JPH08133716A - Carbon nanocapsule and its production - Google Patents
Carbon nanocapsule and its productionInfo
- Publication number
- JPH08133716A JPH08133716A JP6301399A JP30139994A JPH08133716A JP H08133716 A JPH08133716 A JP H08133716A JP 6301399 A JP6301399 A JP 6301399A JP 30139994 A JP30139994 A JP 30139994A JP H08133716 A JPH08133716 A JP H08133716A
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- Prior art keywords
- calcium
- carbon
- substance
- sulfur
- nanocapsules
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カーボンナノカプセル
及びその製造方法に関するもので、エレクトロニクス産
業などの広い分野で使用されるカーボンナノカプセル及
びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon nanocapsule and a method for producing the same, and more particularly to a carbon nanocapsule used in a wide field such as the electronics industry and a method for producing the same.
【０００２】[0002]
【従来の技術】最近脚光を浴びているものに、カーボン
クラスタ、いわゆるサッカーボール状カーボンＣ60、Ｃ
70や、フラーレンや、カーボンナノチューブがある。こ
れらは何れも黒鉛のアーク放電などで作られるが、生産
規模が小さく且つ得られたスス状炭素物質中に数％しか
含まれていないため高価であり、またスス状炭素物質か
らの分離も液体クロマトグラフィ等機器分析に頼るとこ
ろが多く手間暇がかかり、せいぜい研究者が研究規模で
その機能を追求しているのが現状である。2. Description of the Related Art Carbon clusters, so-called soccer ball-like carbons C 60 and C, have been recently spotlighted.
There are 70 , fullerenes, and carbon nanotubes. All of these are produced by arc discharge of graphite, etc., but they are expensive because the production scale is small and the obtained soot-like carbon material contains only a few%, and the separation from the soot-like carbon material is also a liquid. Many of them rely on instrumental analysis such as chromatography, which takes time and labor, and at the present time, researchers are pursuing their functions on a research scale at best.
【０００３】[0003]
【発明が解決しようとする課題】上記したように、これ
らのカーボンクラスタは、その生産規模が小さく且つ得
られたごく微量のスス状炭素物質中に数％しか含まれて
いないため、工業規模の生産で歩留まりよく簡単に製造
され得ることが求められている。そこで、本発明の目的
は、カーボンナノカプセルを工業規模で生産する方法を
提供するとともに、得られたカーボンナノカプセルを提
供することである。As described above, since these carbon clusters have a small production scale and contain only a few% in the obtained trace amount of soot-like carbonaceous material, they have an industrial scale. There is a demand for high yield in production and easy manufacture. Therefore, an object of the present invention is to provide a method for producing carbon nanocapsules on an industrial scale, and to provide the obtained carbon nanocapsules.
【０００４】[0004]
【課題を解決するための手段】本発明のカーボンナノカ
プセルは、上記目的を達成すべく、炭素化又は黒鉛化可
能で、硫化カルシウム又はカルシウム物質及び硫黄物質
を含む有機物を、７００〜１０００℃の温度で一次焼成
し、次いで１４００℃以上の温度で二次焼成してなるも
のであることを特徴とする。ここで、二次焼成の温度は
１４００〜２５００℃の範囲であることが好ましい。ま
た、前記二次焼成で得られた炭素材料に超音波振動を与
えてカーボンナノカプセルを分離せしめることが好まし
い。In order to achieve the above object, the carbon nanocapsule of the present invention can be carbonized or graphitized and contains calcium sulfide or an organic substance containing a calcium substance and a sulfur substance at 700 to 1000 ° C. It is characterized by being primarily fired at a temperature and then secondarily fired at a temperature of 1400 ° C. or higher. Here, the temperature of the secondary firing is preferably in the range of 1400 to 2500 ° C. Further, it is preferable that the carbon nanocapsules are separated by applying ultrasonic vibration to the carbon material obtained by the secondary firing.
