JP5605908B2 - Four-layer catalyst base for CNT production, CNT with substrate carbonized layer, CNT with carbonized layer, CNT production method, CNT recovery method, and CNT continuous production apparatus - Google Patents
Four-layer catalyst base for CNT production, CNT with substrate carbonized layer, CNT with carbonized layer, CNT production method, CNT recovery method, and CNT continuous production apparatus Download PDFInfo
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Description
本発明は、配向カーボンナノチューブを効率的に合成する触媒基体、製法及び装置に関し、更に詳細には、ＣＮＴ合成時に触媒層から基板層への熱的影響を極力遮断して配向カーボンナノチューブを高効率に合成すると同時に基板の再利用を可能にする触媒基体、製法及び装置に関する。 The present invention relates to a catalyst substrate, a manufacturing method, and an apparatus for efficiently synthesizing aligned carbon nanotubes. More specifically, the present invention relates to a highly efficient method of aligning carbon nanotubes by cutting off the thermal influence from the catalyst layer to the substrate layer as much as possible during CNT synthesis. The present invention relates to a catalyst substrate, a manufacturing method, and an apparatus that enable the substrate to be reused while being synthesized.
配向カーボンナノチューブ（「ブラシ状ＣＮＴ又は配向ＣＮＴ」とも称される）を合成する方法として、触媒を利用して炭化水素などの原料ガスを分解し、触媒表面にカーボンナノチューブを成長させる触媒化学的気相成長法（ＣＣＶＤ法、Catalyst Chemical Vapor Deposition）がある。本発明における「配向カーボンナノチューブ」とは、カーボンナノチューブが基体上に一定方向に林立したものであり、基体上に一定方向に成長したカーボンナノチューブを指称する。配向カーボンナノチューブを製造する技術には、特許文献１として国際公開第ＷＯ２００８／００７７５０号、非特許文献１としてＨｉｒａｏｋａ ｅｔ．ａｌ．，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１２８（２００６）１３３３８及び非特許文献２としてＨ．Ｓ．Ｋｉｍ ｅｔ．ａｌ．，Ｊ．Ｐｈｙｓ．Ｃｈｅｍ，Ｃ１１３（２００９）１７９８３がある。 As a method of synthesizing aligned carbon nanotubes (also referred to as “brush-like CNTs or aligned CNTs”), a catalytic chemical gas that decomposes a raw material gas such as hydrocarbon using a catalyst and grows carbon nanotubes on the catalyst surface is used. There is a phase growth method (CCVD method, Catalyst Chemical Vapor Deposition). The “aligned carbon nanotube” in the present invention refers to a carbon nanotube in which carbon nanotubes are grown in a certain direction on a substrate, and grows in a certain direction on the substrate. As a technique for producing oriented carbon nanotubes, International Publication No. WO2008 / 007750 as Patent Document 1 and Hiraoka et. al. , J .; Am. Chem. Soc. 128 (2006) 13338 and Non-Patent Document 2 S. Kim et. al. , J .; Phys. Chem, C113 (2009) 17983.
特許文献１では、図１５の（１５Ａ）に示すように、例えばシリコン基板層１０２の表面に触媒層１０８を形成した触媒基体１０１を用いて、前記ＣＣＶＤ法により、触媒層１０８の表面にブラシ状ＣＮＴを成長させる方法が記載されている。また、非特許文献１では、図１５の（１５Ｂ）に示すように、ＳＵＳ層１０２の上にＡｌ２Ｏ３層１０５を形成し、その上に触媒層１０８を形成した触媒基体１０１を用いて、前記ＣＣＶＤ法により、触媒層１０８の表面にブラシ状ＣＮＴを成長させる方法が記載されている。更に、非特許文献２では、図１５の（１５Ｃ）に示すように、ＳＵＳ層１０２の上にエポキシ樹脂層１０４を形成し、その上にＡｌ層１０６を形成して、その上に触媒層１０８を形成した触媒基体１０１を用いて、前記ＣＣＶＤ法により、触媒層１０８の表面にブラシ状ＣＮＴを成長させる方法が記載されている。 In Patent Document 1, as shown in FIG. 15 (15A), for example, a catalyst base 101 having a catalyst layer 108 formed on the surface of a silicon substrate layer 102 is used, and the surface of the catalyst layer 108 is brushed by the CCVD method. A method for growing CNTs is described. Further, in Non-Patent Document 1, as shown in FIG. 15 (15B), the CCVD is performed using the catalyst base 101 in which the Al2O3 layer 105 is formed on the SUS layer 102 and the catalyst layer 108 is formed thereon. A method of growing brush-like CNTs on the surface of the catalyst layer 108 by the method is described. Further, in Non-Patent Document 2, as shown in FIG. 15 (15C), an epoxy resin layer 104 is formed on the SUS layer 102, an Al layer 106 is formed thereon, and a catalyst layer 108 is formed thereon. A method is described in which brush-like CNTs are grown on the surface of the catalyst layer 108 by the CCVD method using the catalyst base 101 on which is formed.
特許文献１の技術では、触媒層１０８の表面に原料ガスが流通すると、触媒層１０８が微粒子化すると同時に、この触媒微粒子によりＣＮＴは成長し、形態的にはシリコン基板層１０２の表面にＣＮＴが林立成長する。ＣＮＴをシリコン基板層１０２から機械的に分離すると、ＣＮＴは回収できる。しかし、分離されたシリコン基板層１０２の表面には機械分離による多少の傷が付き、新たなＣＮＴ製造に際しシリコン基板層として再利用できないという欠点があった。また、シリコン基板は柔軟性の無い剛体基板であるから外力により破断し易く、そのため大面積化できず、ＣＮＴの大量製造には向かないという欠点を有する。可撓性・柔軟性のある基板層としてステンレス基板であるＳＵＳ基板を用いることが別に検討された。しかし、（１５Ａ）のシリコン基板層１０２をＳＵＳ基板層１０２に交換した場合には、ＣＮＴ製造用の触媒層１０８にＦｅやＭｏなどが含まれ、同時にＳＵＳ基板層１０２にＦｅが含まれるため、ＣＮＴ合成時に触媒層１０８とＳＵＳ基板層１０２との間で金属同士の融合反応が生じ、ＣＮＴ合成が困難になるという弱点があった。これを改善するために、ＳＵＳ基板層を使用する場合には、前記金属融合反応を遮断するために、ＳＵＳ基板層１０２と触媒層１０８の間にバッファ層を介装するアイデアが提案された。 In the technique of Patent Document 1, when the raw material gas flows on the surface of the catalyst layer 108, the catalyst layer 108 becomes fine particles, and at the same time, CNT grows by the catalyst fine particles, and morphologically forms CNT on the surface of the silicon substrate layer 102. The forest grows. When the CNTs are mechanically separated from the silicon substrate layer 102, the CNTs can be recovered. However, the surface of the separated silicon substrate layer 102 has some defects due to mechanical separation, and has a drawback that it cannot be reused as a silicon substrate layer in the production of new CNTs. In addition, since the silicon substrate is a rigid substrate having no flexibility, it is easily broken by an external force, and therefore cannot have a large area and is not suitable for mass production of CNTs. Another consideration was to use a SUS substrate, which is a stainless steel substrate, as the flexible and flexible substrate layer. However, when the (15A) silicon substrate layer 102 is replaced with the SUS substrate layer 102, the catalyst layer 108 for CNT production contains Fe, Mo, and the like, and at the same time, the SUS substrate layer 102 contains Fe. At the time of CNT synthesis, a fusion reaction between metals occurs between the catalyst layer 108 and the SUS substrate layer 102, which makes it difficult to synthesize CNT. In order to improve this, when a SUS substrate layer is used, an idea has been proposed in which a buffer layer is interposed between the SUS substrate layer 102 and the catalyst layer 108 in order to block the metal fusion reaction.
