ＣＮＴ）、フラーレン等の導電性物質又はダイヤモンドライクカーボン（ＤＬＣ）、ナノダイヤパウダー等の非導電性物質からなる粉体可溶化方法である。 According to a fourth aspect of the present invention, in the first, second, or third aspect, the hardly soluble powder is a conductive material such as carbon nanoball (CNB), single-walled or multi-walled carbon nanotube (CNT), or fullerene. It is a powder solubilization method made of a non-conductive substance such as a conductive substance, diamond-like carbon (DLC), or nano diamond powder.

本発明の第５の形態は、前記第１〜第４形態のいずれかにおいて、前記溶媒が、水等の水酸基を含む液体、あるいはアンモニア水等のアミノ基を含む液体のいずれかからなる粉体可溶化方法である。 The fifth aspect of the present invention is the powder according to any one of the first to fourth aspects, wherein the solvent is either a liquid containing a hydroxyl group such as water or a liquid containing an amino group such as aqueous ammonia. Solubilization method.

本発明の第６の形態は、第１〜第５の形態のいずれかにおいて、前記高電圧高周波パルスは、１ｋＶ〜２０ｋＶの範囲のいずれかのピーク間電圧値を有する粉体可溶化方法である。 A sixth aspect of the present invention is the powder solubilization method according to any one of the first to fifth aspects, wherein the high-voltage high-frequency pulse has any peak-to-peak voltage value in the range of 1 kV to 20 kV. .

本発明の第７の形態は、第１〜第６の形態のいずれかにおいて、前記高電圧高周波パルスは、０．１ｋＨｚ〜３００ｋＨｚの範囲のいずれかの周波数を有する粉体可溶化方法である。 A seventh aspect of the present invention is the powder solubilization method according to any one of the first to sixth aspects, wherein the high-voltage high-frequency pulse has any frequency in the range of 0.1 kHz to 300 kHz.

本発明の第８の形態は、第１〜第６の形態のいずれかにおいて、前記高電圧高周波パルスは、０．１μＳ〜１００μＳの範囲のいずれかのパルス幅を有する粉体可溶化方法である。 An eighth aspect of the present invention is the powder solubilization method according to any one of the first to sixth aspects, wherein the high-voltage high-frequency pulse has any pulse width in the range of 0.1 μS to 100 μS. .

本発明の第９の形態は、第１〜第８の形態のいずれかにおいて、前記高電圧高周波パルスは、高周波パルスにＲＦ電圧を重畳した合成電圧からなる粉体可溶化方法である。 A ninth aspect of the present invention is the powder solubilization method according to any one of the first to eighth aspects, wherein the high-voltage high-frequency pulse is a composite voltage in which an RF voltage is superimposed on the high-frequency pulse.

本発明の第１０の形態は、溶媒を収容した溶媒槽と、前記溶媒槽の液中に配置した少なくとも１つの液中電極と、前記液中電極に対向して配置した少なくとも１つの対向電極と、前記溶媒槽内の前記溶媒の液面に難溶解性粉体を供給する難溶解性粉体供給部と、前記難溶解性粉体により構成された粉体電極と前記液中電極との電極間に高電圧高周波パルスを印加する高電圧高周波パルス発生装置とを有し、前記電極間に前記高電圧高周波パルスを印加して高電圧放電を発生させ、前記難溶解性粉体を前記液中に溶解させる粉体可溶化装置である。 A tenth aspect of the present invention includes a solvent tank containing a solvent, at least one submerged electrode disposed in the liquid of the solvent tank, and at least one counter electrode disposed opposite to the submerged electrode. , A hardly soluble powder supply unit for supplying a hardly soluble powder to the liquid level of the solvent in the solvent tank, a powder electrode composed of the hardly soluble powder, and an electrode of the submerged electrode A high-voltage, high-frequency pulse generator for applying a high-voltage, high-frequency pulse between the electrodes, generating a high-voltage discharge by applying the high-voltage, high-frequency pulse between the electrodes, It is a powder solubilizer to be dissolved in.

本発明の第１１の形態は、第１０の形態において、前記液中電極に対して前記溶媒の液面を介して前記対向電極を配置し、前記電極間に前記難溶解性粉体供給部により非導電性物質からなる前記難溶解性粉体を供給し、前記液中電極と前記対向電極との電極間に前記高電圧高周波パルスを印加したとき、前記難溶解性粉体が、前記対向電極と前記液面間に介在する前記難溶解性粉体により形成される誘電体層により前記粉体電極を構成して、前記高電圧放電による液中プラズマを発生させる粉体可溶化装置である。 According to an eleventh aspect of the present invention, in the tenth aspect, the counter electrode is disposed via the liquid surface of the solvent with respect to the submerged electrode, and the hardly soluble powder supply unit is interposed between the electrodes. When the hardly soluble powder made of a non-conductive substance is supplied and the high-voltage high-frequency pulse is applied between the electrode in the liquid and the counter electrode, the hardly soluble powder becomes the counter electrode And a dielectric layer formed by the hardly soluble powder interposed between the liquid surfaces and the powder electrode solubilizing apparatus that generates plasma in liquid by the high voltage discharge.

本発明の第１２の形態は、第１０又は第１１の形態において、前記溶媒槽の液面近傍に配置され、前記難溶解性粉体を撹拌する撹拌部材を備え、前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加し、前記撹拌部材により撹拌しながら前記難溶解性粉体を前記液面側に供給する粉体可溶化装置である。 A twelfth aspect of the present invention includes, in the tenth or eleventh aspect, a stirring member that is disposed in the vicinity of the liquid surface of the solvent tank and that stirs the hardly soluble powder. In the powder solubilizer, the high-voltage, high-frequency pulse is applied as the counter electrode, and the hardly soluble powder is supplied to the liquid surface side while being stirred by the stirring member.

本発明の第１３の形態は、第１０、第１１又は第１２の形態において、前記高電圧高周波パルス発生装置は、基本高周波信号を複数に分周すると共に位相を複数段にずらしたスイッチング信号に基づき直流電力をスイッチングして得られたパルス電圧を合成した高周波パルスを発生させる高周波パルス発生回路からなる粉体可溶化装置である。 According to a thirteenth aspect of the present invention, in the tenth, eleventh, or twelfth aspect, the high-voltage high-frequency pulse generator generates a switching signal in which the basic high-frequency signal is divided into a plurality of phases and the phase is shifted to a plurality of stages. This is a powder solubilizer comprising a high-frequency pulse generation circuit for generating a high-frequency pulse by synthesizing a pulse voltage obtained by switching DC power based on the above.

本発明の第１４の形態は、第１０〜第１３の形態のいずれかにおいて、前記高電圧高周波パルス発生装置は、ＲＦ電源と、前記ＲＦ電源のＲＦ電圧を前記高電圧高周波パルス発生回路により発生された高周波パルスに重畳する重畳装置とを含み、前記高周波パルスに前記ＲＦ電圧を重畳した合成電圧を前記高電圧高周波パルスとして印加する粉体可溶化装置である。 According to a fourteenth aspect of the present invention, in any one of the tenth to thirteenth aspects, the high voltage high frequency pulse generator generates an RF power source and an RF voltage of the RF power source by the high voltage high frequency pulse generation circuit. A powder solubilizer that applies a combined voltage obtained by superimposing the RF voltage on the high-frequency pulse as the high-voltage high-frequency pulse.

本発明の第１の形態によれば、溶媒を収容した溶媒槽の液中に少なくとも１つの液中電極を配置し、前記溶媒槽内の前記溶媒の液面に難溶解性粉体を供給し、前記難溶解性粉体により構成された粉体電極と前記液中電極との電極間に高電圧高周波パルスを印加して高電圧放電による液中プラズマを発生させ、前記難溶解性粉体を前記液中に溶解させるので、前記液中電極を配置するだけの簡単な構成で、前記難溶解性粉体を前記溶媒の液面に供給することにより、前記難溶解性粉体の親水化のための表面修飾処理を液中プラズマによって高速化して連続処理し、大量の表面修飾処理を低コストで行うことができる。 According to the first aspect of the present invention, at least one submerged electrode is disposed in a liquid in a solvent tank containing a solvent, and the hardly soluble powder is supplied to the liquid level of the solvent in the solvent tank. Applying a high-voltage, high-frequency pulse between a powder electrode composed of the hardly soluble powder and the in-liquid electrode to generate in-liquid plasma by high-voltage discharge, Since it is dissolved in the liquid, it is possible to make the hardly soluble powder hydrophilic by supplying the hardly soluble powder to the liquid surface of the solvent with a simple configuration by simply placing the electrode in liquid. Therefore, a large amount of surface modification treatment can be performed at low cost by increasing the speed of the surface modification treatment using plasma in liquid and performing continuous treatment.

本発明における表面修飾処理は、水に限らず、アルコール、各種有機溶媒、ナトリウム含有液等の溶媒に適用することができる。また、前記難溶解性粉体には、水、アルコール、有機溶媒などに溶解しにくいＣＮＭに限らず、難溶解性を有する炭素由来の微粉末やナノ粒子、炭素被覆をしたセラミック粒子等を使用することができ、また導電性物質に限らず非導電性物質にも適用することができる。
前記液中電極の設置数は少なくとも１つあればよく、多数個設置することにより、液中プラズマの発生率を高め、より効率的な表面修飾処理を行うことができる。 The surface modification treatment in the present invention can be applied not only to water but also to solvents such as alcohol, various organic solvents, and sodium-containing liquids. In addition, the hardly soluble powder is not limited to CNM which is difficult to dissolve in water, alcohol, organic solvent, etc., but uses fine powder or nanoparticles derived from carbon having difficulty solubility, ceramic particles coated with carbon, etc. In addition, the present invention can be applied not only to a conductive material but also to a non-conductive material.
The number of the submerged electrodes need only be at least one. By installing a large number of submerged electrodes, the generation rate of submerged plasma can be increased and more efficient surface modification treatment can be performed.