【０００５】前記カルシウム物質が、カルシウム並びに
塩化カルシウム、炭酸カルシウム、酸化カルシウム及び
水酸化カルシウムからなるカルシウム化合物から選ばれ
た少なくとも一種であり又前記硫黄物質が、硫黄並びに
硫酸ジメチル、硫酸ジエチル、ジメチルスルホキシド、
スルホラン、硫化ナトリウム、水硫化ナトリウム及び硫
酸ナトリウムからなる硫黄化合物から選ばれた少なくと
も一種であることが好ましい。The calcium substance is at least one selected from calcium and calcium compounds consisting of calcium chloride, calcium carbonate, calcium oxide and calcium hydroxide, and the sulfur substance is sulfur and dimethyl sulfate, diethyl sulfate and dimethyl sulfoxide. ,
It is preferably at least one selected from the sulfur compounds consisting of sulfolane, sodium sulfide, sodium hydrosulfide and sodium sulfate.
【０００６】また、本発明のカーボンナノカプセルの製
造方法は、炭素化又は黒鉛化可能な有機物に硫化カルシ
ウムをカルシウム換算で１〜５０００ｐｐｍ又はカルシ
ウム物質をカルシウム換算で１〜５０００ｐｐｍ及び硫
黄物質を硫黄換算で５〜１００００ｐｐｍの量で添加し
た材料を不活性雰囲気中で７００〜１０００℃の温度で
一次焼成し、次いで同じ雰囲気中又は真空中で１４００
℃以上の温度で二次焼成し、前記材料の表面にカーボン
ナノカプセルを生成させることをも包含する。ここで、
二次焼成の温度は１４００〜２５００℃の範囲であるこ
とが好ましい。Further, the method for producing carbon nanocapsules of the present invention is characterized in that an organic substance capable of being carbonized or graphitized contains calcium sulfide in an amount of 1 to 5000 ppm in terms of calcium, or a calcium substance in an amount of 1 to 5000 ppm in terms of calcium, and a sulfur substance in terms of sulfur. The material added in an amount of 5 to 10000 ppm at 1400 is primarily fired at a temperature of 700 to 1000 ° C. in an inert atmosphere, and then 1400 in the same atmosphere or in a vacuum.
It also includes secondary calcination at a temperature of ℃ or more to form carbon nanocapsules on the surface of the material. here,
The temperature of the secondary firing is preferably in the range of 1400 to 2500 ° C.
【０００７】上記製造方法において、前記二次焼成され
た材料に有機溶媒又は純水中で超音波振動を与えてカー
ボンナノカプセルを分離し、回収することが好ましく、
また、前記カルシウム物質が、カルシウム並びに塩化カ
ルシウム、炭酸カルシウム、酸化カルシウム及び水酸化
カルシウムからなるカルシウム化合物から選ばれた少な
くとも一種であり又前記硫黄物質が、硫黄並びに硫酸ジ
メチル、硫酸ジエチル、ジメチルスルホキシド、スルホ
ラン、硫化ナトリウム、水硫化ナトリウム及び硫酸ナト
リウムからなる硫黄化合物から選ばれた少なくとも一種
であることが好ましい。また、上記カーボンナノカプセ
ルの製造方法において、前記一次焼成後の材料に有機溶
媒又は純水中で超音波振動を与えて、材料の表面に形成
した生成物を分離、回収して、この回収物について前記
二次焼成を行ってもよい。In the above manufacturing method, it is preferable that the secondary fired material is subjected to ultrasonic vibration in an organic solvent or pure water to separate and recover the carbon nanocapsules.
Further, the calcium substance is at least one selected from calcium compounds consisting of calcium and calcium chloride, calcium carbonate, calcium oxide and calcium hydroxide, and the sulfur substance is sulfur and dimethyl sulfate, diethyl sulfate, dimethyl sulfoxide, It is preferably at least one selected from the sulfur compounds consisting of sulfolane, sodium sulfide, sodium hydrosulfide and sodium sulfate. In the method for producing carbon nanocapsules described above, ultrasonic vibration is applied to the material after the primary firing in an organic solvent or pure water to separate and collect the product formed on the surface of the material, and the collected product For the above, the secondary firing may be performed.