非特許文献１の技術では、バッファ層として金属酸化物であるＡｌ２Ｏ３層１０５が使用されている。多くの金属酸化物からＡｌ２Ｏ３を選択した理由は、触媒層１０８が触媒微粒子に変化するときに、Ａｌ２Ｏ３が微粒子化を促進する作用を有するからである。ＣＮＴ合成温度で触媒層１０８の表面に原料ガスを流通させると、触媒層１０８が微粒子化すると同時に、この触媒微粒子をＣＮＴの根元に内包しながらＣＮＴは成長し、形態的にはＳＵＳ基板層１０２の表面にＣＮＴが林立形成される点は特許文献１と同様である。しかし、金属酸化物であるＡｌ２Ｏ３層１０５の融点は極めて高いから、ＣＮＴ合成時の６００℃〜９００℃の高温でもＡｌ２Ｏ３層１０５は触媒層１０８とＳＵＳ基板層１０２の間を完全に遮断している。しかし、金属酸化物であるＡｌ２Ｏ３層１０５はＳＵＳ基板層１０２と強力に接合する特徴を有する。従って、形成されたＣＮＴ層を分離できても、Ａｌ２Ｏ３層１０５をＳＵＳ基板層１０２から分離することは殆ど不可能である。また、ＳＵＳ基板層１０２の表面に残ったＦｅやＭｏの炭化物の除去も困難である。従って、ＳＵＳ層基板１０２を基板層として再利用することは不可能である。ＣＮＴの大量製造において、基板価格が極めて高く、ＳＵＳ基板層を再利用できない限り、ＣＮＴを低価格で大量製造することは不可能に近い。 In the technique of Non-Patent Document 1, an Al2O3 layer 105 that is a metal oxide is used as a buffer layer. The reason why Al2O3 is selected from many metal oxides is that when the catalyst layer 108 changes to catalyst fine particles, Al2O3 has an action of promoting the fine particle formation. When the raw material gas is circulated on the surface of the catalyst layer 108 at the CNT synthesis temperature, the catalyst layer 108 becomes fine particles, and at the same time, the CNTs grow while encapsulating the catalyst fine particles in the roots of the CNTs. The point that CNTs are formed on the surface is the same as in Patent Document 1. However, since the melting point of the Al2O3 layer 105, which is a metal oxide, is extremely high, the Al2O3 layer 105 completely blocks between the catalyst layer 108 and the SUS substrate layer 102 even at a high temperature of 600C to 900C during CNT synthesis. . However, the Al2O3 layer 105, which is a metal oxide, has a characteristic of being strongly bonded to the SUS substrate layer 102. Therefore, even if the formed CNT layer can be separated, it is almost impossible to separate the Al 2 O 3 layer 105 from the SUS substrate layer 102. Further, it is difficult to remove Fe and Mo carbides remaining on the surface of the SUS substrate layer 102. Therefore, it is impossible to reuse the SUS layer substrate 102 as a substrate layer. In mass production of CNTs, it is almost impossible to mass produce CNTs at a low price unless the substrate price is extremely high and the SUS substrate layer cannot be reused.
そこで、非特許文献２の技術が提案されたのである。（１５Ｃ）において、ＳＵＳ基板層１０２の上に、エポキシ樹脂層１０４とＡｌ層１０６と触媒層１０８が積層されている。Ａｌ層１０６は触媒層１０８の微粒子化を促進する素材である。また、ＣＮＴ合成時に、Ａｌ層は触媒微粒子をエポキシ樹脂層１０４から隔て、この触媒微粒子がＣＮＴの根元に位置してＣＮＴが成長する。他方、エポキシ樹脂の耐熱温度の上限は２００℃であり、６００℃〜９００℃のＣＮＴ合成温度では、エポキシ樹脂の耐熱性は完全に破綻する。即ち、エポキシ樹脂層１０４の耐熱温度が低く過ぎるため、ＣＮＴ合成時の高温では、エポキシ樹脂層１０４は分解消失する。たとえ炭化物が残っても、微細孔だらけの炭化層になる。これらの微細孔を通じてＳＵＳ層１０２のＦｅやＭｏが触媒層１０８のＦｅと融合反応を生起し、触媒層上に秀麗なＣＮＴ層を形成できないという欠点がある。同時に、ＣＮＴ形成後に、ＣＮＴ層をＳＵＳ層１０２から分離すると、ＳＵＳ層１０２の表面には無数のエポキシ樹脂の炭化物やＦｅとＭｏの炭化物が残り、ＳＵＳ層の再利用ができず、基板の再利用不能性はＣＮＴの高価格化を招来するという弱点を露呈する。 Therefore, the technique of Non-Patent Document 2 has been proposed. In (15C), the epoxy resin layer 104, the Al layer 106, and the catalyst layer 108 are laminated on the SUS substrate layer 102. The Al layer 106 is a material that promotes the atomization of the catalyst layer 108. Further, during the synthesis of CNTs, the Al layer separates the catalyst fine particles from the epoxy resin layer 104, and the catalyst fine particles are located at the base of the CNTs so that the CNTs grow. On the other hand, the upper limit of the heat resistance temperature of the epoxy resin is 200 ° C., and the heat resistance of the epoxy resin completely fails at the CNT synthesis temperature of 600 ° C. to 900 ° C. That is, since the heat resistant temperature of the epoxy resin layer 104 is too low, the epoxy resin layer 104 decomposes and disappears at a high temperature during CNT synthesis. Even if carbide remains, it becomes a carbonized layer full of fine pores. There is a drawback that Fe and Mo of the SUS layer 102 cause a fusion reaction with Fe of the catalyst layer 108 through these fine holes, and an excellent CNT layer cannot be formed on the catalyst layer. At the same time, when the CNT layer is separated from the SUS layer 102 after CNT formation, numerous epoxide resin carbides and Fe and Mo carbides remain on the surface of the SUS layer 102, and the SUS layer cannot be reused. Unusability exposes the weakness of incurring high CNT prices.
従って、本発明においては、基板層の上に耐熱性樹脂層を形成し、この耐熱性樹脂層の上にＡｌ層と触媒層を形成した四層型触媒基体を提案し、特に４００℃以上の耐熱温度を有した耐熱性樹脂層を形成することによって、ＣＮＴ合成時に耐熱性樹脂層が基板層を熱的に保護しながら、触媒層上に秀麗な配向ＣＮＴを合成でき、しかもＣＮＴを分離回収しても基板層表面は合成前の状態を保持できるから、基板層の再利用を実現することができる。 Therefore, in the present invention, a four-layer type catalyst substrate is proposed in which a heat-resistant resin layer is formed on a substrate layer, and an Al layer and a catalyst layer are formed on the heat-resistant resin layer. By forming a heat-resistant resin layer with a heat-resistant temperature, excellent oriented CNTs can be synthesized on the catalyst layer while the heat-resistant resin layer thermally protects the substrate layer during CNT synthesis, and CNTs are separated and recovered Even so, since the surface of the substrate layer can maintain the state before synthesis, the reuse of the substrate layer can be realized.
本発明は、上記課題を解決するために提案されたものであって、本発明の第１の形態は、基板層の上に耐熱性樹脂層を形成し、前記耐熱性樹脂層の上にＡｌ層を形成し、前記Ａｌ層の上にＣＮＴ合成用の触媒層を形成したことを特徴とするＣＮＴ製造用の四層型触媒基体である。 The present invention has been proposed in order to solve the above-mentioned problems. In the first embodiment of the present invention, a heat resistant resin layer is formed on a substrate layer, and Al is formed on the heat resistant resin layer. A four-layer catalyst substrate for producing CNTs, wherein a layer is formed and a catalyst layer for CNT synthesis is formed on the Al layer.
本発明の第２の形態は、前記四層型触媒基体がＣＮＴ合成のために還元性雰囲気の高温環境に配置されたとき前記耐熱性樹脂層が炭化層に変化するＣＮＴ製造用の四層型触媒基体である。 The second embodiment of the present invention is a four-layer type for CNT production in which the heat-resistant resin layer changes to a carbonized layer when the four-layer catalyst substrate is placed in a high temperature environment of a reducing atmosphere for CNT synthesis. It is a catalyst substrate.
本発明の第３の形態は、前記基板が、セラミックス材、無機非金属、無機非金属化合物、金属を含む材料からなり、６００℃〜９００℃のＣＮＴ合成温度で耐熱性を有する材料から形成されるＣＮＴ製造用の四層型触媒基体である。 According to a third aspect of the present invention, the substrate is made of a material including a ceramic material, an inorganic nonmetal, an inorganic nonmetallic compound, and a metal, and is formed of a material having heat resistance at a CNT synthesis temperature of 600 ° C. to 900 ° C. This is a four-layer catalyst substrate for producing CNTs.
