JP4817103B2 - Method for producing boron nitride nanotubes - Google Patents
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本発明は、窒化ホウ素ナノチューブ及びその製造方法に関する。 The present invention relates to a boron nitride nanotube and a method for producing the same.
窒化ホウ素は、高強度、耐酸化性、熱的・化学的安定性などの優れた特性を有しているため、そのナノチューブは、電子デバイスや機能性ナノ材料としての価値を高めている。今まで、窒化ホウ素ナノチューブは、窒化ホウ素を充填したタングステン棒をプラズマ放電させる方法（たとえば、非特許文献１参照。）、ホウ化ハフニウム棒をプラズマ反応させる方法（例えば、非特許文献２参照。）、六方晶系窒化ホウ素を高圧窒素中でレーザー加熱する方法（例えば、非特許文献３参照。）、鉄触媒の存在のもとでホウ酸−活性炭−多層カーボンナノチューブを原料としアンモニア中で加熱する方法（例えば、非特許文献４参照。）、六方晶系窒化ホウ素とタンタルを窒素ガス雰囲気中でアーク放電させる方法（例えば、非特許文献５参照。）等により製造されている。しかしながら、これらの方法は、信頼性のある大量合成法とは言えず、未だスケールアップのための合成ルートが確立されていない。 Since boron nitride has excellent properties such as high strength, oxidation resistance, thermal and chemical stability, the nanotubes are increasing the value as electronic devices and functional nanomaterials. Until now, for boron nitride nanotubes, a tungsten rod filled with boron nitride is plasma-discharged (see, for example, Non-Patent Document 1), and a hafnium boride rod is plasma-reacted (for example, see Non-Patent Document 2). A method of laser heating hexagonal boron nitride in high-pressure nitrogen (for example, see Non-Patent Document 3), heating in ammonia using boric acid-activated carbon-multi-walled carbon nanotubes in the presence of an iron catalyst And a method of arc discharge of hexagonal boron nitride and tantalum in a nitrogen gas atmosphere (for example, see Non-Patent Document 5). However, these methods are not reliable mass synthesis methods, and a synthesis route for scale-up has not yet been established.
本発明は、上記の現状に鑑み、毒性が低く、安価な単一の原料を窒化ホウ素源として用いて窒化ホウ素ナノチューブ並びにその製造方法を提供することを目的とする。 An object of the present invention is to provide a boron nitride nanotube and a method for producing the same using a single raw material that is low in toxicity and inexpensive as a boron nitride source.
本発明は、上記の課題を解決するものとして、まず、発明１の窒化ホウ素ナノチューブは、長さ１μｍ以上、外径２０〜１２０ｎｍ、チューブ壁の厚さ３〜２０ｎｍを有することを特徴とする。
発明２は、発明１の窒化ホウ素ナノチューブの製造方法であって、窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを加熱して、フッ化マグネシウムを蒸発させることを特徴とする。
発明３は、発明２の窒化ホウ素ナノチューブの製造方法であって、無水塩化マグネシウム塊を加熱炉の中央部に配置し、テトラフルオロホウ酸アンモニウムを該加熱炉の一端に配置すると共に、前記テトラフルオロホウ酸アンモニウムを配置した方の端から該加熱炉内へ不活性ガスを流しながら、無水塩化マグネシウム塊を７×１０２〜１０×１０２℃に、テトラフルオロホウ酸アンモニウムを３２０±１０℃に加熱することにより、窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを製造した後、第二段階として、ここで製造した前記窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを加熱炉に設置し、不活性ガスを流しながら、１２×１０２〜１６×１０２℃に加熱することにより、フッ化マグネシウムを蒸発させることを特徴とする。
発明４は、発明２又は３の窒化ホウ素ナノチューブの製造方法において、テトラフルオロホウ酸アンモニウムと無水塩化マグネシウムのモル比が３：１〜５：１の範囲であることを特徴とする。
発明５は、発明２から４のいずれかの窒化ホウ素ナノチューブの製造方法において、不活性ガスがアルゴンガスあるいは窒素ガスであることを特徴とする。
In order to solve the above-described problems, the present invention is characterized in that the boron nitride nanotube of the invention 1 has a length of 1 μm or more, an outer diameter of 20 to 120 nm, and a tube wall thickness of 3 to 20 nm.