【０００８】本発明では、カーボンナノカプセル成長の
核として硫化カルシウムの存在が重要である。このた
め、硫化カルシウムが母材炭素材料の表面に形成される
必要がある。硫化カルシウムが存在しないとカーボンナ
ノカプセルは発生しない。これらの化合物がカルシウム
換算で５０００ｐｐｍを越える量であると、カーボンナ
ノカプセルの発生が少なくなること、カーボンナノカプ
セルと余剰のカルシウム化合物、硫黄化合物との分離回
収が必要になる等の問題を生じる。In the present invention, the presence of calcium sulfide is important as a nucleus for growth of carbon nanocapsules. Therefore, calcium sulfide needs to be formed on the surface of the base carbon material. Carbon nanocapsules do not occur in the absence of calcium sulfide. If the amount of these compounds exceeds 5000 ppm in terms of calcium, the generation of carbon nanocapsules is reduced, and problems such as the need to separate and recover the carbon nanocapsules from excess calcium compounds and sulfur compounds arise.
【０００９】本発明のカーボンナノカプセルは、より具
体的には、次のようにして生成され得る。例えば、ＰＡ
Ｎ，レーヨン、フェノール、ピッチ等のような炭素化又
は黒鉛化可能な有機物で、硫化カルシウムをカルシウム
換算で１〜５０００ｐｐｍ又はカルシウム若しくはその
化合物をカルシウム換算で１〜５０００ｐｐｍ及び硫黄
若しくはその化合物を硫黄換算で５〜１００００ｐｐｍ
含んでいる有機材料を繊維状、シート状、ペレット状又
は粉状等に賦形し、必要に応じ、酸素雰囲気下で２００
〜３００℃の温度で前処理した後、Ｎ2 、Ａｒ又はＨｅ
等の不活性雰囲気中で７００〜１０００℃、好ましくは
１０００℃前後の温度で一次焼成し、次いで同様な雰囲
気中又は真空中で約１４００℃以上の温度、好ましくは
約１４００〜２５００℃の温度で二次焼成し、繊維状、
シート状、ペレット状又は粉状等の炭素材料の表面に、
多面体であって、そのそれぞれの面が四角形、五角形、
六角形等の多角形の偏平面が重なり合った層状又はシー
ト状のグラフェンシートからなる構造を備えたカーボン
ナノカプセルを生成せしめる。また、前記二次焼成され
た炭素材料にアルコール、アセトンなどの有機溶媒又は
純水中で超音波振動を与えて炭素材料からカーボンナノ
カプセルを分離し、カーボンナノカプセルを回収する。
二次焼成を行った後、超音波を掛けるだけで得られるの
で、簡単にかつ大量に生産可能である。More specifically, the carbon nanocapsules of the present invention can be produced as follows. For example, PA
An organic substance that can be carbonized or graphitized, such as N, rayon, phenol, pitch, etc., and calcium sulfide is 1 to 5000 ppm in terms of calcium, or calcium or a compound thereof is 1 to 5000 ppm in terms of calcium, and sulfur or a compound thereof is in terms of sulfur. 5 to 10,000 ppm
The contained organic material is shaped into a fibrous, sheet-shaped, pellet-shaped or powder-shaped material, and if necessary, 200
After pre-treatment at a temperature of ~300 ℃, N 2, Ar or He
Etc. in an inert atmosphere such as 700 to 1000 ° C., preferably around 1000 ° C., and then in a similar atmosphere or in vacuum at a temperature of about 1400 ° C. or higher, preferably about 1400 to 2500 ° C. Secondary firing, fibrous,
On the surface of carbon material such as sheet, pellet or powder,
A polyhedron, each side of which is a square, a pentagon,
A carbon nanocapsule having a structure composed of a layered or sheet-shaped graphene sheet in which polygonal planes such as a hexagon are overlapped is produced. Further, ultrasonic vibration is applied to the secondarily fired carbon material in an organic solvent such as alcohol or acetone, or pure water to separate the carbon nanocapsules from the carbon material and recover the carbon nanocapsules.
Since it can be obtained simply by applying ultrasonic waves after the secondary firing, it can be easily and mass-produced.