本発明の第４の形態は、前記耐熱性樹脂層が、ポリイミド樹脂、ポリアミドイミド樹脂、全芳香族ポリエステル系樹脂、その他の炭素骨格樹脂を含む材料からなり、４００℃以上の耐熱温度を有した耐熱性樹脂から形成されるＣＮＴ製造用の四層型触媒基体である。 According to a fourth aspect of the present invention, the heat resistant resin layer is made of a material containing a polyimide resin, a polyamideimide resin, a wholly aromatic polyester resin, or other carbon skeleton resin, and has a heat resistant temperature of 400 ° C. or higher. It is a four-layer catalyst base for producing CNTs formed from a heat-resistant resin.
本発明の第５の形態は、前記触媒層がＦｅ、Ｃｏ、Ｎｉ、Ｍｏ、Ｐｔを含む遷移金属の一種以上から形成されるＣＮＴ製造用の四層型触媒基体である。 According to a fifth aspect of the present invention, there is provided a four-layer catalyst substrate for producing CNTs, wherein the catalyst layer is formed from one or more transition metals including Fe, Co, Ni, Mo, and Pt.
本発明の第６の形態は、前記基板層がベルト状に形成された金属製の基板ベルトであり、前記基板ベルトの上に前記耐熱性樹脂層、前記Ａｌ層及び前記触媒層を積層して四層型触媒基体ベルトを構成したＣＮＴ製造用の四層型触媒基体である。 A sixth aspect of the present invention is a metal substrate belt in which the substrate layer is formed in a belt shape, and the heat-resistant resin layer, the Al layer, and the catalyst layer are laminated on the substrate belt. This is a four-layer catalyst substrate for producing CNTs constituting a four-layer catalyst substrate belt.
本発明の第７の形態は、ＣＮＴ製造用の四層型触媒基体を反応室に配置し、反応室内をＣＮＴ合成温度に加熱して、原料ガスを前記四層型触媒基体の触媒層の表面に接触させ、前記触媒層の表面にＣＮＴを成長させるＣＮＴ製造方法である。 According to a seventh aspect of the present invention, a four-layer catalyst substrate for producing CNTs is disposed in a reaction chamber, the reaction chamber is heated to a CNT synthesis temperature, and the raw material gas is supplied to the surface of the catalyst layer of the four-layer catalyst substrate. CNT production method in which CNT is grown on the surface of the catalyst layer.
本発明の第８の形態は、前記四層型触媒基体を前記四層型触媒基体ベルトで構成し、前記四層型触媒基体ベルトを前記反応室に走行させながら、前記触媒層の表面にＣＮＴを成長させ、前記四層型触媒基体ベルトの表面にＣＮＴを大量合成するＣＮＴ製造方法である。 According to an eighth aspect of the present invention, the four-layer catalyst substrate is constituted by the four-layer catalyst substrate belt, and the CNT is formed on the surface of the catalyst layer while running the four-layer catalyst substrate belt into the reaction chamber. Is produced, and a large amount of CNT is synthesized on the surface of the four-layer catalyst substrate belt.
本発明の第９の形態は、ＣＮＴ製造方法により製造され、前記合成温度により前記耐熱性樹脂層が炭化層に変化し、前記Ａｌ層と前記触媒層が合成されたＣＮＴからなるＣＮＴ層に組み込まれ、前記基板層の上に前記炭化層と前記ＣＮＴ層がこの順に積層された基板炭化層付きＣＮＴである。 The ninth embodiment of the present invention is manufactured by a CNT manufacturing method, wherein the heat-resistant resin layer is changed to a carbonized layer by the synthesis temperature, and is incorporated into a CNT layer composed of CNT in which the Al layer and the catalyst layer are synthesized. The carbonized layer and the CNT layer are laminated in this order on the substrate layer.
本発明の第１０の形態は、基板炭化層付きＣＮＴから基板層を剥離して得られ、前記炭化層の上に前記ＣＮＴ層が配置された炭化層付きＣＮＴである。 A tenth aspect of the present invention is a CNT with a carbonized layer obtained by peeling a substrate layer from a CNT with a substrate carbonized layer, and the CNT layer is disposed on the carbonized layer.
本発明の第１１の形態は、炭化層付きＣＮＴを酸化雰囲気中で加熱して前記炭化層を燃焼気散させ、前記ＣＮＴ層だけをＣＮＴとして回収するＣＮＴ回収方法である。 The eleventh aspect of the present invention is a CNT recovery method in which the carbonized layer-attached CNTs are heated in an oxidizing atmosphere to burn off the carbonized layer and recover only the CNT layer as CNTs.
本発明の第１２の形態は、基板ベルトを駆動ローラと従動ローラの周囲に卷回して無端ベルトを構成し、前記基板ベルトの表面に前記耐熱性樹脂層、前記Ａｌ層及び前記触媒層をこの順に積層して前記四層型触媒基体ベルトを形成する耐熱性樹脂層形成手段、Ａｌ層形成手段及び触媒層形成手段を配置し、形成された前記四層型触媒基体ベルトの表面にＣＮＴを合成するＣＶＤ反応手段を配置して、前記四層型触媒基体ベルトを走行させながら前記四層型触媒基体ベルト上にＣＮＴ層を形成し、前記ＣＮＴ層を形成した前記四層型触媒基体ベルトでは、前記触媒層と前記Ａｌ層がＣＮＴに組み込まれた前記ＣＮＴ層が、前記耐熱性樹脂層が変化した炭化層を介して前記基板ベルト上に積層された形態を有するＣＮＴ連続製造装置である。 In a twelfth aspect of the present invention, an endless belt is formed by winding a substrate belt around a driving roller and a driven roller, and the heat-resistant resin layer, the Al layer, and the catalyst layer are disposed on the surface of the substrate belt. Heat-resistant resin layer forming means, Al layer forming means, and catalyst layer forming means for forming the four-layer catalyst substrate belt by stacking in order are arranged, and CNT is synthesized on the surface of the formed four-layer catalyst substrate belt. In the four-layer catalyst substrate belt in which the CNT layer is formed by forming a CNT layer on the four-layer catalyst substrate belt while running the four-layer catalyst substrate belt, The CNT continuous manufacturing apparatus having a form in which the CNT layer in which the catalyst layer and the Al layer are incorporated in CNT is laminated on the substrate belt through a carbonized layer in which the heat-resistant resin layer is changed.
本発明の第１３の形態は、基板ベルトを卷回した基板ロールと、前記基板ロールから送出される前記基板ベルトの表面に前記耐熱性樹脂層、前記Ａｌ層及び前記触媒層をこの順に積層して前記四層型触媒基体ベルトを形成する耐熱性樹脂層形成手段、Ａｌ層形成手段及び触媒層形成手段を配置し、形成された前記四層型触媒基体ベルトを卷回した四層型触媒基体ロールを製造する四層型触媒基体ロールの製造装置である。 In a thirteenth embodiment of the present invention, a substrate roll wound around a substrate belt, and the heat-resistant resin layer, the Al layer, and the catalyst layer are laminated in this order on the surface of the substrate belt fed from the substrate roll. A four-layer type catalyst substrate in which a heat-resistant resin layer forming means, an Al layer forming means and a catalyst layer forming means for forming the four-layer catalyst substrate belt are arranged and the formed four-layer catalyst substrate belt is wound It is a manufacturing apparatus of a four-layer type catalyst substrate roll for manufacturing a roll.
本発明の第１４の形態は、四層型触媒基体ロールと、前記四層型触媒基体ロールから送出される前記四層型触媒基体ベルトの表面に前記ＣＮＴ層を形成するＣＶＤ反応手段を配置し、前記ＣＮＴ層を形成された前記四層型触媒基体ベルトを卷回して回収する回収ロールを配置し、前記ＣＮＴ層を形成された前記四層型触媒基体ベルトでは、前記触媒層と前記Ａｌ層がＣＮＴに組み込まれた前記ＣＮＴ層が、前記耐熱性樹脂層が変化した炭化層を介して前記基板ベルト上に積層された形態を有するＣＮＴ連続製造装置である。 In a fourteenth aspect of the present invention, a four-layer catalyst substrate roll and a CVD reaction means for forming the CNT layer on the surface of the four-layer catalyst substrate belt fed from the four-layer catalyst substrate roll are arranged. A recovery roll that winds and collects the four-layer catalyst substrate belt on which the CNT layer is formed is disposed, and the catalyst layer and the Al layer are arranged on the four-layer catalyst substrate belt on which the CNT layer is formed. The CNT continuous manufacturing apparatus has a form in which the CNT layer incorporated in the CNT is laminated on the substrate belt through a carbonized layer in which the heat-resistant resin layer is changed.