本発明の第２の形態によれば、前記難溶解性粉体が非導電性物質からなり、前記液中電極に対して前記溶媒の液面を介して対向電極を配置し、前記対向電極と前記液面間に前記難溶解性粉体を供給し、前記液中電極と前記対向電極との電極間に前記高電圧高周波パルスを印加したとき、前記対向電極と前記液面間に介在する前記難溶解性粉体により形成される誘電体層により前記粉体電極を構成して、前記高電圧放電による液中プラズマを発生させるので、前記液中電極を配置するだけの簡単な構成で、前記難溶解性粉体を前記対向電極と前記液面間に介在するように供給することにより、非導電性物質からなる難溶解性粉体の表面修飾処理を液中プラズマによって高速化して連続処理し、大量の表面修飾処理を低コストで行うことができる。 According to the second aspect of the present invention, the hardly soluble powder is made of a non-conductive substance, and the counter electrode is disposed through the liquid surface of the solvent with respect to the in-liquid electrode, The hardly soluble powder is supplied between the liquid surfaces, and when the high-voltage high-frequency pulse is applied between the electrodes in the liquid and the counter electrode, the intervening between the counter electrode and the liquid surface Since the powder electrode is constituted by a dielectric layer formed of a hardly soluble powder and the plasma in liquid due to the high voltage discharge is generated, the simple configuration in which only the liquid electrode is arranged, By supplying the hardly soluble powder so as to be interposed between the counter electrode and the liquid surface, the surface modification treatment of the hardly soluble powder made of a non-conductive substance is accelerated by the plasma in the liquid and continuously processed. A large amount of surface modification treatment can be performed at low cost

本発明の第３の形態によれば、前記難溶解性粉体を撹拌する撹拌部材を前記溶媒槽の液面近傍に配置し、前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加し、前記撹拌部材により撹拌しながら前記難溶解性粉体を前記液面側に供給するので、前記撹拌部材の撹拌作用により前記難溶解性粉体を前記液面側に連続的な供給を行え、しかも前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加することにより、液中プラズマによる表面修飾処理の高速化及び連続処理を促進して、より一層の大量処理化及び低コスト化を実現することができる。
前記撹拌部材は、スクリュー、羽根板、螺旋部材、コイル状部材等、前記難溶解性粉体を前記液面側に連続的な供給可能な形態の搬送回転翼部材を使用することができる。 According to the third aspect of the present invention, the stirring member for stirring the hardly soluble powder is disposed in the vicinity of the liquid surface of the solvent tank, and the terminal portion of the stirring member is used as the counter electrode to perform the high-voltage high-frequency pulse. And supplying the hardly soluble powder to the liquid surface side while stirring by the stirring member, so that the hardly soluble powder is continuously supplied to the liquid surface side by the stirring action of the stirring member. In addition, by applying the high-voltage and high-frequency pulse with the end portion of the stirring member as the counter electrode, the surface modification process by the plasma in liquid is accelerated and the continuous process is promoted, and the mass processing is further increased. In addition, cost reduction can be realized.
As the stirring member, a conveying rotary blade member that can continuously supply the hardly soluble powder to the liquid surface side, such as a screw, a blade, a spiral member, and a coiled member, can be used.

本発明の第４の形態によれば、カーボンナノボール（ＣＮＢ）、単層又は多層のカーボンナノチューブ（ＣＮＴ）、フラーレン等の導電性物質又はダイヤモンドライクカーボン（ＤＬＣ）、ナノダイヤパウダー等の非導電性物質からなるＣＮＭに適用することにより、難溶解性粉体であるＣＮＭに対して液中プラズマによる表面修飾処理を高速且つ大量に施した修飾ＣＮＭを生成して低価格な高機能化結合材料を得ることができる。 According to the fourth embodiment of the present invention, conductive materials such as carbon nanoballs (CNB), single-walled or multi-walled carbon nanotubes (CNT), fullerene, or non-conductive materials such as diamond-like carbon (DLC), nanodia powder, etc. By applying to a CNM made of the above, a low-cost highly functional binding material is obtained by generating a modified CNM that is obtained by subjecting a CNM, which is a hardly soluble powder, to surface modification treatment with plasma in liquid at high speed and in large quantities. be able to.

本発明の第５の形態によれば、水等の水酸基を含む液体、あるいはアンモニア水等のアミノ基を含む液体のいずれかからなる前記溶媒を使用することにより、例えば、水酸基を含む液体を使用してＣＮＭの表面にＯＨ基を結合可能なラジカルを液中プラズマにより発生させたり、またアミノ基を含む液体を使用してアミノ基を結合可能なラジカルを発生させたりして、前記難溶解性粉体の表面修飾処理の高速化且つ大量処理化を実現することができる。 According to the fifth aspect of the present invention, by using the solvent consisting of either a liquid containing a hydroxyl group such as water or a liquid containing an amino group such as aqueous ammonia, for example, a liquid containing a hydroxyl group is used. The radicals capable of binding OH groups to the surface of CNM are generated by plasma in liquid, or radicals capable of binding amino groups are generated using a liquid containing amino groups. It is possible to realize high-speed and large-scale processing of the powder surface modification treatment.

本発明の第６の形態によれば、前記高電圧高周波パルスは、１ｋＶ〜２０ｋＶの範囲のいずれかのピーク間電圧値を有するので、表面修飾処理に好適な液中プラズマ放電を発生させて、前記難溶解性粉体の表面修飾処理の高速化且つ大量処理化を実現することができる。 According to the sixth aspect of the present invention, since the high-voltage high-frequency pulse has any peak-to-peak voltage value in the range of 1 kV to 20 kV, it generates an in-liquid plasma discharge suitable for surface modification treatment, The surface modification treatment of the hardly soluble powder can be speeded up and processed in a large amount.

本発明の第７の形態によれば、前記高電圧高周波パルスは、０．１ｋＨｚ〜３００ｋＨｚの範囲のいずれかの周波数を有するので、表面修飾処理に好適な液中プラズマ放電を発生させて、前記難溶解性粉体の表面修飾処理の高速化且つ大量処理化を実現することができる。 According to the seventh aspect of the present invention, since the high-voltage high-frequency pulse has any frequency in the range of 0.1 kHz to 300 kHz, the plasma discharge in liquid suitable for the surface modification treatment is generated, It is possible to realize a high-speed and large-scale surface modification treatment of the hardly soluble powder.

本発明の第８の形態によれば、前記高電圧高周波パルスは、０．１μＳ〜１００μＳの範囲のいずれかのパルス幅を有するので、表面修飾処理に好適な液中プラズマ放電を発生させて、前記難溶解性粉体の表面修飾処理の高速化且つ大量処理化を実現することができる。 According to the eighth aspect of the present invention, since the high-voltage high-frequency pulse has any pulse width in the range of 0.1 μS to 100 μS, it generates a plasma discharge in liquid suitable for surface modification treatment, The surface modification treatment of the hardly soluble powder can be speeded up and processed in a large amount.

本発明の第９の形態によれば、前記高電圧高周波パルスは、高周波パルスにＲＦ電圧を重畳した合成電圧からなるので、ＲＦ電圧（高周波電力）によりプラズマ発生を促進し、高周波パルスによるプラズマ中のラジカルやイオンの誘引を行え、表面修飾処理に好適な液中プラズマ放電を発生させることができ、前記難溶解性粉体の表面修飾処理の高速化且つ大量処理化を実現することができる。 According to the ninth aspect of the present invention, since the high-voltage high-frequency pulse is composed of a composite voltage obtained by superimposing the RF voltage on the high-frequency pulse, plasma generation is promoted by the RF voltage (high-frequency power), and the plasma is generated by the high-frequency pulse. Radicals and ions can be attracted, plasma discharge in liquid suitable for the surface modification treatment can be generated, and the surface modification treatment of the hardly soluble powder can be speeded up and mass-treated.

本発明の第１０の形態によれば、前記溶媒槽の液中に少なくとも１つの液中電極を配置し、前記溶媒槽内の前記溶媒の液面に難溶解性粉体を前記難溶解性粉体供給部により供給し、前記難溶解性粉体により構成された粉体電極と前記液中電極との電極間に前記高電圧高周波パルス発生装置により高電圧高周波パルスを印加して高電圧放電による液中プラズマを発生させ、前記難溶解性粉体を前記液中に溶解させるので、前記液中電極を配置するだけの簡単な構成で、前記難溶解性粉体を前記溶媒の液面に供給することにより、前記難溶解性粉体の親水化のための表面修飾処理を液中プラズマによって高速化して連続処理し、大量の表面修飾処理を低コストで行うことのできる粉体可溶化装置を提供することができる。 According to the tenth aspect of the present invention, at least one submerged electrode is disposed in the liquid in the solvent tank, and the hardly soluble powder is placed on the liquid surface of the solvent in the solvent tank. A high-voltage high-frequency pulse is applied by the high-voltage high-frequency pulse generator between the powder electrode composed of the hardly soluble powder and the submerged electrode, which is supplied by a body supply unit, and by high-voltage discharge Since the in-liquid plasma is generated and the hardly soluble powder is dissolved in the liquid, the hardly soluble powder is supplied to the liquid surface of the solvent with a simple configuration simply by arranging the in-liquid electrode. Thus, a powder solubilizing apparatus capable of performing a large amount of surface modification treatment at a low cost by performing a surface treatment for hydrophilization of the hardly soluble powder at a high speed by a plasma in liquid and continuously treating the powder. Can be provided.