【００１０】上記のようにして得られたカーボンナノカ
プセルは、例えば、約４０〜２００ｎｍの大きさに成長
した多面体形状のナノカプセルであり、上記したよう
に、その各面が四角形や五角形や六角形等の多角形の偏
平面が重なり合ったグラフェンシートからなる構造を備
えた入れ子構造の多面体であって、その閉じた中空部分
に金属結晶等を内包せしめることができるので、エレク
トロニクス産業及び化学工業などの広い分野で使用され
得る。また、かかるカーボンナノカプセルの回収方法と
しては、カーボンナノカプセルを濾過分離した後、溶媒
の蒸発除去、遠心分離処理、凝集剤を用いる沈降分離・
濾過分離処理等により行うことができる。The carbon nanocapsules obtained as described above are, for example, polyhedral nanocapsules grown to a size of about 40 to 200 nm, and as described above, each surface has a square shape, a pentagonal shape, or a hexagonal shape. It is a polyhedron of nesting structure with a structure consisting of graphene sheets in which polygonal planes such as polygons are overlapped, and it is possible to enclose metal crystals etc. in the closed hollow part, so electronics industry and chemical industry etc. Can be used in a wide range of fields. Further, as a method for recovering such carbon nanocapsules, after the carbon nanocapsules are separated by filtration, the solvent is removed by evaporation, the centrifugal separation treatment, and the sedimentation separation using a coagulant.
It can be performed by filtration separation treatment or the like.
【００１１】前記の一次焼成工程において、８００℃程
度の焼成段階で、グラフェンシートになったものも存在
するが、大部分はアモルファスな状態である。しかしな
がら、８００℃程度で一次焼成した後、このグラフェン
シートを分離・回収し、二次焼成処理してカーボンナノ
カプセルを生成せしめてもよい。ここで、グラフェンシ
ートとは、黒鉛の単結晶が層状又はシート状になったも
のを意味する。In the above-mentioned primary firing step, there are some graphene sheets which have been fired at about 800 ° C., but most of them are in an amorphous state. However, after the primary firing at about 800 ° C., the graphene sheet may be separated and collected, and the secondary firing treatment may be performed to generate the carbon nanocapsules. Here, the graphene sheet means a layered or sheet-shaped single crystal of graphite.
【００１２】[0012]
【作用】本発明によれば、硫化カルシウム又はカルシウ
ム物質及び硫黄物質を含んだ炭素化又は黒鉛化可能な有
機物を用いて、二段階焼成法によりカーボンナノカプセ
ルの工業規模の生産が可能となる。According to the present invention, carbon nanocapsules can be produced on an industrial scale by a two-step firing method using an organic substance containing calcium sulfide or a calcium substance and a sulfur substance that can be carbonized or graphitized.
【００１３】[0013]
【実施例】以下、本発明を実施例に基づいて詳細に説明
する。 （実施例１）カルシウム５ｐｐｍ、硫黄１０００ｐｐｍ
を含むＰＡＮ繊維織物を約３００℃の酸素雰囲気で前処
理し、次いでＮ2 雰囲気下、圧力＋２〜＋５０ｍｍＨ2
Ｏ に制御した炉中で８００℃で焼成し、さらにＮ2 で
置換後１〜０．１Ｔｏｒｒに制御した炉中で１５００℃
で処理し、長辺が約５０〜２００ｎｍで、５〜１０層の
グラフェンシートからなる面を有する多面体形状のカー
ボンナノカプセルを大量に表面に有する母材炭素材料を
生成させた。かくして生成されたカーボンナノカプセル
を表面に有する母材炭素材料をアセトン浴中に浸漬し、
超音波振動（２０〜３０ＫＨｚ）を与えて母材炭素材料
表面からカーボンナノカプセルを分離し、母材炭素材料
を濾過除去した後、溶剤を乾燥除去して、カーボンナノ
カプセルを得た。かくして得られたカプセルの収量は、
母材炭素材料に対して０．１重量％以上であった。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. (Example 1) 5 ppm of calcium and 1000 ppm of sulfur
The PAN fiber woven fabric containing C is pretreated in an oxygen atmosphere at about 300 ° C., and then under a N 2 atmosphere, the pressure is +2 to +50 mmH 2.