Invention 2 is a method for producing a boron nitride nanotube according to Invention 1, characterized in that magnesium fluoride nanowires coated with a boron nitride film are heated to evaporate the magnesium fluoride.
Invention 3 is a method for producing boron nitride nanotubes of Invention 2, wherein an anhydrous magnesium chloride lump is disposed in the center of the heating furnace, ammonium tetrafluoroborate is disposed at one end of the heating furnace, and the tetrafluoro While flowing an inert gas into the heating furnace from the end on which the ammonium borate is arranged, the anhydrous magnesium chloride block is set to 7 × 10 2 to 10 × 10 2 ° C, and the ammonium tetrafluoroborate is set to 320 ± 10 ° C. After manufacturing the magnesium fluoride nanowire coated with the boron nitride film by heating, the magnesium fluoride nanowire coated with the boron nitride film manufactured here is installed in a heating furnace as a second step. , while flowing an inert gas, by heating to 12 × 10 2 ~16 × 10 2 ℃, evaporation of magnesium fluoride Characterized in that to.
Invention 4 is characterized in that, in the method for producing boron nitride nanotubes of Invention 2 or 3, the molar ratio of ammonium tetrafluoroborate to anhydrous magnesium chloride is in the range of 3: 1 to 5: 1.
Invention 5 is characterized in that in the method for producing boron nitride nanotubes of any one of Inventions 2 to 4, the inert gas is argon gas or nitrogen gas.
本発明により、長さ１μｍ以上、外径２０〜１２０ｎｍ、チューブ壁の厚さ３〜２０ｎｍを有する窒化ホウ素ナノチューブが実現される。また、本発明の方法により、毒性の低い安全な原料を用いて簡便なプロセスで窒化ホウ素ナノチューブを製造することが出来る。 According to the present invention, a boron nitride nanotube having a length of 1 μm or more, an outer diameter of 20 to 120 nm, and a tube wall thickness of 3 to 20 nm is realized. Further, by the method of the present invention, boron nitride nanotubes can be produced by a simple process using a safe raw material with low toxicity.
本発明の窒化ホウ素ナノチューブは、長さ１μｍ以上、外径２０〜１２０ｎｍ、チューブ壁の厚さ３〜２０ｎｍを有している。該窒化ホウ素ナノチューブの製造方法は、二段階からなり、第１段階では、無水塩化マグネシウム塊を穴の開いたふたを有するアルミナボートに入れ、このアルミナボートを加熱炉の中央部に設置し、該加熱炉の一端にテトラフルオロホウ酸アンモニウムを入れた窒化ホウ素製ボートを配置すると共に、該一端から不活性ガスを流しながら、無水塩化マグネシウム塊を７×１０２〜１０×１０２℃に、テトラフルオロホウ酸アンモニウムを３２０±１０℃に加熱して窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを製造する。
ＮＨ４ＢＦ４ ＋ ２ＭｇＣｌ２ → ＢＮ ＋ ２ＭｇＦ２ ＋ ４ＨＣｌ
The boron nitride nanotube of the present invention has a length of 1 μm or more, an outer diameter of 20 to 120 nm, and a tube wall thickness of 3 to 20 nm. The method for producing the boron nitride nanotubes comprises two stages. In the first stage, an anhydrous magnesium chloride lump is placed in an alumina boat having a lid with a hole, and the alumina boat is installed in the center of a heating furnace. A boron nitride boat containing ammonium tetrafluoroborate is placed at one end of the heating furnace, and while flowing an inert gas from the one end, the anhydrous magnesium chloride mass is brought to 7 × 10 2 to 10 × 10 2 ° C. Magnesium fluoride nanowires coated with a boron nitride film are manufactured by heating ammonium fluoroborate to 320 ± 10 ° C.