本発明の第１５の形態は、前記基板ベルトから、前記ＣＮＴ層が前記炭化層と一体に積層された炭化層付きＣＮＴを分離回収する分離手段を設け、前記炭化層付きＣＮＴを酸化雰囲気中で燃焼気散させて前記ＣＮＴ層だけを回収する炭化層燃焼手段を設けるＣＮＴ連続製造装置である。 According to a fifteenth aspect of the present invention, there is provided separation means for separating and collecting the CNT with a carbonized layer in which the CNT layer is laminated integrally with the carbonized layer from the substrate belt, and the CNT with the carbonized layer is placed in an oxidizing atmosphere. It is a CNT continuous manufacturing apparatus provided with a carbonized layer combustion means for recovering only the CNT layer by diffusing combustion.
本発明の第１の形態によれば、基板層の上に耐熱性樹脂層とＡｌ層とＣＮＴ合成用の触媒層をこの順に形成したＣＮＴ製造用の四層型触媒基体が提供される。本発明の触媒基体は四層型触媒基体に特徴があり、触媒層は６００℃〜９００℃のＣＮＴ合成温度で微粒子化してＣＮＴを成長させる材料であり、Ａｌ層は触媒層の微粒子化を促進する材料である。Ａｌ金属の融点は６６０℃であり、蒸気圧が０．０１３Paになる蒸発温度は９２７℃と高温である。従って、触媒層の一種として利用されるＦｅが微粒子となって機能する温度、即ちＣＮＴ合成が為される通常温度の７００℃程度では、Ａｌ溶液状であるが蒸気圧は極めて低い。そして、その場に存在するＡｌの促進作用により形成された触媒微粒子を根元に含みながら、高度に配向したＣＮＴが触媒層上に成長し、ＣＮＴ層が形成されてゆく。耐熱性樹脂層は、合成温度環境下でＣＮＴ層と基板を熱的に遮断する作用を行い、触媒金属とＡｌが基板中に熱的に拡散することを防止する作用を奏する。また、耐熱性樹脂層が耐熱性有機樹脂で形成される場合には、ＣＮＴを合成する原料ガスなどの還元性雰囲気中で、耐熱性樹脂層は炭化して炭化層（炭素膜）になり、この炭化層が下にある基板を保護する作用を奏する。しかも、この炭化層は下の基板層と分離（剥離）し易いから、ＣＮＴ層が炭化層と一体になって基板から分離され、基板の表面が秀麗であり、基板の再利用を図ることができる。ＣＮＴ層が炭化層と一体になって基板から分離されると、このＣＮＴ層を酸化性雰囲気中で燃焼すれば、エッジの多い炭化層はＣＯ２になって気散し、純粋のＣＮＴ層だけを取出すことが容易になる。つまり、耐熱性有機樹脂の場合には、基板の再利用を実現でき、同時にＣＮＴを純粋に精製することができるのである。 According to the first aspect of the present invention, there is provided a four-layer catalyst substrate for CNT production in which a heat-resistant resin layer, an Al layer, and a catalyst layer for CNT synthesis are formed in this order on a substrate layer. The catalyst substrate of the present invention is characterized by a four-layer catalyst substrate. The catalyst layer is a material that grows CNTs by growing them at a CNT synthesis temperature of 600 ° C. to 900 ° C., and the Al layer promotes the atomization of the catalyst layers. Material. The melting point of Al metal is 660 ° C., and the evaporation temperature at which the vapor pressure becomes 0.013 Pa is as high as 927 ° C. Therefore, at a temperature at which Fe used as a kind of catalyst layer functions as fine particles, that is, a normal temperature of about 700 ° C. at which CNT synthesis is performed, although it is in the form of an Al solution, the vapor pressure is extremely low. Then, highly oriented CNT grows on the catalyst layer while containing catalyst fine particles formed by the promoting action of Al present at the site, and a CNT layer is formed. The heat-resistant resin layer acts to thermally shut off the CNT layer and the substrate under the synthesis temperature environment, and acts to prevent the catalyst metal and Al from thermally diffusing into the substrate. When the heat resistant resin layer is formed of a heat resistant organic resin, the heat resistant resin layer is carbonized into a carbonized layer (carbon film) in a reducing atmosphere such as a raw material gas for synthesizing CNTs. This carbonized layer acts to protect the underlying substrate. Moreover, since this carbonized layer is easily separated (peeled) from the underlying substrate layer, the CNT layer is separated from the substrate together with the carbonized layer, the surface of the substrate is excellent, and the substrate can be reused. it can. When the CNT layer is integrated with the carbonized layer and separated from the substrate, if this CNT layer is burned in an oxidizing atmosphere, the carbonized layer with a lot of edges is diffused as CO2, and only the pure CNT layer is removed. It becomes easy to take out. That is, in the case of a heat-resistant organic resin, the substrate can be reused, and at the same time, CNT can be purified purely.
触媒層の膜厚は、合成されるＣＮＴの断面直径を決める因子であり、１ｎｍ〜１００ｎｍ、好適には１ｎｍ〜２０ｎｍがよく、上記範囲内であれば自在に取捨選択できる。Ａｌ層の厚みは、樹脂層との隔たりを保持しながら触媒層の微粒子化を促進する意味から、触媒層の厚みと相関関係を有し、触媒層の厚みと同程度に調整される。従って、Ａｌ層の厚みとしては、１ｎｍ〜１００ｎｍ、好適には１ｎｍ〜２０ｎｍがよく、上記範囲内であれば自在に取捨選択できる。耐熱性樹脂層は、ＣＮＴ合成温度環境下で触媒層と基板層を合成時間の間、熱的に遮断できる耐熱性を有することが求められ、耐熱温度としては３５０℃以上、好適には４００℃以上、更に好適には４５０℃以上あればよい。樹脂は高温により徐々に分解してゆくから、耐熱性樹脂層の厚みは合成の進行に従って低減するが、合成終了時点で耐熱性樹脂層が薄く残留していてもよいし、合成の終了時点では樹脂層の全量が炭化層に変化していてもよい。ＣＮＴ合成中に耐熱性樹脂層が存在すれば、この耐熱性樹脂層が触媒層と基板層とを物理的に遮断する作用を奏する。また、耐熱性樹脂層の全量が炭化層に変化しても、この炭化層が触媒層と基板層とを物理的に遮断する作用を奏する。この物理的遮断作用が基板層を保護して基板層の再利用性を可能にし、しかも合成されたＣＮＴ層と基板層とを物理的に隔壁するからＣＮＴ層への基板層の影響を遮断することができる。従って、耐熱性樹脂層の厚みとして０．１μｍ〜１００μｍ、好ましくは１μｍ〜２０μｍが好ましい。基板層は合成されるＣＮＴを支持する基体であり、剛体からなる非可撓性素材、自由に撓む性質を有し曲げ変形も可能な可撓性素材、特に合金を含む金属、特に非錆性金属を使用した巻取可能素材が好適である。形態保持性及び再利用の観点から、基板層の厚みは剛体では１０μｍ以上で、特に３０μｍ以上が好ましい。形状は、平板、長手平板、巻取可能なベルト、その他各種形状がある。
耐熱性樹脂層を基板層に形成するには、耐熱性樹脂の溶液やペーストを塗布する方法、印刷する方法、具体的にはスピンコート法、スクリーン印刷法、インクジェット法、その他の公知の塗布方法が利用でき、塗布後乾燥して耐熱性樹脂層とする。Ａｌ層と触媒層は薄膜形成するため、物理的蒸着法、化学的蒸着法、スパッタリング法などその他の公知の塗布方法が利用できる。
The film thickness of the catalyst layer is a factor that determines the cross-sectional diameter of the synthesized CNT, and is 1 nm to 100 nm, preferably 1 nm to 20 nm, and can be freely selected within the above range. The thickness of the Al layer has a correlation with the thickness of the catalyst layer and is adjusted to be approximately the same as the thickness of the catalyst layer in order to promote the atomization of the catalyst layer while maintaining a separation from the resin layer. Therefore, the thickness of the Al layer is 1 nm to 100 nm, preferably 1 nm to 20 nm, and can be freely selected within the above range. The heat resistant resin layer is required to have heat resistance capable of thermally shutting off the catalyst layer and the substrate layer during the synthesis time in a CNT synthesis temperature environment, and the heat resistant temperature is 350 ° C. or higher, preferably 400 ° C. As described above, 450 ° C. or higher is more preferable. Since the resin gradually decomposes at a high temperature, the thickness of the heat-resistant resin layer decreases as the synthesis progresses, but the heat-resistant resin layer may remain thin at the end of synthesis, or at the end of synthesis. The total amount of the resin layer may be changed to a carbonized layer. If a heat resistant resin layer is present during CNT synthesis, the heat resistant resin layer has an effect of physically blocking the catalyst layer and the substrate layer. Moreover, even if the total amount of the heat resistant resin layer is changed to the carbonized layer, the carbonized layer exerts an action of physically blocking the catalyst layer and the substrate layer. This physical blocking action protects the substrate layer and enables the reuse of the substrate layer, and also physically separates the synthesized CNT layer and the substrate layer, thereby blocking the influence of the substrate layer on the CNT layer. be able to. Therefore, the thickness of the heat resistant resin layer is preferably 0.1 μm to 100 μm, and more preferably 1 μm to 20 μm. The substrate layer is a base that supports the CNT to be synthesized, and is a non-flexible material made of a rigid body, a flexible material that can bend freely and bendable, especially metals including alloys, especially non-rust. A rollable material using a conductive metal is suitable. From the viewpoint of shape retention and reuse, the thickness of the substrate layer is preferably 10 μm or more, particularly preferably 30 μm or more, for a rigid body. The shape includes a flat plate, a long flat plate, a belt that can be wound, and various other shapes.