本発明の第１１の形態によれば、前記液中電極に対して前記溶媒の液面を介して対向電極を配置し、前記対向電極と前記液面間に前記難溶解性粉体供給部により、非導電性物質からなる前記難溶解性粉体を供給し、前記液中電極と前記対向電極との電極間に前記高電圧高周波パルスを印加したとき、前記対向電極と前記液面間に介在する前記難溶解性粉体により形成される誘電体層により前記粉体電極を構成して、前記高電圧放電による液中プラズマを発生させるので、前記液中電極を配置するだけの簡単な構成で、前記難溶解性粉体を前記対向電極と前記液面間に介在するように供給することにより、非導電性物質からなる難溶解性粉体の表面修飾処理を液中プラズマによって高速化して連続処理し、大量の表面修飾処理を低コストで行うことのできる粉体可溶化装置を提供することができる。 According to the eleventh aspect of the present invention, the counter electrode is disposed through the liquid level of the solvent with respect to the submerged electrode, and the hardly soluble powder supply unit is provided between the counter electrode and the liquid level. When the high-voltage high-frequency pulse is supplied between the electrode in the liquid and the counter electrode when the hardly soluble powder made of a non-conductive substance is supplied and interposed between the counter electrode and the liquid surface Since the powder electrode is constituted by the dielectric layer formed by the hardly soluble powder and the plasma in liquid due to the high voltage discharge is generated, it is possible to simply arrange the liquid electrode. By supplying the hardly soluble powder so as to be interposed between the counter electrode and the liquid surface, the surface modification treatment of the hardly soluble powder made of a non-conductive substance is accelerated and continuously performed in the liquid plasma. Process and do a lot of surface modification at low cost It is possible to provide a powder solubilization device capable of and.

本発明の第１２の形態によれば、前記溶媒槽の液面近傍に配置され、前記難溶解性粉体を撹拌する撹拌部材を備え、前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加し、前記撹拌部材により撹拌しながら前記難溶解性粉体を前記液面側に供給するので、前記撹拌部材の撹拌作用により前記難溶解性粉体を前記液面側に連続的な供給を行え、しかも前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加することにより、液中プラズマによる表面修飾処理の高速化及び連続処理を促進して、より一層の大量処理化及び低コスト化を実現することのできる粉体可溶化装置を提供することができる。 According to a twelfth aspect of the present invention, the high voltage is provided with a stirring member that is disposed in the vicinity of the liquid surface of the solvent tank and stirs the hardly soluble powder, with the terminal portion of the stirring member as the counter electrode. A high-frequency pulse is applied, and the hardly soluble powder is supplied to the liquid surface side while being stirred by the stirring member. Therefore, the hardly soluble powder is continuously supplied to the liquid surface side by the stirring action of the stirring member. By applying the high-voltage, high-frequency pulse using the terminal portion of the stirring member as the counter electrode, the surface modification treatment with liquid plasma is accelerated and the continuous treatment is promoted, so that a larger amount can be obtained. It is possible to provide a powder solubilizing apparatus that can realize processing and cost reduction.

本発明の第１３の形態によれば、前記高電圧高周波パルス発生装置は、基本高周波信号を複数に分周すると共に位相を複数段にずらしたスイッチング信号に基づき直流電力をスイッチングして得られたパルス電圧を合成した高周波パルスを発生させる高周波パルス発生回路からなるので、前記高周波パルスの印加により表面修飾処理に好適な液中プラズマ放電を発生させて、前記難溶解性粉体の表面修飾処理の高速化且つ大量処理化を実現することのできる粉体可溶化装置を提供実現することができる。 According to a thirteenth aspect of the present invention, the high-voltage high-frequency pulse generator is obtained by switching DC power based on a switching signal that divides a basic high-frequency signal into a plurality of frequencies and shifts the phase to a plurality of stages. Since it comprises a high-frequency pulse generation circuit that generates a high-frequency pulse synthesized with a pulse voltage, by applying the high-frequency pulse, a plasma discharge in liquid suitable for surface modification treatment is generated, and the surface modification treatment of the hardly soluble powder is performed. It is possible to provide and realize a powder solubilizer capable of realizing high speed and mass processing.

本発明の第１４の形態によれば、前記高電圧高周波パルス発生装置は、ＲＦ電源と、前記ＲＦ電源のＲＦ電圧を前記高電圧高周波パルス発生回路により発生された高周波パルスに重畳する重畳装置とを含み、前記高周波パルスに前記ＲＦ電圧を重畳した合成電圧を前記高電圧高周波パルスとして印加するので、表面修飾処理により好適な液中プラズマ放電を発生させて、前記難溶解性粉体の表面修飾処理の高速化且つ大量処理化を実現することのできる粉体可溶化装置を提供実現することができる。 According to a fourteenth aspect of the present invention, the high-voltage high-frequency pulse generator includes an RF power source, a superimposing device that superimposes an RF voltage of the RF power source on a high-frequency pulse generated by the high-voltage high-frequency pulse generator circuit, And the composite voltage obtained by superimposing the RF voltage on the high-frequency pulse is applied as the high-voltage high-frequency pulse, so that a suitable in-liquid plasma discharge is generated by a surface modification treatment to modify the surface of the hardly soluble powder. It is possible to provide and realize a powder solubilizing apparatus capable of realizing high-speed processing and mass processing.

本発明の一実施形態に係るＣＮＴ可溶化装置の概略構成図である。It is a schematic block diagram of the CNT solubilization apparatus which concerns on one Embodiment of this invention. 前記実施形態に用いる高電圧高周波パルスの波形図である。It is a wave form diagram of the high voltage high frequency pulse used for the said embodiment. 前記実施形態におけるＣＮＴ表面修飾処理制御部の概略構成ブロック図である。It is a schematic block diagram of the CNT surface modification processing control unit in the embodiment. 前記ＣＮＴ表面修飾処理制御部における表面修飾処理手順を示すフローチャートである。It is a flowchart which shows the surface modification process procedure in the said CNT surface modification process control part. 本発明の別の実施形態に係る粉体可溶化装置の概略構成図である。It is a schematic block diagram of the powder solubilization apparatus which concerns on another embodiment of this invention. 図５の粉体可溶化装置におけるプラズマ発生機構を説明するための等価回路図である。It is an equivalent circuit diagram for demonstrating the plasma generation mechanism in the powder solubilization apparatus of FIG.

以下、本発明に係るプラズマ処理装置の実施形態を添付図面に基づいて詳細に説明する。 Embodiments of a plasma processing apparatus according to the present invention will be described below in detail with reference to the accompanying drawings.

図１は本発明の一実施形態に係るＣＮＴ可溶化装置の概略構成を示す。
本実施形態に係るＣＮＴ可溶化装置は本発明の可溶化方法に基づきＣＮＴ（難溶解性粉体）を水に溶解させて、表面修飾処理を行うための親水化処理装置である。本発明に係る可溶化方法によれば、水（溶媒）３１を収容した溶媒槽１の水中に２つの液中電極１４を配置し、溶媒槽１内の溶媒の水面にＣＮＴ７を供給し、ＣＮＴ７により構成された粉体電極と液中電極１４との電極間に高電圧高周波パルスを印加して高電圧放電による液中プラズマ放電２７を発生させてＣＮＴ７を水中に溶解させることができる。 FIG. 1 shows a schematic configuration of a CNT solubilizer according to an embodiment of the present invention.
The CNT solubilizer according to the present embodiment is a hydrophilization treatment device for performing surface modification treatment by dissolving CNT (hardly soluble powder) in water based on the solubilization method of the present invention. According to the solubilization method according to the present invention, the two submerged electrodes 14 are arranged in the water of the solvent tank 1 containing water (solvent) 31, CNT 7 is supplied to the water surface of the solvent in the solvent tank 1, and CNT 7 A high-voltage high-frequency pulse is applied between the powder electrode and the submerged electrode 14 configured as described above to generate a submerged plasma discharge 27 by high-voltage discharge and dissolve the CNT 7 in water.

溶媒槽１の開放口には、中央部が開口した蓋体２が取り付けられている。溶媒槽１内に溶媒の水３１がほぼ満たされ、溶媒槽１上部に蓋体２がシール部材２６を介してねじ部２５により螺着して冠着されている。蓋体２の中央部は水面３２側に垂下された筒形状を有する。各液中電極１４は蓋体２の開口に向けて配置されている。蓋体２の開口周辺からは、液中電極１４の配線が導出されている。溶媒槽１及び蓋体２は絶縁性樹脂により形成されている。液中電極１４は導電線の先端部分を上方に向けた針状電極を形成している。導電線の両端以外はポリテトラフルオロエチレン（ＰＴＦＥ）製の絶縁カバー材１５により覆われて、水中及び蓋体２を経て外延されている。液中電極１４の先端は水面３２から５〜２０ｍｍの位置に設定されている。 A lid 2 having an opening at the center is attached to the opening of the solvent tank 1. The solvent tank 1 is almost filled with solvent water 31, and the lid body 2 is screwed onto the upper part of the solvent tank 1 by a screw portion 25 via a seal member 26 and is attached. The center part of the lid body 2 has a cylindrical shape that hangs down to the water surface 32 side. Each submerged electrode 14 is arranged toward the opening of the lid 2. From the periphery of the opening of the lid 2, the wiring of the submerged electrode 14 is led out. The solvent tank 1 and the lid body 2 are formed of an insulating resin. The submerged electrode 14 forms a needle-like electrode with the tip of the conductive wire facing upward. Except for both ends of the conductive wire, it is covered with an insulating cover material 15 made of polytetrafluoroethylene (PTFE), and is extended outwardly through water and the lid 2. The tip of the in-liquid electrode 14 is set at a position of 5 to 20 mm from the water surface 32.