NH 4 BF 4 + 2MgCl 2 → BN + 2MgF 2 + 4HCl
このとき、テトラフルオロホウ酸アンモニウムと無水塩化マグネシウムのモル比は３：１〜５：１の範囲であることが好ましい。テトラフルオロホウ酸アンモニウムの量がこの範囲よりも多いと未反応のまま残存するテトラフルオロホウ酸アンモニウムが生成した窒化ホウ素膜を侵食することが懸念される。逆に、テトラフルオロホウ酸アンモニウムの量が上記の範囲よりも少ないと生成物であるナノワイヤーの収量が低下する。 At this time, the molar ratio of ammonium tetrafluoroborate to anhydrous magnesium chloride is preferably in the range of 3: 1 to 5: 1. When the amount of ammonium tetrafluoroborate is larger than this range, there is a concern that the boron nitride film produced by the remaining ammonium tetrafluoroborate remaining unreacted is eroded. On the other hand, when the amount of ammonium tetrafluoroborate is less than the above range, the yield of the nanowire as a product is lowered.
無水塩化マグネシウムの加熱温度は、上述した７×１０２〜１０×１０２℃の範囲が好ましい。１０×１０２℃よりも高いと板状粒子の生成や塩化マグネシウムの蒸気が反応系外へ逸散してしまう。７×１０２℃よりも低いと、反応が起こらない。 The heating temperature of anhydrous magnesium chloride is preferably in the range of 7 × 10 2 to 10 × 10 2 ° C described above. When the temperature is higher than 10 × 10 2 ° C., the generation of plate-like particles and the magnesium chloride vapor are dissipated out of the reaction system. If it is lower than 7 × 10 2 ° C., no reaction occurs.
不活性ガスは、テトラフルオロホウ酸アンモニウムの蒸気を無水塩化マグネシウム塊のほうへ移送することと酸化防止が目的であるので、アルゴンガスや窒素ガスを使用することができる。その流量は反応装置の大きさ等によって異なるので一概には決められないが、たとえば、加熱反応管の内径が５０ｍｍ程度の場合は、不活性ガスの流量を５０〜２００ｓｃｃｍの範囲とすることが好ましい。２００ｓｃｃｍよりも多量に流すと蒸気が反応系外へ逸散し、フッ化マグネシウムの生成量が低下する。５０ｓｃｃｍよりも流量が少ないと反応管が詰まることが懸念される。また、テトラフルオロホウ酸アンモニウムは、３20℃近傍が昇華温度であるので、この近傍の温度で加熱することが望ましい。すなわち、加熱装置の精度にも依るが、現在市販されている加熱装置を使用する場合は、320±10℃にすることは十分制御可能である。このような操作を２時間程度続けることにより、無水塩化マグネシウム塊の表面がわずかに半融し無色のウール状物質が生成する。この無色のウール状物質は、分析することにより、長さ１μｍ以上、外径２０〜１２０ｎｍを有する窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーであることが確認される。 The purpose of the inert gas is to transfer the vapor of ammonium tetrafluoroborate to the anhydrous magnesium chloride mass and to prevent oxidation, so argon gas or nitrogen gas can be used. Since the flow rate varies depending on the size of the reaction apparatus and the like, it cannot be determined unconditionally. For example, when the inner diameter of the heated reaction tube is about 50 mm, the flow rate of the inert gas is preferably in the range of 50 to 200 sccm. . When the flow is larger than 200 sccm, the vapor is dissipated out of the reaction system, and the amount of magnesium fluoride produced decreases. If the flow rate is less than 50 sccm, the reaction tube may be clogged. In addition, ammonium tetrafluoroborate has a sublimation temperature in the vicinity of 320 ° C., so it is desirable to heat at a temperature in the vicinity of this temperature. That is, although depending on the accuracy of the heating device, when using a commercially available heating device, the temperature can be sufficiently controlled to be 320 ± 10 ° C. By continuing such an operation for about 2 hours, the surface of the anhydrous magnesium chloride block is slightly melted to produce a colorless wool-like substance. This colorless wool-like substance is confirmed to be a magnesium fluoride nanowire coated with a boron nitride film having a length of 1 μm or more and an outer diameter of 20 to 120 nm by analysis.