Baking at 800 ° C. in a furnace controlled to O 2 , further replacing with N 2 and 1500 ° C. in a furnace controlled to 1 to 0.1 Torr
To produce a base carbon material having a large amount of polyhedral carbon nanocapsules having a long side of about 50 to 200 nm and a surface composed of 5 to 10 layers of graphene sheets. The base material carbon material having the carbon nanocapsules thus produced on the surface is immersed in an acetone bath,
Ultrasonic vibration (20 to 30 KHz) was applied to separate the carbon nanocapsules from the surface of the base carbon material, the base carbon material was filtered off, and then the solvent was dried to obtain carbon nanocapsules. The yield of the capsules thus obtained is
It was 0.1% by weight or more with respect to the base material carbon material.
【００１４】次に、本発明のカーボンナノカプセルの構
造について、試料として、炭素繊維（ピッチ系、１０μ
ｍφ：日本カーボン（株）製）を用いて上記実施例記載
の方法と同様にして得たカーボンナノカプセルを使用
し、ＴＥＭ／トプコン社製００２Ｂの電子顕微鏡で観察
した。図１乃至３は、カーボンナノカプセルの構造につ
いて示す電子顕微鏡写真である。図１は、２０００℃で
焼成処理を行ったピッチ系炭素繊維の表面上に気相成長
したと考えられる三次元的に閉じた多層巨大フラーレン
（キューブカプセル）を示している。ほぼ直角にカーブ
したグラフェンシートが数十層重なって殻を作っている
様子が観察された。大きさは４０ｎｍから１００ｎｍ程
度のものが多くみられ、グラフェンシートも数層のもの
から数十層のものまで観察された。Next, regarding the structure of the carbon nanocapsule of the present invention, carbon fiber (pitch type, 10 μm) was used as a sample.
mφ: manufactured by Nippon Carbon Co., Ltd., and the carbon nanocapsules obtained in the same manner as in the above-described example were used, and observed with a TEM / 002B electron microscope manufactured by Topcon. 1 to 3 are electron micrographs showing the structure of carbon nanocapsules. FIG. 1 shows a three-dimensionally closed multi-layered giant fullerene (cube capsule) which is considered to have undergone vapor phase growth on the surface of a pitch-based carbon fiber that has been subjected to a firing treatment at 2000 ° C. It was observed that dozens of graphene sheets that were curved at approximately right angles were stacked to form a shell. The size is often about 40 nm to 100 nm, and graphene sheets having several layers to several tens of layers have been observed.
【００１５】図１中の殻の部分（ａ）と白く抜けた中心
部分（ｂ）との領域からのミクロ回折（ｍｉｃｒｏ ｄ
ｉｆｆｒａｃｔｉｏｎ）を行った。その結果、（ａ）領
域では、００２反射のみが強く現れているが、中心部領
域（ｂ）では１００と１１０反射のみのリングパターン
が観察された。このことは、中心部はグラフェンシート
に垂直な方向から観察していることを示している。つま
り、中心部にも写真面の上下にグラファイト層が存在し
ており、グラファイト殻はキュービックなカプセル形状
を形成しているものと考えられる。また、（ｂ）領域の
グラファイト殻はかなり乱層構造の状態であった。Microdiffraction (micro d) from the region of the shell portion (a) and the white central portion (b) in FIG.
effectration) was performed. As a result, in the area (a), only the 002 reflection strongly appeared, but in the central area (b), a ring pattern with only 100 and 110 reflections was observed. This indicates that the center part is observed from the direction perpendicular to the graphene sheet. That is, it is considered that the graphite layers also exist above and below the photographic surface in the central portion, and the graphite shell forms a cubic capsule shape. In addition, the graphite shell in the region (b) had a considerably disordered structure.