蓋体２の開口部分にはＣＮＴ材を収容する導電性筒体３が嵌着されている。筒体３の上側部にはＣＮＴ導入口９が開口されており、ＣＮＴ導入口９にＣＮＴ搬入部６の搬入管８が連通接続されている。ＣＮＴ搬入部６には開閉蓋１２が取着されており、開閉蓋１２を開いてＣＮＴ７をＣＮＴ搬入部６内に投入可能になっている。ＣＮＴは水等に難溶解性を有しており、水面３２上に浮遊した状態で供給される。搬入管８はＣＮＴ導入口９に向けて緩やかに湾曲した管路を形成し、投入されたＣＮＴ７が自然落下により搬入管８に沿って筒体３に徐々に導入されていく。搬入管８のＣＮＴ導入口９手前側にはＣＮＴ投入検知センサ２４が設置されている。ＣＮＴ投入検知センサ２４は、ＣＮＴの通過を検出して、センサ付近における搬入管８内の残存ＣＮＴの有無を検出する。 A conductive cylinder 3 that accommodates the CNT material is fitted into the opening of the lid 2. A CNT inlet 9 is opened on the upper side of the cylinder 3, and a carry-in tube 8 of the CNT carry-in section 6 is connected to the CNT inlet 9. An open / close lid 12 is attached to the CNT carry-in section 6 so that the CNT 7 can be put into the CNT carry-in section 6 by opening the open / close lid 12. CNT is hardly soluble in water or the like, and is supplied in a floating state on the water surface 32. The carry-in pipe 8 forms a gently curved pipe line toward the CNT introduction port 9, and the introduced CNT 7 is gradually introduced into the cylinder 3 along the carry-in pipe 8 by natural fall. A CNT insertion detection sensor 24 is installed on the front side of the CNT introduction port 9 of the carry-in pipe 8. The CNT insertion detection sensor 24 detects the passage of CNT and detects the presence or absence of residual CNT in the carry-in pipe 8 in the vicinity of the sensor.

筒体３内には、ＣＮＴ導入口９より搬入されたＣＮＴ材を攪拌する導電性攪拌部材４が配設されている。攪拌部材４はコイル状の攪拌翼体を有し、該攪拌翼体の回転軸１９は筒体３を貫通して上方に外延され、連結部材２２を介して駆動モータ２１の回転軸に連結されている。攪拌部材４は縦状に配置されており、その攪拌体の上端部はＣＮＴ導入口９に付近に達し、終端部５は蓋体２の中央部を経て水面３２に所定距離（５〜２０ｍｍ）を隔てて空中に配置されている。ＣＮＴ材はＣＮＴ導入口９より攪拌体全体を覆う充填状態まで搬入可能である。攪拌部材４を毎秒数回転の回転数で回転させると、その攪拌輸送作用により、筒体３内に充填されたＣＮＴ１０は水面３２側に向けて供給される。 A conductive stirring member 4 for stirring the CNT material carried from the CNT introduction port 9 is disposed in the cylindrical body 3. The agitating member 4 has a coiled agitating blade body, and the rotating shaft 19 of the agitating blade body extends upward through the cylindrical body 3 and is connected to the rotating shaft of the drive motor 21 via a connecting member 22. ing. The stirring member 4 is arranged vertically, the upper end portion of the stirring body reaches the vicinity of the CNT inlet 9, and the end portion 5 passes through the central portion of the lid body 2 to the water surface 32 at a predetermined distance (5 to 20 mm). It is arranged in the air with a gap. The CNT material can be carried in from the CNT introduction port 9 to a filling state covering the entire stirring member. When the stirring member 4 is rotated at a rotational speed of several revolutions per second, the CNT 10 filled in the cylindrical body 3 is supplied toward the water surface 32 side by the stirring and transporting action.

本実施形態においては、筒体３内のＣＮＴ材に通電してＣＮＴ自体を粉体電極とすることにより、液中電極１４との間に高電圧高周波パルスを印加して液中プラズマ放電を発生させるプラズマ発生機構を構成している。 In this embodiment, by energizing the CNT material in the cylindrical body 3 and using the CNT itself as a powder electrode, a high-voltage high-frequency pulse is applied between the submerged electrode 14 to generate submerged plasma discharge. The plasma generation mechanism is configured.

図２は高電圧高周波パルス発生装置１７の高電圧高周波パルス波形を示す。図３は本実施形態におけるＣＮＴ表面修飾処理制御部４０の概略構成を示す。
高電圧高周波パルス発生装置１７は、発振器４２の基準周波数に基づき高電圧高周波パルスを発生する高電圧高周波パルス発生回路４１と、ＲＦ電源４３と、ＲＦ電源４３のＲＦ電圧を高電圧高周波パルス発生回路４１により発生された高周波パルスに重畳する重畳装置４４とからなる。重畳装置４４によりＲＦ電源電圧が重畳された高電圧高周波パルスが印加電圧Ｖとして粉体電極と液中電極１４間に印加可能となっている。高電圧高周波パルス発生回路４１は、発振器４２の基準周波数に基づき高周波を発生させ、それを多数個に分周し、且つ位相をずらす分周位相制御回路と、分周位相制御回路の複数個の出力信号をスイッチングして合成し高電圧高周波パルスを生成するスイッチング回路を含む。 FIG. 2 shows a high voltage high frequency pulse waveform of the high voltage high frequency pulse generator 17. FIG. 3 shows a schematic configuration of the CNT surface modification processing control unit 40 in the present embodiment.
The high-voltage high-frequency pulse generator 17 generates a high-voltage high-frequency pulse generation circuit 41 that generates a high-voltage high-frequency pulse based on the reference frequency of the oscillator 42, an RF power source 43, and the RF voltage of the RF power source 43 as a high-voltage high-frequency pulse generation circuit. And a superimposing device 44 that superimposes the high frequency pulse generated by 41. A high-voltage, high-frequency pulse on which the RF power supply voltage is superimposed by the superimposing device 44 can be applied as the applied voltage V between the powder electrode and the submerged electrode 14. The high-voltage, high-frequency pulse generation circuit 41 generates a high frequency based on the reference frequency of the oscillator 42, divides it into a large number and divides the phase, and a plurality of frequency division phase control circuits. It includes a switching circuit that generates a high-voltage high-frequency pulse by switching and combining the output signals.

図２の（２Ａ）、（２Ｂ）は夫々、高電圧高周波パルス発生回路４１、ＲＦ電源４３の電圧波形を示す。同図（２Ｃ）はこれらの出力電圧（Ｖａ、Ｖｂ）を重畳装置４４により合成した合成電圧Ｖの波形を示す。（２Ｂ）及び（２Ｃ）においては（２Ａ）の電圧波形に対し模式的に図示している。 (2A) and (2B) in FIG. 2 show voltage waveforms of the high-voltage and high-frequency pulse generation circuit 41 and the RF power source 43, respectively. FIG. 2C shows a waveform of a combined voltage V obtained by combining these output voltages (Va, Vb) by the superimposing device 44. In (2B) and (2C), the voltage waveform of (2A) is schematically illustrated.

液中プラズマ放電の発生には、高電圧高周波パルス（合成電圧Ｖ）の周波数を高くし、あるいは立ち上がりを急峻にすることにより、効率的に放電発生を誘引することができる。即ち、本実施形態では、液中プラズマ放電発生の効率を高めるために、以下のパルス発生条件に基づいて高電圧高周波パルス（合成電圧Ｖ）が高電圧高周波パルス発生装置１７から出力される。
高電圧高周波パルス発生回路４１の高電圧高周波パルスＶａは１ｋＶ〜２０ｋＶの範囲のいずれかのピーク間電圧値Ｖｐｐに設定される。高電圧高周波パルスＶａの周波数Ｆは、０．１ｋＨｚ〜３００ｋＨｚの範囲のいずれかの周波数値に設定される。高電圧高周波パルスＶａのパルス幅Ｗは、０．１μＳ〜１００μＳの範囲のいずれかのパルス幅値に設定される。ＲＦ電源４３のＲＦ電圧Ｖｂは１３．５６ＭＨｚ、２７．１２ＭＨｚあるいは４０．６８ＭＨｚのいずれかの周波数に基づいて発生される。 In the generation of plasma discharge in the liquid, the generation of the discharge can be efficiently induced by increasing the frequency of the high-voltage high-frequency pulse (synthetic voltage V) or by making the rise steep. That is, in the present embodiment, in order to increase the efficiency of in-liquid plasma discharge generation, a high voltage high frequency pulse (synthetic voltage V) is output from the high voltage high frequency pulse generator 17 based on the following pulse generation conditions.
The high voltage high frequency pulse Va of the high voltage high frequency pulse generating circuit 41 is set to a peak-to-peak voltage value Vpp in the range of 1 kV to 20 kV. The frequency F of the high voltage high frequency pulse Va is set to any frequency value in the range of 0.1 kHz to 300 kHz. The pulse width W of the high voltage high frequency pulse Va is set to any pulse width value in the range of 0.1 μS to 100 μS. The RF voltage Vb of the RF power source 43 is generated based on any frequency of 13.56 MHz, 27.12 MHz, or 40.68 MHz.