次に、第２段階では、上記で生成した窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを加熱炉中に配置し、不活性ガスを流しながら、１２×１０２〜１６×１０２℃に加熱することにより、フッ化マグネシウムが蒸発し、該ナノワイヤーから除去されるので窒化ホウ素ナノチューブが得られる。 Next, in the second stage, the magnesium fluoride nanowires coated with the boron nitride film generated above are placed in a heating furnace, and while flowing an inert gas, the temperature is set to 12 × 10 2 to 16 × 10 2 ° C. By heating, magnesium fluoride evaporates and is removed from the nanowire, so that boron nitride nanotubes are obtained.
この際、加熱する温度は、上述の１２×１０２〜１６×１０２℃の範囲が好ましく、１６×１０２℃で十分にフッ化マグネシウムが蒸発除去されるので、これ以上の温度にする必要はない。１２×１０２℃未満では、フッ化マグネシウムを完全に除去できない。このような操作を行うことにより、白色のウール状の窒化ホウ素ナノチューブが得られる。
次に、実施例を示してさらに具体的に説明する。
At this time, the heating temperature is preferably in the range of 12 × 10 2 to 16 × 10 2 ° C described above, and magnesium fluoride is sufficiently removed by evaporation at 16 × 10 2 ° C. There is no. If it is less than 12 × 10 2 ° C., magnesium fluoride cannot be completely removed. By performing such an operation, white wool-like boron nitride nanotubes can be obtained.
Next, an example is shown and it demonstrates still more concretely.
和光純薬工業（株）製のテトラフルオロホウ酸アンモニウム（純度９８％）２０ｇを窒化ホウ素製ボートに入れ、この窒化ホウ素製ボートを横型アルミナ管状炉の一端に設置した。和光純薬工業（株）製の無水塩化マグネシウム塊（純度９９．５％）２ｇを穴あきのふたつきアルミナボートに入れ、このアルミナボートを前記横型アルミナ管状炉の中央部に配置した。前記テトラフルオロホウ酸アンモニウムを入れた窒化ホウ素製ボートを設置した方の炉の一端から流量８０ｓｃｃｍのアルゴンガスを流しながら、テトラフルオロホウ酸アンモニウムを３２０℃に加熱すると同時に、無水塩化マグネシウム塊を７００℃に２時間加熱した。無水塩化マグネシウム塊の表面がわずかに半融状態となり、その表面に無色のウール状物質がおよそ１００ｍｇ堆積した。同様に、テトラフルオロホウ酸アンモニウムの量、無水塩化マグネシウム塊の量、アルゴンガスの流量並びに加熱時間を同じ値にして、加熱温度だけを、それぞれ、８００℃、９００℃および１０００℃の３点に代えて実験し、無水塩化マグネシウム塊の表面に無色のウール状物質を堆積させた。
なお、上記において、無水塩化マグネシウムの代わりに、含水の塩化マグネシウムを使用した場合には、ウール状物質はほとんど得られなかった。
20 g of ammonium tetrafluoroborate (purity 98%) manufactured by Wako Pure Chemical Industries, Ltd. was placed in a boron nitride boat, and this boron nitride boat was installed at one end of a horizontal alumina tubular furnace. 2 g of anhydrous magnesium chloride block (purity 99.5%) manufactured by Wako Pure Chemical Industries, Ltd. was placed in a perforated alumina boat with a lid, and this alumina boat was placed in the center of the horizontal alumina tubular furnace. While flowing argon gas at a flow rate of 80 sccm from one end of the furnace in which the boron nitride boat containing the ammonium tetrafluoroborate is installed, the ammonium tetrafluoroborate is heated to 320 ° C., and at the same time, anhydrous magnesium chloride lump is added to 700 ° C. Heated to ° C for 2 hours. The surface of the anhydrous magnesium chloride lump was slightly semi-melted, and about 100 mg of colorless wool-like material was deposited on the surface. Similarly, the amount of ammonium tetrafluoroborate, the amount of anhydrous magnesium chloride mass, the flow rate of argon gas and the heating time are set to the same value, and only the heating temperature is set to three points of 800 ° C, 900 ° C and 1000 ° C, respectively. Instead, an experiment was conducted to deposit a colorless wooly substance on the surface of the anhydrous magnesium chloride mass.