【００１６】図２は、カーボンナノカプセルの各面が６
層のグラフェンシートからなっているＣａＳ結晶を内包
したナノカプセルの構造を示す電子顕微鏡写真であり、
一部中空の部分が存在していることが分かる。即ち、カ
プセル生成機構として、まず周りのグラファイト殻が生
成したことを示している。図３はカプセルの成長途中の
段階を示すものであり、アモルファス粒子の表面には微
小なグラファイト結晶が成長している。微結晶が電子線
の照射で徐々に成長し行く様子が捉えられた。FIG. 2 shows that each surface of the carbon nanocapsule has 6
2 is an electron micrograph showing the structure of a nanocapsule encapsulating a CaS crystal composed of a single-layer graphene sheet,
It can be seen that there is a partially hollow portion. That is, it is shown that the surrounding graphite shell was first generated as the capsule formation mechanism. FIG. 3 shows a stage during the growth of the capsule, in which minute graphite crystals are growing on the surface of the amorphous particles. It was observed that the microcrystals gradually grew by electron beam irradiation.
【００１７】[0017]
【発明の効果】以上詳細に説明したように、本発明によ
れば、カーボンナノカプセルが、硫化カルシウム又はカ
ルシウム物質及び硫黄物質を含む炭素化又は黒鉛化可能
な有機物を使用して二段階焼成により工業規模で生産さ
れ得る。かかる材料は、エレクトロニクス産業等の分野
において、例えば走査型トンネル顕微鏡用のチップ、エ
ネルギー貯蔵用機器の電極、極細電子回路用の軽量部品
やワイヤー等の素材としての活用が期待され、又異物質
内包カーボンナノカプセルとしてエレクトロニクス産業
における素材としての応用が期待され、その工業的有用
性は極めて高い。As described in detail above, according to the present invention, the carbon nanocapsules are subjected to two-step firing using a carbonizable or graphitizable organic substance containing calcium sulfide or a calcium substance and a sulfur substance. It can be produced on an industrial scale. Such a material is expected to be used as a material for a chip for a scanning tunneling microscope, an electrode of an energy storage device, a lightweight component for an ultrafine electronic circuit, a wire, or the like in a field such as an electronics industry, and inclusion of foreign substances. The carbon nanocapsule is expected to be applied as a material in the electronics industry, and its industrial utility is extremely high.
【図１】本発明のカーボンナノカプセルの構造について
示す電子顕微鏡写真。FIG. 1 is an electron micrograph showing the structure of carbon nanocapsules of the present invention.
【図２】本発明のカーボンナノカプセルの構造について
示す電子顕微鏡写真。FIG. 2 is an electron micrograph showing the structure of carbon nanocapsules of the present invention.
【図３】本発明のカーボンナノカプセルの成長途中の段
階を示す電子顕微鏡写真。FIG. 3 is an electron micrograph showing a stage during the growth of carbon nanocapsules of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 楠 美智子 愛知県名古屋市熱田区六野二丁目４番１号 財団法人ファインセラミックスセンター 内 (72)発明者 幾原 雄一 愛知県名古屋市熱田区六野二丁目４番１号 財団法人ファインセラミックスセンター 内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michiko Kusunoki 2-4-1, Rokuno, Atsuta-ku, Nagoya-shi, Aichi Prefectural Fine Ceramics Center (72) Inventor Yuichi Ikuhara Rokuno, Atsuta-ku, Nagoya-shi, Aichi 2-4-1, Fine Ceramics Center Foundation
Claims (8)
ム又はカルシウム物質及び硫黄物質を含む有機物を、７
００〜１０００℃の温度で一次焼成し、次いで１４００
℃以上の温度で二次焼成してなるカーボンナノカプセ
ル。1. An organic substance which can be carbonized or graphitized and contains calcium sulfide or a calcium substance and a sulfur substance.
Primary calcination at a temperature of 00 to 1000 ° C., then 1400
Carbon nanocapsules formed by secondary firing at a temperature of ℃ or above.