In order to form the heat-resistant resin layer on the substrate layer, a method of applying a heat-resistant resin solution or paste, a method of printing, specifically, a spin coating method, a screen printing method, an inkjet method, or other known application methods Can be used and dried after application to form a heat-resistant resin layer. Since the Al layer and the catalyst layer are formed into thin films, other known coating methods such as physical vapor deposition, chemical vapor deposition, and sputtering can be used.
本発明の第２の形態によれば、前記四層型触媒基体がＣＮＴ合成のために還元性雰囲気の高温環境に配置されたとき前記耐熱性樹脂層が炭化層に変化するＣＮＴ製造用の四層型触媒基体が提供される。還元性雰囲気の高温環境とは、ＣＮＴ合成温度で炭化水素などの原料ガスをキャリアガスとともに触媒層の表面に対し流通させた高温環境を意味しており、炭化層に変化する耐熱性樹脂とは、耐熱性有機樹脂を意味する。有機樹脂が還元性雰囲気と反応して、有機樹脂が炭化して最終的に炭化層に変化する。この炭化層（又はＣ層）は炭素膜と言い換えてもよく、合成されたＣＮＴ層の根元部分に炭化層が形成され、この炭化層を介してＣＮＴ層は基板層と接合している。前述したように、触媒層はＣＮＴの根元に含まれており、四層型触媒基体にＣＮＴ層が合成されると、ＣＮＴ層とＡｌ原子又はＡｌ層を介して炭化層と基板層の四層体に変化し、本発明ではこの四層体を基板炭化層付きＣＮＴと称する。 According to the second embodiment of the present invention, when the four-layer type catalyst substrate is placed in a high temperature environment of a reducing atmosphere for CNT synthesis, the heat-resistant resin layer changes into a carbonized layer. A layered catalyst substrate is provided. The high-temperature environment in a reducing atmosphere means a high-temperature environment in which a source gas such as hydrocarbon is circulated to the surface of the catalyst layer together with a carrier gas at the CNT synthesis temperature. What is a heat-resistant resin that changes to a carbonized layer? , Meaning heat resistant organic resin. The organic resin reacts with the reducing atmosphere, and the organic resin is carbonized and finally changed into a carbonized layer. This carbonized layer (or C layer) may be rephrased as a carbon film, and a carbonized layer is formed at the base of the synthesized CNT layer, and the CNT layer is bonded to the substrate layer via the carbonized layer. As described above, the catalyst layer is included at the base of the CNT, and when the CNT layer is synthesized on the four-layer catalyst base, the four layers of the carbonized layer and the substrate layer through the CNT layer and the Al atom or Al layer. In the present invention, this four-layer body is referred to as a substrate carbonized layer-attached CNT.
本発明の第３の形態によれば、前記基板が、セラミックス材、無機非金属、無機非金属化合物、金属を含む材料からなり、６００℃〜９００℃のＣＮＴ合成温度で耐熱性を有する材料から形成されたＣＮＴ製造用の四層型触媒基体が提供される。セラミックス材の一例として金属酸化物、石英板、サファイヤ板などの剛体素材、無機非金属化合物の一例として水晶板、溶融シリカ板などの剛体素材、無機非金属の一例としては、シリコン板、グラファイト板などの剛体素材があり、これらの材料は非可撓性素材である。これらの非可撓性素材から基板層を形成すると、平板状の基板層が形成できる。他方、合金を含む金属、特に耐熱性金属で非錆性金属（又は耐食性金属）の一例として、ニッケル、チタン、ジルコニウム、タンタルなどがあり、また鉄基合金としてＳＵＳ（ステンレス）、インコロイ、ニッケル基合金としてインコネル、ハステロイ、コバルト基合金としてＳ８１６、ニッケル銅合金としてモネルなどが利用できる。特に、ＳＵＳは安価で大量生産が可能であり、本発明の基板層として有用である。金属は可撓性素材であるから、基板を薄く形成することにより巻取可能基板、即ち金属フィルムを多重に卷回した金属ロールの形成が可能になる。例えばＳＵＳ基板をロールにしたＳＵＳロールを基板層に用いると、この基板層上に耐熱性樹脂層・Ａｌ層・触媒層を形成した長尺の四層型触媒基体を構成でき、ＣＮＴの安価な大量生産が可能になる。しかも、ＣＮＴ層形成後に炭化層付きＣＮＴを分離し、炭化層を燃焼気散させれば、金属ロールの再使用が可能になる。 According to the 3rd form of this invention, the said board | substrate consists of a ceramic material, an inorganic nonmetal, an inorganic nonmetallic compound, and the material containing a metal, and is from the material which has heat resistance at the CNT synthesis temperature of 600 to 900 degreeC. A four-layer catalyst substrate for producing formed CNTs is provided. Rigid materials such as metal oxides, quartz plates and sapphire plates as examples of ceramic materials, rigid materials such as quartz plates and fused silica plates as examples of inorganic nonmetallic compounds, silicon plates and graphite plates as examples of inorganic nonmetals These materials are non-flexible materials. When a substrate layer is formed from these inflexible materials, a flat substrate layer can be formed. On the other hand, nickel, titanium, zirconium, tantalum, etc. are examples of metals including alloys, particularly heat-resistant metals and non-rusting metals (or corrosion-resistant metals), and SUS (stainless steel), incoloy, nickel-based alloys as iron-based alloys. Inconel, Hastelloy as the alloy, S816 as the cobalt base alloy, Monel as the nickel copper alloy, and the like can be used. In particular, SUS is inexpensive and can be mass-produced, and is useful as a substrate layer of the present invention. Since metal is a flexible material, it is possible to form a rollable substrate, that is, a metal roll in which metal films are wound in multiple layers by forming a thin substrate. For example, when a SUS roll made of a SUS substrate is used as a substrate layer, a long four-layer type catalyst base in which a heat-resistant resin layer, an Al layer, and a catalyst layer are formed on the substrate layer can be configured. Mass production becomes possible. In addition, if the carbonized layer-attached CNTs are separated after the CNT layer is formed and the carbonized layer is burned off, the metal roll can be reused.