高電圧高周波パルス発生装置１７によって発生された合成電圧Ｖは、図１に示すように、接続線１６を通じて液中電極１４と、接続線１８及び導電性リング２０を通じて攪拌部材４に印加されている。筒体３に充填されているＣＮＴ１０全体に与えるように合成電圧Ｖが接続線１８、２３を通じて筒体３にも印加されている。合成電圧Ｖを使用すれば、ＲＦ電圧（高周波電力）によってプラズマ発生が促進され、且つ、高周波パルスによるプラズマ中のラジカルやイオンの誘引を行って、より効率的な液中プラズマ放電を発生させることが可能になる。 As shown in FIG. 1, the synthesized voltage V generated by the high-voltage high-frequency pulse generator 17 is applied to the submerged electrode 14 through the connection line 16, and the stirring member 4 through the connection line 18 and the conductive ring 20. . The composite voltage V is also applied to the cylinder 3 through the connection lines 18 and 23 so as to be applied to the entire CNT 10 filled in the cylinder 3. If the synthesized voltage V is used, plasma generation is promoted by the RF voltage (high frequency power), and radicals and ions in the plasma are attracted by the high frequency pulse to generate more efficient plasma discharge in liquid. Is possible.

上記構成のＣＮＴ可溶化装置において、攪拌部材４の終端部５を液中電極１４の対向電極として、両電極間に高電圧高周波パルス発生装置１７の合成電圧Ｖが印加される。合成電圧Ｖの印加により、水面３２近傍のＣＮＴあるいは水面３２に浮遊するＣＮＴ１１が粉体電極となって、液中電極１４との間で液中プラズマ放電２７を発生させる。液中プラズマ放電２７により液中電極１４の周囲が沸騰状態に達し、Ｈ^＋やＯＨ⁻等のラジカルを含む活性水蒸気２８が生ずる。この活性水蒸気２８及び液中プラズマに接触することにより、浮遊ＣＮＴ粉体はＣＮＴ周囲に水和層が形成され親水化（水溶化）される。活性水蒸気２８は上昇して、水面３２近傍の空中ＣＮＴを通過するので、液面上の空中ＣＮＴも親水化することができる。親水化された修飾ＣＮＴ２９、３０は水中に溶解して自重により溶媒槽１の底部に落下していく。溶媒槽１の底部に堆積した修飾ＣＮＴ３３を回収することにより、修飾ＣＮＴからなる高機能化結合材料を得ることができる。 In the CNT solubilizer having the above-described configuration, the combined voltage V of the high-voltage, high-frequency pulse generator 17 is applied between both electrodes, with the terminal portion 5 of the stirring member 4 as the counter electrode of the submerged electrode 14. By applying the composite voltage V, the CNT near the water surface 32 or the CNT 11 floating on the water surface 32 becomes a powder electrode, and a submerged plasma discharge 27 is generated between the submerged electrode 14. Due to the plasma discharge 27 in the liquid, the periphery of the liquid electrode 14 reaches a boiling state, and active water vapor 28 containing radicals such as H ⁺ and OH ⁻ is generated. By contacting the activated water vapor 28 and the plasma in liquid, the suspended CNT powder is hydrophilized (water-solubilized) by forming a hydrated layer around the CNT. Since the active water vapor 28 rises and passes through the airborne CNTs near the water surface 32, the airborne CNTs on the liquid surface can also be hydrophilized. Hydrophilic modified CNTs 29 and 30 are dissolved in water and fall to the bottom of the solvent tank 1 by their own weight. By recovering the modified CNT 33 deposited on the bottom of the solvent tank 1, a highly functional binding material composed of the modified CNT can be obtained.

上記ＣＮＴ可溶化装置によれば、攪拌部材４によるＣＮＴ材の輸送撹拌を行いながら、水の界面付近において液中プラズマによる親水化処理を行うことができる。従って、上記ＣＮＴ可溶化装置の稼働により、ＣＮＴの表面修飾の連続処理化及び高速化を実現でき、しかも大量に修飾ＣＮＭを生成して高機能化結合材料の低価格化を実現することができる。 According to the CNT solubilizing apparatus, the hydrophilization treatment with plasma in liquid can be performed in the vicinity of the water interface while transporting and stirring the CNT material by the stirring member 4. Therefore, by the operation of the CNT solubilizer, it is possible to realize continuous processing and speeding up of the surface modification of CNT, and also to produce a large amount of modified CNM and to realize a low cost of highly functional binding material. .

上記ＣＮＴ可溶化装置は図３に示すＣＮＴ表面修飾処理制御部４０による表面修飾処理の連続処理管理機能を具備する。 The CNT solubilizer has a continuous process management function of the surface modification process by the CNT surface modification process control unit 40 shown in FIG.

ＣＮＴ表面修飾処理制御部４０はＣＰＵ、表面修飾処理制御プログラムを記憶するプログラム記憶メモリのＲＯＭ及びワーキングメモリのＲＡＭからなるマイクロプロセッサにより構成されている。ＣＮＴ表面修飾処理制御部４０には、ＣＮＴ投入検知センサ２４及び起動ＳＷ４５による入力信号が入力される。起動ＳＷ４５の押下により表面修飾処理制御プログラムを起動させることができる。また、ＣＮＴ表面修飾処理制御部４０には、各種データの設定入力を行うためのキー入力装置４６が接続されており、キー入力装置４６による設定データは液晶表示装置４７に外部出力されて表示される。 The CNT surface modification processing control unit 40 includes a microprocessor including a CPU, a ROM of a program storage memory for storing a surface modification processing control program, and a RAM of a working memory. Input signals from the CNT insertion detection sensor 24 and the activation SW 45 are input to the CNT surface modification processing control unit 40. The surface modification processing control program can be activated by pressing the activation SW 45. The CNT surface modification processing control unit 40 is connected to a key input device 46 for inputting various data settings. The setting data from the key input device 46 is output to the liquid crystal display device 47 and displayed. The

搬入管８途中に設置されたＣＮＴ投入検知センサ２４によって、搬入管８内の残存ＣＮＴがないことを検出してから一定時間ｔの経過によりＣＮＴ導入口９付近の投入ＣＮＴ１３がすべて筒体３内に投入されたと判断され、その判断時点から、筒体３内の一定量のＣＮＴ１０がすべて親水化されるまでの所要処理時間Ｔデータを予め計測して取得しておき、所要処理時間Ｔデータに基づき表面修飾処理の連続処理管理が実行される。終了検知時間（ｔ＋Ｔ）は終了検知タイマ設定モードにおいてキー入力装置４６による設定入力操作により予め前記ＲＯＭに設定、記憶される。 The CNT input detection sensor 24 installed in the middle of the carry-in pipe 8 detects that there is no remaining CNT in the carry-in pipe 8, and all the charged CNTs 13 near the CNT introduction port 9 are all within the cylinder 3 after a lapse of a predetermined time t. The required processing time T data from when the determination is made until the fixed amount of CNT 10 in the cylindrical body 3 is all hydrophilized is measured and acquired in advance, and the required processing time T data is obtained. Based on this, continuous process management of the surface modification process is executed. The end detection time (t + T) is preset and stored in the ROM by a setting input operation by the key input device 46 in the end detection timer setting mode.

外部出力手段として、高電圧高周波パルス発生回路４１、ＲＦ電源４３及び撹拌部材４用の駆動モータ２１がＣＮＴ表面修飾処理制御部４０に接続されている。ＣＮＴ表面修飾処理制御部４０は高電圧高周波パルス発生回路４１、ＲＦ電源４３及び駆動モータ２１に夫々、駆動制御信号を出力する。ＣＮＴ表面修飾処理制御部４０には、表面修飾処理の開始及び終了状態、撹拌部材４の駆動状態、ＣＮＴ投入有無を夫々、報知するＬＥＤランプからなる稼働状態表示器４８が接続され、各稼働状態に応じたランプ点灯信号が稼働状態表示器４８に出力される。 As external output means, a high voltage high frequency pulse generation circuit 41, an RF power source 43, and a drive motor 21 for the stirring member 4 are connected to the CNT surface modification processing control unit 40. The CNT surface modification processing control unit 40 outputs drive control signals to the high-voltage, high-frequency pulse generation circuit 41, the RF power source 43, and the drive motor 21, respectively. The CNT surface modification processing control unit 40 is connected to an operation state indicator 48 including an LED lamp for notifying the start and end states of the surface modification treatment, the driving state of the stirring member 4, and whether or not CNT is inserted, A lamp lighting signal corresponding to is output to the operating state indicator 48.

図４は表面修飾処理制御プログラムに基づき実行される表面修飾処理手順を示す。
表面修飾処理の実行に先立ち、終了検知タイマ設定モードにおいて、キー入力装置４６を操作して、表面修飾処理の終了検知時間（ｔ＋Ｔ）の入力設定が行われる。次に、起動ＳＷ４５のＯＮにより表面修飾処理制御プログラムが起動すると、ＣＮＴの投入済みか否か判断する(ステップＳ１、Ｓ２)。ＣＮＴ投入検知センサ２４がＯＮか否かによりＣＮＴの投入済みが確認される。ＣＮＴ投入検知センサ２４がＯＮしていないとき、ＣＮＴ材投入未了と判断して稼働状態表示器４８のＣＮＴ材投入未了ランプの点灯で報知される。ＣＮＴ材投入未了時には、開閉蓋１２を開いてＣＮＴ７をＣＮＴ搬入部６内に投入し、ＣＮＴ投入検知センサ２４がＯＮするまで筒体３内に充填する(ステップＳ８)。 FIG. 4 shows a surface modification processing procedure executed based on the surface modification processing control program.
Prior to the execution of the surface modification process, in the end detection timer setting mode, the key input device 46 is operated to set the input of the end detection time (t + T) of the surface modification process. Next, when the surface modification processing control program is activated by turning on the activation SW 45, it is determined whether or not CNT has been inserted (steps S1 and S2). Whether or not CNT has been inserted is confirmed by whether or not the CNT insertion detection sensor 24 is ON. When the CNT input detection sensor 24 is not ON, it is determined that the CNT material has not been input, and a notification is given by the lighting of the CNT material input incomplete lamp of the operation status indicator 48. When the introduction of the CNT material has not been completed, the opening / closing lid 12 is opened and the CNT 7 is introduced into the CNT carry-in section 6 and filled into the cylinder 3 until the CNT insertion detection sensor 24 is turned on (step S8).