ム又はカルシウム物質及び硫黄物質を含む有機物を、７
００〜１０００℃の温度で一次焼成し、次いで１４００
℃以上の温度で二次焼成して得られた炭素材料に超音波
振動を与えてカーボンナノカプセルを分離せしめてなる
カーボンナノカプセル。2. An organic substance which can be carbonized or graphitized and contains calcium sulfide or a calcium substance and a sulfur substance,
Primary calcination at a temperature of 00 to 1000 ° C., then 1400
Carbon nanocapsules obtained by subjecting a carbon material obtained by secondary firing at a temperature of ℃ or more to ultrasonic vibration to separate the carbon nanocapsules.
に塩化カルシウム、炭酸カルシウム、酸化カルシウム及
び水酸化カルシウムからなるカルシウム化合物から選ば
れた少なくとも一種であり又前記硫黄物質が、硫黄並び
に硫酸ジメチル、硫酸ジエチル、ジメチルスルホキシ
ド、スルホラン、硫化ナトリウム、水硫化ナトリウム及
び硫酸ナトリウムからなる硫黄化合物から選ばれた少な
くとも一種であることを特徴とする請求項１又は２に記
載のカーボンナノカプセル。3. The calcium substance is at least one selected from calcium and calcium compounds consisting of calcium chloride, calcium carbonate, calcium oxide and calcium hydroxide, and the sulfur substance is sulfur and dimethyl sulfate, diethyl sulfate, The carbon nanocapsule according to claim 1 or 2, wherein the carbon nanocapsule is at least one selected from sulfur compounds consisting of dimethyl sulfoxide, sulfolane, sodium sulfide, sodium hydrosulfide and sodium sulfate.
ルシウムをカルシウム換算で１〜５０００ｐｐｍ又はカ
ルシウム物質をカルシウム換算で１〜５０００ｐｐｍ及
び硫黄物質を硫黄換算で５〜１００００ｐｐｍの量で添
加した材料を不活性雰囲気中で７００〜１０００℃の温
度で一次焼成し、次いで同じ雰囲気中又は真空中で１４
００℃以上の温度で二次焼成し、前記材料の表面にカー
ボンナノカプセルを生成させることを特徴とするカーボ
ンナノカプセルの製造方法。4. A material obtained by adding calcium sulfide in an amount of 1 to 5000 ppm in terms of calcium, or a calcium substance in an amount of 1 to 5000 ppm in terms of calcium, and a sulfur substance in an amount of 5 to 10,000 ppm in terms of sulfur, to a carbonizable or graphitizable organic substance. Primary calcination at a temperature of 700-1000 ° C. in an inert atmosphere, then 14 in the same atmosphere or in vacuum
A method for producing carbon nanocapsules, which comprises performing secondary calcination at a temperature of 00 ° C. or higher to generate carbon nanocapsules on the surface of the material.
溶媒又は純水中で超音波振動を与えてカーボンナノカプ
セルを分離し、回収することを特徴とする請求項４記載
のカーボンナノカプセルの製造方法。5. The carbon nanocapsule according to claim 4, wherein the material obtained by the secondary firing is subjected to ultrasonic vibration in an organic solvent or pure water to separate and recover the carbon nanocapsule. Manufacturing method.
に塩化カルシウム、炭酸カルシウム、酸化カルシウム及
び水酸化カルシウムからなるカルシウム化合物から選ば
れた少なくとも一種であり又前記硫黄物質が、硫黄並び
に硫酸ジメチル、硫酸ジエチル、ジメチルスルホキシ
ド、スルホラン、硫化ナトリウム、水硫化ナトリウム及
び硫酸ナトリウムからなる硫黄化合物から選ばれた少な
くとも一種であることを特徴とする請求項４又は５に記
載のカーボンナノカプセルの製造方法。6. The calcium substance is at least one selected from calcium and calcium compounds consisting of calcium chloride, calcium carbonate, calcium oxide and calcium hydroxide, and the sulfur substance is sulfur and dimethyl sulfate, diethyl sulfate, The method for producing carbon nanocapsules according to claim 4 or 5, wherein the carbon nanocapsules are at least one selected from sulfur compounds consisting of dimethyl sulfoxide, sulfolane, sodium sulfide, sodium hydrosulfide and sodium sulfate.