In the above, when water-containing magnesium chloride was used instead of anhydrous magnesium chloride, almost no wooly substance was obtained.
図１に、生成したウール状物質のＸ線回折のパターンを示した。（００２）面及び星印で示した位置に六方晶系の窒化ホウ素に基づくピークが見られる。他のピークは格子定数ａ＝０．４６２ｎｍ、ｂ＝０．３０４ｎｍを有する正方晶系のフッ化マグネシウムの回折ピークであることが分かった。特に、（１１０）面、（２２０）面のフッ化マグネシウムに基づくピークが強く現れている。したがって、ウール状物質は窒化ホウ素とフッ化マグネシウムを含んでいることが分かった。 FIG. 1 shows an X-ray diffraction pattern of the produced wool-like substance. Peaks based on hexagonal boron nitride are observed at the positions indicated by the (002) plane and asterisks. The other peaks were found to be diffraction peaks of tetragonal magnesium fluoride having lattice constants of a = 0.462 nm and b = 0.304 nm. In particular, peaks based on magnesium fluoride on the (110) plane and the (220) plane appear strongly. Therefore, it was found that the wool-like material contains boron nitride and magnesium fluoride.
図２ａ〜ｄに無水塩化マグネシウム塊を１０００℃、９００℃、８００℃および７００℃にそれぞれ加熱して得たウール状物質の走査型電子顕微鏡像の写真を示した。これらの写真から、得られたウール状物質は、すべて繊維状の形態であった。また、９００℃よりも高い温度で合成したウール状物質には板状の物質が含まれている。９００℃、１０００℃で合成した繊維状物質は長さが数百ｎｍから数μｍまでの比較的短い繊維であり、その直径は１００ｎｍよりも少し大きい程度である。それに対して、７００℃と８００℃で合成したウール状物質は、直径が２０〜５０ｎｍで、長さが１０μｍ以上と非常に長い。
FIGS. 2a to 2d show photographs of scanning electron microscope images of wool-like materials obtained by heating anhydrous magnesium chloride masses to 1000 ° C., 900 ° C., 800 ° C. and 700 ° C. , respectively. From these photographs, all the obtained wool-like substances were in a fibrous form. Moreover, the wool-like substance synthesized at a temperature higher than 900 ° C. contains a plate-like substance. The fibrous material synthesized at 900 ° C. and 1000 ° C. is a relatively short fiber having a length of several hundred nm to several μm, and its diameter is a little larger than 100 nm. On the other hand, the wool-like material synthesized at 700 ° C. and 800 ° C. has a diameter of 20 to 50 nm and a very long length of 10 μm or more.