本発明の第４の形態によれば、前記耐熱性樹脂層が、ポリイミド樹脂、ポリアミドイミド樹脂、全芳香族ポリエステル系樹脂、その他の有機樹脂を含む材料からなり、４００℃以上の耐熱温度を有した耐熱性樹脂から形成されるＣＮＴ製造用の四層型触媒基体が提供できる。本発明の要点は、耐熱性樹脂層を基板層とＡｌ層の間に形成した点にある。ＣＮＴ合成温度で基板層を熱的に保護するために耐熱性樹脂でなければならず、しかもＣＮＴ合成時の還元性雰囲気中で炭化する素材、即ち有機樹脂が重要である。耐熱性有機樹脂は還元性雰囲気中で炭化し、耐熱性有機樹脂層は炭化層になる。ＣＮＴ合成温度が、６００℃〜９００℃と高温であるため、合成時間に依存するが、耐熱温度としては、４００℃以上、好ましくは４５０℃以上、更に好ましくは５００℃以上がよい。第４形態では、４００℃を耐熱温度の下限としている。ポリイミド樹脂の耐熱温度は一般に４００℃以上であり、現在５５０℃の耐熱温度が提供される素材がある。ポリアミドイミド樹脂も熱分解開始温度が４００℃以上であり、４００℃以上の耐熱温度を有すると云える。全芳香族ポリエステル系樹脂でも４００℃で溶融変形しない材料が開発されている。第４形態では、耐熱温度が４００度以上の耐熱性有機樹脂が利用される。 According to the fourth aspect of the present invention, the heat resistant resin layer is made of a material containing polyimide resin, polyamideimide resin, wholly aromatic polyester resin, or other organic resin, and has a heat resistant temperature of 400 ° C. or higher. It is possible to provide a four-layer catalyst substrate for producing CNTs formed from the heat resistant resin. The main point of the present invention is that a heat resistant resin layer is formed between the substrate layer and the Al layer. In order to thermally protect the substrate layer at the CNT synthesis temperature, it must be a heat resistant resin, and a material that is carbonized in a reducing atmosphere during CNT synthesis, that is, an organic resin is important. The heat resistant organic resin is carbonized in a reducing atmosphere, and the heat resistant organic resin layer becomes a carbonized layer. Since the CNT synthesis temperature is as high as 600 ° C. to 900 ° C., depending on the synthesis time, the heat resistant temperature is 400 ° C. or higher, preferably 450 ° C. or higher, more preferably 500 ° C. or higher. In the fourth embodiment, 400 ° C. is the lower limit of the heat resistant temperature. The heat resistance temperature of the polyimide resin is generally 400 ° C. or higher, and there is a material that currently provides a heat resistance temperature of 550 ° C. Polyamideimide resin also has a thermal decomposition starting temperature of 400 ° C. or higher, and has a heat resistant temperature of 400 ° C. or higher. A material that does not melt and deform at 400 ° C. even with wholly aromatic polyester resins has been developed. In the fourth embodiment, a heat resistant organic resin having a heat resistant temperature of 400 degrees or more is used.
本発明の第５の形態によれば、前記触媒層がＦｅ、Ｃｏ、Ｎｉ、Ｍｏ、Ｐｔを含む遷移金属の一種以上から形成されるＣＮＴ製造用の四層型触媒基体が提供される。例えば、Ｆｅ層、Ｃｏ層、Ｎｉ層、Ｍｏ層、Ｐｔ層が最も簡単であるが、Ｆｅ−Ｃｏ層や、Ｆｅ−Ｎｉ層、Ｆｅ−Ｍｏ層などの複合金属層や合金層としてもよい。効率よく配向ＣＮＴ層を形成できる触媒層なら利用できる。 According to a fifth aspect of the present invention, there is provided a four-layer catalyst substrate for producing CNTs, wherein the catalyst layer is formed from one or more transition metals including Fe, Co, Ni, Mo, and Pt. For example, the Fe layer, the Co layer, the Ni layer, the Mo layer, and the Pt layer are the simplest, but a composite metal layer such as an Fe—Co layer, an Fe—Ni layer, or an Fe—Mo layer, or an alloy layer may be used. Any catalyst layer that can efficiently form an aligned CNT layer can be used.
本発明の第６の形態によれば、前記基板層がベルト状に形成された金属製の基板ベルトであり、前記基板ベルトの上に前記耐熱性樹脂層、前記Ａｌ層及び前記触媒層を積層して四層型触媒基体ベルトを構成したＣＮＴ製造用の四層型触媒基体が提供される。金属製基板ベルトとは、ロール状に卷回して巻き取れる金属ベルトのことであり、四層型触媒基体ベルトとは極めて長尺のベルトであり、合金を含む金属ベルトから容易に形成できる。従って、触媒層の表面が大面積化でき、ＣＮＴの大量合成が可能になる。一方から他方にベルトを走行させながら、触媒層表面にＣＮＴを連続的に合成することが可能になる。 According to the sixth aspect of the present invention, the substrate layer is a metal substrate belt formed in a belt shape, and the heat-resistant resin layer, the Al layer, and the catalyst layer are laminated on the substrate belt. Thus, a four-layer catalyst substrate for producing CNTs constituting a four-layer catalyst substrate belt is provided. The metal substrate belt is a metal belt that can be wound in a roll shape, and the four-layer catalyst base belt is an extremely long belt, and can be easily formed from a metal belt containing an alloy. Therefore, the surface of the catalyst layer can be enlarged, and a large amount of CNT can be synthesized. It is possible to continuously synthesize CNTs on the surface of the catalyst layer while running the belt from one side to the other.
本発明の第７の形態によれば、ＣＮＴ製造用の四層型触媒基体を反応室に配置し、反応室内をＣＮＴ合成温度に加熱して、原料ガスを前記四層型触媒基体の触媒層の表面に接触させ、前記触媒層の表面にＣＮＴを成長させるＣＮＴ製造方法を提供できる。四層型触媒基体を反応室に配置するとは、四層型触媒基体を静止状態で配置する場合、多数の四層型触媒基体をベルト上に間隔をおいて載置し、連続走行状態で反応室内に走行配置する場合、又は第６形態の四層型触媒基体ベルトを反応室内に連続走行させて反応室内に走行配置する場合などを含む。このようにすることによって、触媒層の表面にＣＮＴを合成でき、しかも大量合成を可能にする。基板層に炭化層を介してＣＮＴを形成できるから、炭化層付きＣＮＴを基板層から分離（剥離）すれば、無傷の基板層を再利用することもできる。 According to the seventh aspect of the present invention, a four-layer catalyst substrate for producing CNTs is arranged in the reaction chamber, the reaction chamber is heated to the CNT synthesis temperature, and the source gas is supplied to the catalyst layer of the four-layer catalyst substrate. It is possible to provide a CNT manufacturing method in which CNT is grown on the surface of the catalyst layer. The four-layer type catalyst substrate is arranged in the reaction chamber. When the four-layer type catalyst substrate is arranged in a stationary state, a large number of four-layer type catalyst substrates are placed on the belt at intervals and reacted in a continuous running state. This includes a case where the vehicle is placed in a room, or a case where the four-layer catalyst substrate belt of the sixth embodiment is continuously run in a reaction chamber and is placed in a reaction chamber. By doing so, CNT can be synthesized on the surface of the catalyst layer, and mass synthesis is possible. Since the CNTs can be formed on the substrate layer via the carbonized layer, the intact substrate layer can be reused by separating (peeling) the carbonized layer-attached CNTs from the substrate layer.