ＣＮＴ投入検知センサ２４がＯＮし、ＣＮＴの投入済みが確認されたとき(ステップＳ２)、高電圧高周波パルス発生回路４１及びＲＦ電源４３を駆動し、合成電圧Ｖを発生させる(ステップＳ３)。同時に、駆動モータ２１を駆動して撹拌部材４を回転させる(ステップＳ４)。高電圧高周波パルス（合成電圧Ｖ）の発生及び撹拌部材４の回転開始により、水面３２近傍あるいは水面３２に浮遊するＣＮＴ１１が粉体電極となって、液中電極１４との間で液中プラズマ放電２７を発生させるプラズマ発生機構により、筒体３内のＣＮＴ１０が攪拌部材４による撹拌輸送作用を受けて速やかに親水化されていく。 When the CNT input detection sensor 24 is turned on and it is confirmed that CNT has been input (step S2), the high-voltage high-frequency pulse generation circuit 41 and the RF power source 43 are driven to generate a composite voltage V (step S3). At the same time, the drive motor 21 is driven to rotate the stirring member 4 (step S4). Due to the generation of the high-voltage high-frequency pulse (synthetic voltage V) and the rotation of the stirring member 4, the CNT 11 floating near the water surface 32 or on the water surface 32 becomes a powder electrode, and the plasma discharge in liquid between the liquid electrode 14. Due to the plasma generation mechanism that generates 27, the CNTs 10 in the cylinder 3 are quickly hydrophilized by the stirring and transporting action of the stirring member 4.

筒体３内のＣＮＴ１０の表面修飾処理が進行し、ＣＮＴ投入検知センサ２４がＯＦＦとなると、ＣＰＵのタイマ機能が作動して、予め設定された終了検知時間（ｔ＋Ｔ）の計時が開始され、終了検知時間（ｔ＋Ｔ）の経過により投入ＣＮＴの全量の表面修飾処理の終了と判断し(ステップＳ５)、高電圧高周波パルスの発生及び撹拌部材４の回転を停止する(ステップＳ６、Ｓ７)。表面修飾処理の終了時には稼働状態表示器４８の終了ランプの点灯で報知される。 When the surface modification process of the CNT 10 in the cylindrical body 3 proceeds and the CNT insertion detection sensor 24 is turned off, the timer function of the CPU is activated to start and measure the preset end detection time (t + T). When the detection time (t + T) has elapsed, it is determined that the surface modification process for the entire amount of input CNT has been completed (step S5), and the generation of the high-voltage high-frequency pulse and the rotation of the stirring member 4 are stopped (steps S6 and S7). At the end of the surface modification process, a notification is given by turning on the end lamp of the operating state indicator 48.

上記表面修飾処理手順により、表面修飾処理の連続処理管理が行われるので、液中プラズマによる親水化処理を自動化することができ、修飾ＣＮＴの高速且つ大量生成工程の省人化及び低コスト化を図ることができる。 Since the surface modification treatment procedure allows continuous treatment management of the surface modification treatment, hydrophilization treatment using in-liquid plasma can be automated, reducing the labor and cost of the modified CNTs at high speed and in large quantities. Can be planned.

上記実施形態においては、ＣＮＴに限らず、例えば、カーボンナノボール（ＣＮＢ）やフラーレン等の導電性物質からなるＣＮＭ等の難溶解性粉体に対する表面修飾処理を行うことができる。 In the above embodiment, not only CNT but also surface modification treatment can be performed on hardly soluble powder such as CNM made of conductive material such as carbon nanoball (CNB) or fullerene.

図５は本発明の別の実施形態に係る粉体可溶化装置の概略構成を示す。
上記実施形態の粉体可溶化装置は、難溶解性粉体自体に通電し粉体電極として使用するので、ＣＮＴ、ＣＮＢ、フラーレン等の導電性物質からなるＣＮＭ等の難溶解性粉体に対する表面修飾処理に好適であるが、図５は、ダイヤモンドライクカーボン（ＤＬＣ）、ナノダイヤパウダー等の非導電性物質からなる難溶解性粉体に対する表面修飾処理に好適な粉体可溶化装置を示す。以下の実施形態はＤＬＣの水溶化の一例である。 FIG. 5 shows a schematic configuration of a powder solubilizer according to another embodiment of the present invention.
Since the powder solubilization apparatus of the above embodiment is used as a powder electrode by energizing the hardly soluble powder itself, the surface with respect to the hardly soluble powder such as CNM made of a conductive substance such as CNT, CNB, fullerene, etc. Although suitable for the modification treatment, FIG. 5 shows a powder solubilization apparatus suitable for the surface modification treatment of a hardly soluble powder made of a non-conductive substance such as diamond-like carbon (DLC) or nanodiamond powder. The following embodiment is an example of water-solubilization of DLC.

ボトル形状の溶媒槽５０上方の筒部５３には蓋体７０が冠着されている。溶媒の水５１が筒部５３根元付近まで満たされている。４個の液中電極７１は水面５２に向けて配置されている。液中電極７１の配線は溶媒槽５０の側部から漏水防止シール材７３を介して外方に導出されている。溶媒槽５０及び蓋体７０は絶縁性樹脂により形成されている。液中電極７１は、液中電極１４と同様に、導電線の先端部分を上方に向けた針状電極を形成している。導電線の両端以外はＰＴＦＥ製の絶縁カバー材７２により覆われて、水中及び溶媒槽５０を経て外延されている。液中電極７１の先端は水面５２から５〜２０ｍｍの位置に設定されている。 A lid 70 is attached to the cylindrical portion 53 above the bottle-shaped solvent tank 50. The solvent water 51 is filled up to the vicinity of the root of the cylindrical portion 53. The four in-liquid electrodes 71 are arranged toward the water surface 52. The wiring of the submerged electrode 71 is led out from the side portion of the solvent tank 50 through the water leakage preventing sealing material 73. The solvent tank 50 and the lid 70 are made of an insulating resin. The submerged electrode 71 forms a needle-like electrode with the end portion of the conductive wire facing upward, like the submerged electrode 14. Except both ends of the conductive wire, it is covered with an insulating cover material 72 made of PTFE, and is extended through the water and the solvent tank 50. The tip of the submerged electrode 71 is set at a position of 5 to 20 mm from the water surface 52.

筒部５３の側面にはＤＬＣ導入口５８が開口されており、ＤＬＣ導入口５８にＤＬＣ搬入路５９が連通接続されている。ＤＬＣ搬入路５９の上部は開口されており、ＤＬＣ６７を溶媒槽５０内に投入可能になっている。ＤＬＣは水等に難溶解性を有しており、水面５２上に浮遊した状態で供給される。 A DLC introduction port 58 is opened on the side surface of the cylindrical portion 53, and a DLC carry-in path 59 is connected to the DLC introduction port 58. An upper portion of the DLC carry-in path 59 is opened, and the DLC 67 can be put into the solvent tank 50. DLC has poor solubility in water or the like, and is supplied in a state of floating on the water surface 52.

筒部５３内には、ＤＬＣ搬入路５９より搬入されたＤＬＣ材を攪拌する攪拌部材５５が配設されている。攪拌部材５５は積層状に配置した３枚のプロペラ型攪拌翼体からなり、該攪拌翼体の導電性回転軸５４は蓋体７０を貫通して上方に外延され、連結部材７６を介して駆動モータ５７の回転軸に連結されている。攪拌部材５５は縦状に配置されており、最上部の攪拌翼体はＤＬＣ導入口５８付近に位置する。回転軸５４の終端には、多数の貫通穴が形成されたメッシュ状対向電極５６が取着されている。該貫通穴はＤＬＣ粉体が通過可能な大きさ（１ｍｍ径）を有する。対向電極５６は平坦な円板形状を有し、その平坦面を水面５２に並行に、所定距離（５〜２０ｍｍ）を隔てて空中に配置されている。ＤＬＣ６７はＤＬＣ搬入路５９より搬入して攪拌体全体を覆う充填状態まで搬入可能である。攪拌部材５５を毎秒数回転の回転数で回転させると、その攪拌輸送作用により、筒部５３内に充填されたＤＬＣ７８はメッシュ状対向電極５６の貫通穴を通過して水面５２側に向けて供給される。 An agitating member 55 for agitating the DLC material carried in from the DLC carry-in path 59 is disposed in the cylindrical portion 53. The stirring member 55 is composed of three propeller-type stirring blades arranged in a stacked manner, and the conductive rotating shaft 54 of the stirring blade body extends outwardly through the lid 70 and is driven through a connecting member 76. It is connected to the rotating shaft of the motor 57. The stirring member 55 is arranged vertically, and the uppermost stirring blade body is located in the vicinity of the DLC inlet 58. A mesh-like counter electrode 56 having a large number of through holes is attached to the end of the rotating shaft 54. The through hole has a size (1 mm diameter) through which DLC powder can pass. The counter electrode 56 has a flat disk shape, and the flat surface is disposed in the air in parallel with the water surface 52 with a predetermined distance (5 to 20 mm) therebetween. The DLC 67 can be carried in from the DLC carry-in path 59 to a filling state covering the entire stirring body. When the stirring member 55 is rotated at a rotational speed of several revolutions per second, the DLC 78 filled in the cylindrical portion 53 passes through the through hole of the mesh-like counter electrode 56 and is supplied toward the water surface 52 side by the stirring and transporting action. Is done.