８００℃で合成したウール状物質の低倍率透過型電子顕微鏡像の写真を図３ａに示し、その高解像度像の写真を図３ｂに示した。図３ａからウール状の形態であることが確認できる。また、図３ｂからナノワイヤーの中心の外側が無秩序層で覆われている複合構造であることも確認される。この外側の無秩序層の化学組成は、透過型電子顕微鏡に付属されている電子エネルギー損失スペクトルメーターで測定したところ、ほぼ化学量論組成の窒化ホウ素であった。 A photograph of a low magnification transmission electron microscope image of a wool-like material synthesized at 800 ° C. is shown in FIG. 3a, and a photograph of the high resolution image is shown in FIG. 3b. It can confirm that it is a wool-like form from FIG. 3a. It is also confirmed from FIG. 3b that the nanowire has a composite structure in which the outside of the center of the nanowire is covered with a disordered layer. The chemical composition of the outer disordered layer was approximately the stoichiometric boron nitride as measured by an electron energy loss spectrum meter attached to the transmission electron microscope .
図３ｃに８００℃で合成したウール状物質の中心部分の電子線回折の写真を載せたが、これはフッ化マグネシウムの［−１１３］晶帯軸のパターンと帰属される。 FIG. 3c is a photograph of electron diffraction of the central part of the wool-like material synthesized at 800 ° C., which is attributed to the pattern of [−113] zone axis of magnesium fluoride.
図４ａに、９００℃で合成したウール状物質の低倍率透過型電子顕微鏡像の写真を載せた。この図４ａからその直径は１００ｎｍよりも大きい。図４ｂにその高解像度写真を示したが、外側（左側）にコートされた窒化ホウ素の層は結晶化されており、その層間隔は０．３４ｎｍである。内側（右側）のフッ化マグネシウムナノワイヤーの直径は、一定の均一な太さではなく変動している。 The photograph of the low magnification transmission electron microscope image of the wool-like substance synthesize | combined at 900 degreeC was mounted on FIG. From FIG. 4a, the diameter is larger than 100 nm. FIG. 4b shows a high-resolution photograph in which the boron nitride layer coated on the outside (left side) is crystallized and the layer spacing is 0.34 nm. The diameter of the inner (right) magnesium fluoride nanowire varies rather than a constant uniform thickness.
次に、第２段階として、無水塩化マグネシウム塊を７００℃に加熱して得た上述の窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤー１００ｍｇを窒化ホウ素製るつぼに入れ、このるつぼを縦型高周波誘導加熱炉の中央部に設置した。該加熱炉の中に、流量２０００ｓｃｃｍの窒素ガスを流しながら、１６００℃に２時間加熱し、フッ化マグネシウムを蒸発させた。無色のウール状物質が２０ｍｇ得られた。 Next, as a second stage, 100 mg of magnesium fluoride nanowires coated with the above-described boron nitride film obtained by heating anhydrous magnesium chloride mass to 700 ° C. are placed in a boron nitride crucible, and this crucible is placed in a vertical high frequency Installed in the center of the induction furnace. While flowing nitrogen gas at a flow rate of 2000 sccm into the heating furnace, the furnace was heated to 1600 ° C. for 2 hours to evaporate magnesium fluoride. 20 mg of a colorless wooly substance was obtained.
同様に、無水塩化マグネシウム塊を９００℃で加熱して得られた上述の窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを１６００℃に２時間加熱してフッ化マグネシウムを蒸発させた。 Similarly, magnesium fluoride nanowires coated with the above boron nitride film obtained by heating an anhydrous magnesium chloride mass at 900 ° C. were heated to 1600 ° C. for 2 hours to evaporate the magnesium fluoride.