本発明の第８の形態によれば、前記四層型触媒基体を前記四層型触媒基体ベルトで構成し、前記四層型触媒基体ベルトを前記反応室に走行させながら、前記触媒層の表面にＣＮＴを成長させ、前記四層型触媒基体ベルトの表面にＣＮＴを大量合成するＣＮＴ製造方法を提供できる。この第８形態は、前記第７形態のなかでもベルト製造方法に限定した製法である。基板層がベルト状に形成された基板ベルトからなり、この基板ベルトの上に耐熱性樹脂層とＡｌ層と触媒層が積層されて前記四層型触媒基体ベルトが構成されている。この四層型触媒基体ベルトを反応室に走行させれば、キャリアガスと原料ガスにより触媒層の表面にＣＮＴ層が合成される。前記ベルトを連続走行させれば、触媒層の上にＣＮＴ層が連続的に製造されてゆき、ベルトをロール状に卷回回収すれば、大量のＣＮＴを連続製造することが可能になる。しかも、このベルトから炭化層付きＣＮＴを分離すれば、基板ベルトは再利用可能になり、ＣＮＴを安価且つ大量に製造することができる。 According to an eighth aspect of the present invention, the four-layer type catalyst base is constituted by the four-layer type catalyst base belt, and the four-layer type catalyst base belt is allowed to travel to the reaction chamber while CNTs can be grown on the surface of the four-layer catalyst substrate belt to synthesize a large amount of CNTs. The eighth embodiment is a manufacturing method limited to the belt manufacturing method in the seventh embodiment. The substrate layer is composed of a substrate belt formed in a belt shape, and the four-layer catalyst base belt is constituted by laminating a heat-resistant resin layer, an Al layer, and a catalyst layer on the substrate belt. When this four-layer type catalyst substrate belt is run in the reaction chamber, the CNT layer is synthesized on the surface of the catalyst layer by the carrier gas and the raw material gas. If the belt is continuously run, a CNT layer is continuously produced on the catalyst layer, and if the belt is wound and collected in a roll, a large amount of CNT can be continuously produced. Moreover, if the carbonized layer-attached CNTs are separated from the belt, the substrate belt can be reused, and the CNTs can be manufactured at low cost and in large quantities.
本発明の第９の形態によれば、ＣＮＴ製造方法により製造され、前記合成温度により前記耐熱性樹脂層が炭化層に変化し、前記触媒層が合成されたＣＮＴ層に組み込まれ、前記基板層の上に前記炭化層と前記ＣＮＴ層がこの順に積層された基板炭化層付きＣＮＴを提供できる。前述したように、ＣＮＴ合成温度では、触媒層はＡｌ層の微粒子化促進作用により手ごろな触媒微粒子へと変化し、触媒微粒子がＣＮＴの根元に内包されながらＣＮＴ層が成長する。他方、耐熱性樹脂層は高温にさらされて炭化層へと変化し、基板層の上に炭化層とＡｌ層を介してＣＮＴ層が積層された状態でＣＮＴ合成が終了する。この基体全体を基板炭化層付きＣＮＴと称し、本第９形態では、基板炭化層付きＣＮＴが大量に製造できる。これからＣＮＴを分離すれば良い訳である。 According to the ninth aspect of the present invention, the substrate layer is manufactured by a CNT manufacturing method, the heat-resistant resin layer is changed into a carbonized layer by the synthesis temperature, and the catalyst layer is incorporated into the synthesized CNT layer. The carbonized layer with the substrate carbonized layer in which the carbonized layer and the CNT layer are laminated in this order can be provided. As described above, at the CNT synthesis temperature, the catalyst layer changes to a convenient catalyst particle by the action of promoting the atomization of the Al layer, and the CNT layer grows while the catalyst particle is encapsulated at the base of the CNT. On the other hand, the heat-resistant resin layer is exposed to a high temperature to change to a carbonized layer, and CNT synthesis is completed in a state where the carbonized layer and the Al layer are laminated on the substrate layer. This whole substrate is called CNT with a substrate carbonized layer. In the ninth embodiment, a large amount of CNT with a substrate carbonized layer can be produced. The CNTs can be separated from this.
本発明の第１０の形態によれば、基板炭化層付きＣＮＴから基板層を分離して得られ、前記炭化層の上に前記ＣＮＴ層が配置された炭化層付きＣＮＴが提供される。第９形態によって基板炭化層付きＣＮＴが大量に製造されており、この基板炭化層付きＣＮＴから基板層をスクレイパーなどの分離手段で分離すると、基板層と炭化層付きＣＮＴに分離される。基板層は再利用に回され、炭化層付きＣＮＴはＣＮＴ精製処理に回される。基板炭化層付きＣＮＴと炭化層付きＣＮＴはＣＮＴを分離する中で得られる中間体である。 According to the tenth aspect of the present invention, there is provided a CNT with a carbonized layer obtained by separating a substrate layer from a CNT with a substrate carbonized layer, wherein the CNT layer is disposed on the carbonized layer. A large amount of CNTs with a substrate carbonized layer is manufactured according to the ninth embodiment. When the substrate layer is separated from the CNTs with a substrate carbonized layer by a separating means such as a scraper, the substrate layer and the CNTs with the carbonized layer are separated. The substrate layer is reused, and the carbonized CNT is sent to the CNT purification process. The CNT with a substrate carbonized layer and the CNT with a carbonized layer are intermediates obtained in separating CNTs.
本発明の第１１の形態によれば、炭化層付きＣＮＴを酸化雰囲気中で加熱して前記炭化層を燃焼気散させ、前記ＣＮＴ層だけをＣＮＴとして回収するＣＮＴ回収方法が提供される。前記第１０形態により、大量の炭化層付きＣＮＴが中間体として製造される。炭化層付きＣＮＴを酸化性雰囲気、即ち大気中で燃焼すると、炭化層とは炭素膜であるから、酸素と化合してＣＯ２となって気散してゆく。完全に燃焼すると、炭化層は全てＣＯ２になり、最終的にＣＮＴ層だけが回収できる。ＣＮＴの耐熱温度は極めて高いから、燃焼によりＣＮＴは何ら変化せず、ＣＮＴ層だけを回収できる。従って、この方法により、配向ＣＮＴが製造されることになる。基板炭化層付きＣＮＴと炭化層付きＣＮＴ及びこれからＣＮＴを回収する方法は本発明により初めて提案された画期的なＣＮＴ製造方法である。 According to the eleventh aspect of the present invention, there is provided a CNT recovery method in which the carbonized layer-attached CNT is heated in an oxidizing atmosphere to burn and burn the carbonized layer, and only the CNT layer is recovered as CNTs. According to the tenth embodiment, a large amount of carbonized CNTs is produced as an intermediate. When the carbonized layer-attached CNTs are burned in an oxidizing atmosphere, that is, in the air, the carbonized layer is a carbon film, so it combines with oxygen and diffuses into CO2. When completely burned, all the carbonized layer becomes CO2, and finally only the CNT layer can be recovered. Since the heat resistant temperature of CNT is extremely high, the CNT does not change by combustion, and only the CNT layer can be recovered. Accordingly, aligned CNTs are produced by this method. The CNT with a substrate carbonized layer, the CNT with a carbonized layer, and a method for recovering CNT from this are the epoch-making CNT manufacturing methods proposed for the first time by the present invention.
本発明の第１２の形態によれば、基板ベルトを駆動ローラと従動ローラの周囲に卷回して無端ベルトを構成し、前記基板ベルトの表面に前記耐熱性樹脂層、前記Ａｌ層及び前記触媒層をこの順に積層して前記四層型触媒基体ベルトを形成する耐熱性樹脂層形成手段、Ａｌ層形成手段及び触媒層形成手段を配置し、形成された前記四層型触媒基体ベルトの表面にＣＮＴを合成するＣＶＤ反応手段を配置して、前記四層型触媒基体ベルトを走行させながら前記四層型触媒基体ベルト上にＣＮＴ層を形成し、前記ＣＮＴ層を形成した前記四層型触媒基体ベルトでは、前記触媒層がＣＮＴに組み込まれた前記ＣＮＴ層が、前記耐熱性樹脂層が変化した炭化層を介して前記基板ベルト上に積層された形態を有するＣＮＴ連続製造装置が提供される。この第１２形態を簡単に述べると、基板ベルトを無端ベルト状に周回させ、周回中に基板ベルト上に耐熱性樹脂層とＡｌ層と触媒層を連続的に積層して四層型触媒基体ベルトへと変化させ、この四層型触媒基体ベルトの触媒層上にＣＮＴ層を周回中に連続製造するＣＮＴ連続製造装置が実現されている。これにより、従来から平板状の基板にＣＮＴを合成した場合と比較して、大面積のベルト表面にＣＮＴを大量合成する道を開くことができる。 According to the twelfth aspect of the present invention, an endless belt is formed by winding a substrate belt around a driving roller and a driven roller, and the heat-resistant resin layer, the Al layer, and the catalyst layer are formed on the surface of the substrate belt. Are arranged in this order to form a heat-resistant resin layer forming means, an Al layer forming means and a catalyst layer forming means for forming the four-layer catalyst substrate belt, and CNTs are formed on the surface of the formed four-layer catalyst substrate belt. The four-layer type catalyst substrate belt is provided with a CVD reaction means for synthesizing, forming a CNT layer on the four-layer catalyst substrate belt while running the four-layer catalyst substrate belt, and forming the CNT layer. Then, the CNT continuous manufacturing apparatus which has the form with which the said CNT layer in which the said catalyst layer was integrated in CNT was laminated | stacked on the said substrate belt through the carbonization layer in which the said heat resistant resin layer changed is provided. Briefly describing this twelfth embodiment, a four-layer type catalyst substrate belt is obtained by circulating a substrate belt in an endless belt shape and continuously laminating a heat-resistant resin layer, an Al layer and a catalyst layer on the substrate belt during the circulation. Thus, a continuous CNT manufacturing apparatus has been realized that continuously manufactures a CNT layer on the catalyst layer of the four-layer type catalyst substrate belt during circulation. Thereby, compared with the case where CNT is conventionally synthesized on a flat plate-like substrate, it is possible to open a way to synthesize a large amount of CNT on the belt surface of a large area.