℃の範囲にあることを特徴とする請求項４〜６のいずれ
か一項に記載のカーボンナノカプセルの製造方法。7. The secondary firing temperature is 1400 to 2500.
It is in the range of ° C, The manufacturing method of the carbon nanocapsule according to any one of claims 4 to 6.
水中で超音波振動を与えて、材料の表面に形成した生成
物を分離、回収して、この回収物について前記二次焼成
を行うことを特徴とする請求項４〜７のいずれか一項に
記載のカーボンナノカプセルの製造方法。8. The material after the primary firing is subjected to ultrasonic vibration in an organic solvent or pure water to separate and recover the product formed on the surface of the material, and the recovered material is subjected to the secondary firing. It carries out, The manufacturing method of the carbon nanocapsule as described in any one of Claims 4-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30139994A JP3159880B2 (en) | 1994-11-10 | 1994-11-10 | Carbon nanocapsule and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30139994A JP3159880B2 (en) | 1994-11-10 | 1994-11-10 | Carbon nanocapsule and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JPH08133716A true JPH08133716A (en) | 1996-05-28 |
| JP3159880B2 JP3159880B2 (en) | 2001-04-23 |
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ID=17896405
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30139994A Expired - Fee Related JP3159880B2 (en) | 1994-11-10 | 1994-11-10 | Carbon nanocapsule and method for producing the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342839A (en) * | 2002-05-23 | 2003-12-03 | Mitsubishi Heavy Ind Ltd | Carbon nano fibrin |
| JP2005219998A (en) * | 2004-02-09 | 2005-08-18 | Osaka Gas Co Ltd | Amorphous carbon namo-capsule and its production method |
| US7727414B2 (en) * | 2005-11-30 | 2010-06-01 | Industrial Technology Research Institute | Heat transfer fluids with carbon nanocapsules |
| JP2013500922A (en) * | 2009-07-31 | 2013-01-10 | マサチューセッツ インスティテュート オブ テクノロジー | Systems and methods for the formation of carbon-based nanostructures |
| US9663368B2 (en) | 2010-10-28 | 2017-05-30 | Massachusetts Institute Of Technology | Carbon-based nanostructure formation using large scale active growth structures |
| US10195797B2 (en) | 2013-02-28 | 2019-02-05 | N12 Technologies, Inc. | Cartridge-based dispensing of nanostructure films |
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|---|---|---|---|---|
| JP2003191767A (en) | 2001-12-26 | 2003-07-09 | Honda Motor Co Ltd | Two-wheel/four-wheel drive switching device for vehicle |
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1994
- 1994-11-10 JP JP30139994A patent/JP3159880B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342839A (en) * | 2002-05-23 | 2003-12-03 | Mitsubishi Heavy Ind Ltd | Carbon nano fibrin |
| JP2005219998A (en) * | 2004-02-09 | 2005-08-18 | Osaka Gas Co Ltd | Amorphous carbon namo-capsule and its production method |
| JP4557562B2 (en) * | 2004-02-09 | 2010-10-06 | 大阪瓦斯株式会社 | Amorphous carbon nanocapsule and method for producing the same |
| US7727414B2 (en) * | 2005-11-30 | 2010-06-01 | Industrial Technology Research Institute | Heat transfer fluids with carbon nanocapsules |
| JP2013500922A (en) * | 2009-07-31 | 2013-01-10 | マサチューセッツ インスティテュート オブ テクノロジー | Systems and methods for the formation of carbon-based nanostructures |
| US10087079B2 (en) | 2009-07-31 | 2018-10-02 | Massachusetts Institute Of Technology | Systems and methods related to the formation of carbon-based nanostructures |
| US9663368B2 (en) | 2010-10-28 | 2017-05-30 | Massachusetts Institute Of Technology | Carbon-based nanostructure formation using large scale active growth structures |
| US10195797B2 (en) | 2013-02-28 | 2019-02-05 | N12 Technologies, Inc. | Cartridge-based dispensing of nanostructure films |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3159880B2 (en) | 2001-04-23 |
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