液中電極７４と対向電極５６の電極間には、高電圧高周波パルス発生装置６０により、前記実施形態の高電圧高周波パルス発生装置１７によって発生された合成電圧と同様にして、合成電圧Ｖが発生されて印加される。即ち、図５に示すように、合成電圧Ｖが、接続線６１〜６４を通じて各液中電極７１と、接続線６５、導電性リング６６及び回転軸５４を通じて対向電極５６に印加されている。 A composite voltage V is generated between the in-liquid electrode 74 and the counter electrode 56 by the high-voltage high-frequency pulse generator 60 in the same manner as the composite voltage generated by the high-voltage high-frequency pulse generator 17 of the above embodiment. Applied. That is, as shown in FIG. 5, the composite voltage V is applied to each of the liquid electrodes 71 through the connection lines 61 to 64, and to the counter electrode 56 through the connection line 65, the conductive ring 66, and the rotating shaft 54.

図６は図５の実施形態におけるプラズマ発生機構を説明するための等価回路図である。
図５の実施形態においては、液中電極７１と対向電極５６との電極間に高電圧高周波パルス（合成電圧Ｖ）を印加したとき、対向電極５６と液面５２間に介在するＤＬＣ粉体の誘電率により形成される誘電体層によって粉体電極を構成して、高電圧放電による液中プラズマを発生させるプラズマ発生機構を構成している。 FIG. 6 is an equivalent circuit diagram for explaining the plasma generation mechanism in the embodiment of FIG.
In the embodiment of FIG. 5, when a high-voltage high-frequency pulse (synthetic voltage V) is applied between the in-liquid electrode 71 and the counter electrode 56, the DLC powder interposed between the counter electrode 56 and the liquid surface 52 A powder electrode is constituted by a dielectric layer formed by a dielectric constant to constitute a plasma generation mechanism for generating in-liquid plasma by high voltage discharge.

上記構成の粉体可溶化装置において、攪拌部材５５の終端部に設けた対向電極５６と液中電極７１の電極間に高電圧高周波パルス発生装置６０の合成電圧Ｖが印加される。合成電圧Ｖの印加により、対向電極５６の下方で水面５２上に介在するＤＬＣ層７７による誘電体７９が粉体電極を構成して、前記プラズマ発生機構に基づき、液中電極７１との間で液中プラズマ放電７４を発生させる。液中プラズマ放電７４により液中電極７１の周囲が沸騰状態に達し、Ｈ^＋やＯＨ⁻のラジカルを含む活性水蒸気７５が生ずる。この活性水蒸気７５及び液中プラズマに接触することにより、水面５２上に浮遊するＤＬＣ粉体はＤＬＣ周囲に水和層が形成され親水化（水溶化）される。活性水蒸気７５は上昇して、水面５２近傍の空中ＤＬＣを通過するので、液面上の空中ＤＬＣも親水化することができる。親水化された修飾ＤＬＣ６８、６９は水中に溶解して自重により溶媒槽５０の底部に落下していく。溶媒槽５０の底部に堆積した修飾ＤＬＣを回収することにより、修飾ＤＬＣからなる高機能化結合材料を得ることができる。 In the powder solubilizer having the above-described configuration, the composite voltage V of the high-voltage and high-frequency pulse generator 60 is applied between the counter electrode 56 provided at the end portion of the stirring member 55 and the electrode 71 in the liquid. By applying the composite voltage V, the dielectric 79 by the DLC layer 77 interposed on the water surface 52 below the counter electrode 56 constitutes a powder electrode, and between the submerged electrode 71 based on the plasma generation mechanism. An in-liquid plasma discharge 74 is generated. The liquid plasma discharge 74 causes the periphery of the liquid electrode 71 to reach a boiling state, and active water vapor 75 containing radicals of H ⁺ and OH ⁻ is generated. By contacting the active water vapor 75 and the plasma in liquid, the DLC powder floating on the water surface 52 is hydrophilized by forming a hydrated layer around the DLC. Since the active water vapor 75 rises and passes through the air DLC near the water surface 52, the air DLC on the liquid surface can also be hydrophilized. The modified DLC 68 and 69 having been made hydrophilic are dissolved in water and fall to the bottom of the solvent tank 50 by their own weight. By collecting the modified DLC deposited on the bottom of the solvent tank 50, a highly functional binding material composed of the modified DLC can be obtained.

前記プラズマ発生機構に基づいて、高電圧放電による液中プラズマを発生させるので、液中電極７１及び対向電極５６を配置するだけの簡単な構成で、非導電性の難溶解性粉体を対向電極５６と液面５２間に介在するように、攪拌部材５５の撹拌輸送作用により供給することにより、ＤＬＣ等の非導電性物質の表面修飾処理を液中プラズマによって高速化して連続処理し、大量の表面修飾処理を低コストで行うことができる。
る。 Since in-liquid plasma is generated by high-voltage discharge based on the plasma generation mechanism, the non-electroconductive and hardly soluble powder can be applied to the counter electrode with a simple configuration by simply arranging the in-liquid electrode 71 and the counter electrode 56. 56 and the liquid level 52 are supplied by the stirring and transporting action of the stirring member 55, so that the surface modification treatment of the non-conductive substance such as DLC is accelerated by the plasma in the liquid and continuously processed. Surface modification treatment can be performed at low cost.
The

図１及び図５の実施形態では溶媒に水３１、５１を用いた水溶化の例を示したが、アンモニア水を溶媒に使用してアミノ基により修飾した修飾ＣＮＭなどを生成することができる。例えば、ＣＮＴにアミノ基により修飾することにより、ポリアミドとの分散性に優れた修飾ＣＮＴからなる高機能化結合材料を高速且つ大量に製造することができる。 In the embodiment of FIGS. 1 and 5, an example of water solubilization using water 31 and 51 as a solvent has been shown, but modified CNM modified with an amino group can be generated using aqueous ammonia as a solvent. For example, by modifying CNT with an amino group, a highly functional binding material composed of modified CNT excellent in dispersibility with polyamide can be produced at high speed and in large quantities.

本発明は、上記実施形態や変形例に限定されるものではなく、本発明の技術的思想を逸脱しない範囲における種々変形例、設計変更などをその技術的範囲内に包含するものであることは云うまでもない。 The present invention is not limited to the above-described embodiments and modifications, and includes various modifications and design changes within the technical scope without departing from the technical idea of the present invention. Needless to say.

本発明によれば、難溶解性粉体の親水化のための表面修飾処理を液中プラズマによって高速化して連続処理し、大量の表面修飾処理を低コストで行うことができるので、例えばＣＮＭ材の利用分野、特に高機能化結合材料への応用範囲の拡大を図ることができる。 According to the present invention, the surface modification treatment for hydrophilizing the hardly soluble powder can be performed continuously at a high speed by plasma in liquid, and a large amount of surface modification treatment can be performed at low cost. The application range to the high-performance bonding material can be expanded.

１溶媒槽
２蓋体
３筒体
４攪拌部材
５終端部
６ＣＮＴ搬入部
７ＣＮＴ
８搬入管
９ＣＮＴ導入口
１０ＣＮＴ
１１ＣＮＴ
１２開閉蓋
１３ＣＮＴ
１４液中電極
１５絶縁カバー材
１６接続線
１７高電圧高周波パルス発生装置
１８接続線
１９回転軸
２０導電性リング
２１駆動モータ
２２連結部材
２３接続線
２４ＣＮＴ投入検知センサ
２５ねじ部
２６シール部材
２７液中プラズマ放電
２８活性水蒸気
２９修飾ＣＮＴ
３０修飾ＣＮＴ
３１水
３２水面
３３修飾ＣＮＴ
４０ＣＮＴ表面修飾処理制御部
４１高電圧高周波パルス発生回路
４２発振器
４３ＲＦ電源
４４重畳装置
４５起動ＳＷ
４６キー入力装置
４７液晶表示装置
４８稼働状態表示器
５０溶媒槽
５１水
５２水面
５３筒部
５４回転軸
５５攪拌部材
５６対向電極
５７駆動モータ
５８ＤＬＣ導入口
５９ＤＬＣ搬入路
６０高電圧高周波パルス発生装置
６１接続線
６２接続線
６３接続線
６４接続線
６５接続線
６６導電性リング
６７ＤＬＣ
６８修飾ＤＬＣ
６９修飾ＤＬＣ
７０蓋体
７１液中電極
７２絶縁カバー材
７３漏水防止シール材
７４液中プラズマ放電
７５活性水蒸気
７６連結部材
７７ＤＬＣ
７８ＤＬＣ
７９誘電体 DESCRIPTION OF SYMBOLS 1 Solvent tank 2 Lid body 3 Cylinder body 4 Stirring member 5 Termination part 6 CNT carrying-in part 7 CNT
8 Carry-in tube 9 CNT inlet 10 CNT
11 CNT
12 Open / close lid 13 CNT
14 Electrode 15 in liquid 15 Insulating cover material 16 Connection line 17 High-voltage high-frequency pulse generator 18 Connection line 19 Rotating shaft 20 Conductive ring 21 Drive motor 22 Connection member 23 Connection line 24 CNT insertion detection sensor 25 Screw part 26 Seal member 27 Liquid Medium plasma discharge 28 Active water vapor 29 Modified CNT
30 Modified CNT
31 Water 32 Water surface 33 Modified CNT
40 CNT surface modification processing control unit 41 High voltage high frequency pulse generation circuit 42 Oscillator 43 RF power supply 44 Superimposing device 45 Start SW
46 Key input device 47 Liquid crystal display device 48 Operating state indicator 50 Solvent tank 51 Water 52 Water surface 53 Tube portion 54 Rotating shaft 55 Stirring member 56 Counter electrode 57 Drive motor 58 DLC inlet 59 DLC carry-in path 60 High voltage high frequency pulse generator 61 Connection Line 62 Connection Line 63 Connection Line 64 Connection Line 65 Connection Line 66 Conductive Ring 67 DLC
68 Modified DLC
69 Modified DLC
70 Lid 71 Electrode in liquid 72 Insulating cover material 73 Water leakage prevention seal material 74 Plasma discharge in liquid 75 Active water vapor 76 Connecting member 77 DLC
78 DLC
79 Dielectric

Claims

溶媒を収容した溶媒槽の液中に少なくとも１つの液中電極を配置し、前記溶媒槽内の前記溶媒の液面に難溶解性粉体を供給し、前記難溶解性粉体により構成された粉体電極と前記液中電極との電極間に高電圧高周波パルスを印加して高電圧放電による液中プラズマを発生させ、前記難溶解性粉体を前記液中に溶解させることを特徴とする粉体可溶化方法。 At least one submerged electrode is arranged in the liquid of the solvent tank containing the solvent, and the hardly soluble powder is supplied to the liquid surface of the solvent in the solvent tank, and is configured by the hardly soluble powder. A high-voltage high-frequency pulse is applied between the electrode between the powder electrode and the submerged electrode to generate submerged plasma by high-voltage discharge, and the hardly soluble powder is dissolved in the submerged liquid. Powder solubilization method.