図５に、１６００℃で２時間加熱を行う前と後のウール状物質のフーリェ変換赤外吸収スペクトルの測定結果を示した。この図の上のスペクトルは、１６００℃に加熱する前の窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーのスペクトルであるが、フッ化マグネシウムの伸縮振動のピークが５００ｃｍ−１付近に現れていることが確認できる。図５の下のスペクトルは、１６００℃に２時間加熱した後のスペクトルであるが、上述した５００ｃｍ−１付近のピークが消失しており、フッ化マグネシウムが蒸発したことが裏付けられた。そして、窒化ホウ素に基づく８２０ｃｍ−１の面外変角振動および１３７８ｃｍ−１の面内光学モードの吸収の存在が確認できる。 FIG. 5 shows the measurement results of the Fourier transform infrared absorption spectrum of the wool-like material before and after heating at 1600 ° C. for 2 hours. The upper spectrum of this figure is the spectrum of magnesium fluoride nanowires coated with a boron nitride film before heating to 1600 ° C., and the peak of stretching vibration of magnesium fluoride appears in the vicinity of 500 cm −1 . I can confirm that. The lower spectrum in FIG. 5 is a spectrum after heating at 1600 ° C. for 2 hours. The above-mentioned peak in the vicinity of 500 cm −1 disappeared, confirming that magnesium fluoride had evaporated. The presence of out - of-plane vibration at 820 cm −1 and in-plane optical mode absorption at 1378 cm −1 based on boron nitride can be confirmed.
無水塩化マグネシウム塊を７００℃で加熱して得た窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを１６００℃に２時間加熱処理してフッ化マグネシウムを蒸発除去したウール状物質の低倍率透過型電子顕微鏡像の写真を図６ａに示し、無水塩化マグネシウム塊を９００℃に加熱して得た窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを１６００℃に２時間加熱してフッ化マグネシウムを除去したウール状物質の低倍率透過型電子顕微鏡像の写真を図６ｂに示した。図６ａの写真から、窒化ホウ素ナノチューブの長さは１μｍよりも長く、直径は２０〜５０ｎｍであることが分かった。そして、その形態は出発物質として使用した窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーに類似している。すなわち、窒化ホウ素膜（ナノチューブ）は高温処理しても変形せず、形態が維持されていることが分かった。このナノチューブの壁の厚さは、無秩序層のため１０ｎｍよりも大きい。それに対して、９００℃で合成した窒化ホウ素膜がコートされたフッ化マグネシウムナノワイヤーを加熱処理したナノチューブの形態は、上記の７００℃で合成したものとは異なっており、その外径は約１００ｎｍで、チューブ壁の厚さは非常に薄く、３ｎｍから１５ｎｍにわたっている。 Low-magnification transmission type of wooly material obtained by heating magnesium fluoride nanowires coated with boron nitride film obtained by heating anhydrous magnesium chloride mass at 700 ° C to 1600 ° C for 2 hours to evaporate and remove magnesium fluoride A photograph of an electron microscope image is shown in FIG. 6a. Magnesium fluoride nanowires coated with a boron nitride film obtained by heating an anhydrous magnesium chloride mass to 900 ° C. are heated to 1600 ° C. for 2 hours to remove magnesium fluoride. A photograph of a low-magnification transmission electron microscope image of the woolen material thus obtained is shown in FIG. From the photograph of FIG. 6a, it was found that the length of the boron nitride nanotube was longer than 1 μm and the diameter was 20 to 50 nm. And the form is similar to the magnesium fluoride nanowire coated with the boron nitride film used as a starting material. That is, it was found that the boron nitride film (nanotube) was not deformed even when subjected to a high temperature treatment and the form was maintained. The nanotube wall thickness is greater than 10 nm due to the disordered layer. On the other hand, the shape of the nanotube which heat-processed the magnesium fluoride nanowire coated with the boron nitride film synthesized at 900 ° C. is different from that of the above synthesized at 700 ° C., and the outer diameter is about 100 nm. The tube wall is very thin and extends from 3 nm to 15 nm.
本発明により、無秩序層からなる窒化ホウ素ナノチューブの製造が可能となったことから優れた圧電特性、水素吸蔵材料等への応用が期待される。 Since the present invention makes it possible to produce boron nitride nanotubes composed of disordered layers, excellent piezoelectric properties and application to hydrogen storage materials are expected.
Claims (4)
The method for producing a boron nitride nanotube according to any one of claims 1 to 3, wherein the inert gas is argon gas or nitrogen gas .
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