前記難溶解性粉体が非導電性物質からなり、前記液中電極に対して前記溶媒の液面を介して対向電極を配置し、前記対向電極と前記液面間に前記難溶解性粉体を供給し、前記液中電極と前記対向電極との電極間に前記高電圧高周波パルスを印加したとき、前記対向電極と前記液面間に介在する前記難溶解性粉体により形成される誘電体層により前記粉体電極を構成して、前記高電圧放電による液中プラズマを発生させる請求項１に記載の粉体可溶化方法。 The hardly soluble powder is made of a non-conductive substance, and a counter electrode is disposed through the liquid level of the solvent with respect to the in-liquid electrode, and the hardly soluble powder is interposed between the counter electrode and the liquid level. Is formed by the hardly soluble powder interposed between the counter electrode and the liquid surface when the high-voltage high-frequency pulse is applied between the electrode in the liquid and the counter electrode. The powder solubilization method according to claim 1, wherein the powder electrode is constituted by a layer to generate in-liquid plasma by the high voltage discharge.

前記難溶解性粉体を撹拌する撹拌部材を前記溶媒槽の液面近傍に配置し、前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加し、前記撹拌部材により撹拌しながら前記難溶解性粉体を前記液面側に供給する請求項２に記載の粉体可溶化方法。 An agitating member for agitating the hardly soluble powder is disposed in the vicinity of the liquid surface of the solvent tank, and the high-voltage, high-frequency pulse is applied using the terminal portion of the agitating member as the counter electrode, while agitating by the agitating member. The powder solubilization method according to claim 2, wherein the hardly soluble powder is supplied to the liquid surface side.

前記難溶解性粉体が、カーボンナノボール（ＣＮＢ）、単層又は多層のカーボンナノチューブ（ＣＮＴ）、フラーレン等の導電性物質又はダイヤモンドライクカーボン（ＤＬＣ）、ナノダイヤパウダー等の非導電性物質からなる請求項１、２又は３に記載の粉体可溶化方法。 The insoluble powder is made of a conductive material such as carbon nanoball (CNB), single-walled or multi-walled carbon nanotube (CNT), fullerene, or non-conductive material such as diamond-like carbon (DLC) or nanodiameter powder. Item 4. The powder solubilization method according to Item 1, 2, or 3.

前記溶媒が、水等の水酸基を含む液体、あるいはアンモニア水等のアミノ基を含む液体のいずれかからなる請求項１〜４のいずれかに記載の粉体可溶化方法。 The powder solubilization method according to any one of claims 1 to 4, wherein the solvent is one of a liquid containing a hydroxyl group such as water or a liquid containing an amino group such as aqueous ammonia.

前記高電圧高周波パルスは、１ｋＶ〜２０ｋＶの範囲のいずれかのピーク間電圧値を有する請求項１〜５のいずれかに記載の粉体可溶化方法。 The powder solubilization method according to any one of claims 1 to 5, wherein the high-voltage high-frequency pulse has a peak-to-peak voltage value in a range of 1 kV to 20 kV.

前記高電圧高周波パルスは、０．１ｋＨｚ〜３００ｋＨｚの範囲のいずれかの周波数を有する請求項１〜６のいずれかに記載の粉体可溶化方法。 The powder solubilization method according to any one of claims 1 to 6, wherein the high-voltage high-frequency pulse has any frequency within a range of 0.1 kHz to 300 kHz.

前記高電圧高周波パルスは、０．１μＳ〜１００μＳの範囲のいずれかのパルス幅を有する請求項１〜６のいずれかに記載の粉体可溶化方法。 The powder solubilization method according to any one of claims 1 to 6, wherein the high-voltage high-frequency pulse has any pulse width in a range of 0.1 µS to 100 µS.

前記高電圧高周波パルスは、高周波パルスにＲＦ電圧を重畳した合成電圧からなる請求項１〜８のいずれかに記載の粉体可溶化方法。 The powder solubilization method according to any one of claims 1 to 8, wherein the high-voltage high-frequency pulse includes a synthesized voltage obtained by superimposing an RF voltage on the high-frequency pulse.

溶媒を収容した溶媒槽と、前記溶媒槽の液中に配置した少なくとも１つの液中電極と、前記液中電極に対向して配置した少なくとも１つの対向電極と、前記溶媒槽内の前記溶媒の液面に難溶解性粉体を供給する難溶解性粉体供給部と、前記難溶解性粉体により構成された粉体電極と前記液中電極との電極間に高電圧高周波パルスを印加する高電圧高周波パルス発生装置とを有し、前記電極間に前記高電圧高周波パルスを印加して高電圧放電を発生させ、前記難溶解性粉体を前記液中に溶解させることを特徴とする粉体可溶化装置。 A solvent tank containing a solvent, at least one submerged electrode disposed in the liquid of the solvent tank, at least one counter electrode disposed opposite to the submerged electrode, and the solvent in the solvent tank. A high-voltage, high-frequency pulse is applied between the poorly soluble powder supply unit for supplying the hardly soluble powder to the liquid surface, and the electrode between the powder electrode made of the hardly soluble powder and the in-liquid electrode. A high-voltage high-frequency pulse generator, applying the high-voltage high-frequency pulse between the electrodes to generate a high-voltage discharge, and dissolving the hardly soluble powder in the liquid Body solubilizer.

前記液中電極に対して前記溶媒の液面を介して前記対向電極を配置し、前記電極間に前記難溶解性粉体供給部により非導電性物質からなる前記難溶解性粉体を供給し、前記液中電極と前記対向電極との電極間に前記高電圧高周波パルスを印加したとき、前記難溶解性粉体が、前記対向電極と前記液面間に介在する前記難溶解性粉体により形成される誘電体層により前記粉体電極を構成して、前記高電圧放電による液中プラズマを発生させる請求項１０に記載の粉体可溶化装置。 The counter electrode is disposed through the liquid surface of the solvent with respect to the submerged electrode, and the hardly soluble powder made of a non-conductive substance is supplied between the electrodes by the hardly soluble powder supply unit. When the high-voltage, high-frequency pulse is applied between the electrode in the liquid and the counter electrode, the hardly soluble powder is caused by the hardly soluble powder interposed between the counter electrode and the liquid surface. The powder solubilizer according to claim 10, wherein the powder electrode is constituted by the formed dielectric layer, and plasma in liquid by the high voltage discharge is generated.

前記溶媒槽の液面近傍に配置され、前記難溶解性粉体を撹拌する撹拌部材を備え、前記撹拌部材の終端部を前記対向電極として前記高電圧高周波パルスを印加し、前記撹拌部材により撹拌しながら前記難溶解性粉体を前記液面側に供給する請求項１０又は１１に記載の粉体可溶化装置。 A stirring member that is disposed in the vicinity of the liquid surface of the solvent tank and stirs the hardly soluble powder. The high-voltage, high-frequency pulse is applied using the terminal portion of the stirring member as the counter electrode, and stirring is performed by the stirring member. The powder solubilizer according to claim 10 or 11, wherein the hardly soluble powder is supplied to the liquid surface side.

前記高電圧高周波パルス発生装置は、基本高周波信号を複数に分周すると共に位相を複数段にずらしたスイッチング信号に基づき直流電力をスイッチングして得られたパルス電圧を合成した高周波パルスを発生させる高周波パルス発生回路からなる請求項１０、１１又は１２に記載の粉体可溶化装置。 The high-voltage high-frequency pulse generator generates a high-frequency pulse that synthesizes a pulse voltage obtained by switching DC power based on a switching signal in which a basic high-frequency signal is divided into a plurality of phases and a phase is shifted to a plurality of stages. The powder solubilizer according to claim 10, 11 or 12, comprising a pulse generation circuit.

前記高電圧高周波パルス発生装置は、ＲＦ電源と、前記ＲＦ電源のＲＦ電圧を前記高電圧高周波パルス発生回路により発生された高周波パルスに重畳する重畳装置とを含み、前記高周波パルスに前記ＲＦ電圧を重畳した合成電圧を前記高電圧高周波パルスとして印加する請求項１０〜１３のいずれかに記載の粉体可溶化装置。 The high-voltage high-frequency pulse generator includes an RF power source and a superimposing device that superimposes an RF voltage of the RF power source on a high-frequency pulse generated by the high-voltage high-frequency pulse generator circuit, and the RF voltage is applied to the high-frequency pulse. The powder solubilizer according to any one of claims 10 to 13, wherein the superimposed composite voltage is applied as the high-voltage high-frequency pulse.