本発明の第１３の形態によれば、基板ベルトを卷回した基板ロールと、前記基板ロールから送出される前記基板ベルトの表面に前記耐熱性樹脂層、前記Ａｌ層及び前記触媒層をこの順に積層して前記四層型触媒基体ベルトを形成する耐熱性樹脂層形成手段、Ａｌ層形成手段及び触媒層形成手段を配置し、形成された前記四層型触媒基体ベルトを卷回した四層型触媒基体ロールを製造する四層型触媒基体ロールの製造装置を提供することができる。本第１３形態は、基板ロールから送出される基板ベルトに耐熱性樹脂層とＡｌ層と触媒層を順次積層して四層型触媒基体ベルトを形成し、この四層型触媒基体ベルトを卷回して四層型触媒基体ロールを製造する装置を開示している。ＣＮＴ合成の前段階の処理である。この四層型触媒基体ロールは四層型触媒基体ベルトを多重に卷回したものであるから、四層型触媒基体ベルトの全長は極めて長く、その表面積は第１２形態の無端ベルトの周回長と比較しても格段に大面積化されており、次のＣＮＴ合成処理で大量のＣＮＴ合成を可能にするものである。 According to the thirteenth aspect of the present invention, the substrate roll wound around the substrate belt, and the heat-resistant resin layer, the Al layer, and the catalyst layer on the surface of the substrate belt fed from the substrate roll in this order. A four-layer type in which a heat-resistant resin layer forming means, an Al layer forming means, and a catalyst layer forming means that are stacked to form the four-layer catalyst base belt are arranged and the formed four-layer catalyst base belt is wound An apparatus for producing a four-layer type catalyst substrate roll for producing a catalyst substrate roll can be provided. In the thirteenth embodiment, a four-layer catalyst substrate belt is formed by sequentially laminating a heat-resistant resin layer, an Al layer, and a catalyst layer on a substrate belt fed from a substrate roll, and the four-layer catalyst substrate belt is wound. An apparatus for producing a four-layer catalyst substrate roll is disclosed. This is a pre-stage process of CNT synthesis. Since this four-layer catalyst substrate roll is a four-layer catalyst substrate belt wound in multiple layers, the total length of the four-layer catalyst substrate belt is extremely long, and its surface area is the circumference of the endless belt of the twelfth embodiment. Even in comparison, the area is greatly increased, and a large amount of CNT can be synthesized by the next CNT synthesis process.
本発明の第１４の形態によれば、四層型触媒基体ロールと、前記四層型触媒基体ロールから送出される前記四層型触媒基体ベルトの表面に前記ＣＮＴ層を形成するＣＶＤ反応手段を配置し、前記ＣＮＴ層を形成された前記四層型触媒基体ベルトを卷回して回収する回収ロールを配置し、前記ＣＮＴ層を形成された前記四層型触媒基体ベルトでは、前記触媒層がＣＮＴに組み込まれた前記ＣＮＴ層が、前記耐熱性樹脂層が変化した炭化層を介して前記基板ベルト上に積層された形態を有するＣＮＴ連続製造装置を提供することができる。第１３形態によって製造された四層型触媒基体ロールを出発ロールとし、この四層型触媒基体ロールから送出される四層型触媒基体ベルトにＣＮＴを合成してゆき、ＣＮＴを合成された四層型触媒基体ベルトを回収ロールに卷回回収するものである。ＣＮＴを合成することによって、触媒層はＣＮＴに組み込まれてゆき、また耐熱性樹脂層は炭化層に変化し、回収されるベルトは基板ベルトに炭化層を介してＣＮＴ層が形成されたベルトになっている。このベルトをＣＮＴ層を形成された四層型触媒基体ベルトと称している。ベルトの全長に亘ってＣＮＴが合成されているから、ＣＮＴの大量合成を実現することができる。 According to a fourteenth aspect of the present invention, there is provided a CVD reaction means for forming the CNT layer on the surface of the four-layer catalyst substrate roll and the four-layer catalyst substrate belt fed from the four-layer catalyst substrate roll. The four-layer catalyst substrate belt having the CNT layer formed thereon is disposed with a collection roll for winding and collecting the four-layer catalyst substrate belt on which the CNT layer is formed. The CNT continuous manufacturing apparatus which has the form laminated | stacked on the said substrate belt through the carbonized layer in which the said heat resistant resin layer changed can be provided. The four-layer catalyst base roll manufactured according to the thirteenth embodiment is used as a starting roll, and CNTs are synthesized on the four-layer catalyst base belt fed from the four-layer catalyst base roll, and the four-layer synthesized CNTs. The type catalyst substrate belt is collected on a collecting roll. By synthesizing CNT, the catalyst layer is incorporated into the CNT, the heat-resistant resin layer is changed to a carbonized layer, and the recovered belt is a belt in which the CNT layer is formed on the substrate belt via the carbonized layer. It has become. This belt is referred to as a four-layer catalyst substrate belt on which a CNT layer is formed. Since CNTs are synthesized over the entire length of the belt, a large amount of CNTs can be synthesized.
本発明の第１５の形態によれば、前記基板ベルトから、前記ＣＮＴ層が前記炭化層と一体に積層された炭化層付きＣＮＴを分離回収する分離手段を設け、前記炭化層付きＣＮＴを酸化雰囲気中で燃焼気散させて前記ＣＮＴ層だけを回収する炭化層燃焼手段を設けるＣＮＴ連続製造装置を提供することができる。第１２形態の無端ベルト、及び第１４形態の回収ロールにはＣＮＴが接合しており、このＣＮＴを分離して回収する必要がある。両者の基板ベルトには炭化層を介してＣＮＴ層が接合している。これらのベルトに対し、例えばスクレイパーの様な分離手段により炭化層付きＣＮＴ（炭化層が付着したＣＮＴ層）を機械的に分離する。この分離によって炭化層付きＣＮＴは容器に回収される。炭化層付きＣＮＴは基板ベルトから容易に剥離されるから、基板ベルトは無傷のまま秀麗な基板ベルトとして回収され、次のＣＮＴ合成に再利用される。炭化層付きＣＮＴは酸化性雰囲気中、例えば大気中で燃焼させると、炭化層はＣＯ２ガスとして気散され、ＣＮＴ層だけが最終的に容器内に残留し、ＣＮＴの回収が完了する。炭化層燃焼手段とは、例えば加熱手段を付設した大気に連通する容器と考えればよい。本第１５形態の分離装置と炭化層燃焼手段を、第１２形態の無端ベルトに近接配置したり、また第１４形態のベルトに近接配置すれば、炭化層付きＣＮＴの回収と連続してＣＮＴの精製回収を実現でき、同時に基板ベルトの再利用をも実現することができる。 According to a fifteenth aspect of the present invention, there is provided separation means for separating and recovering the carbonized layer-attached CNT in which the CNT layer is laminated integrally with the carbonized layer from the substrate belt, and the carbonized layer-attached CNT is oxidized in an atmosphere. It is possible to provide a CNT continuous production apparatus provided with a carbonized layer combustion means for recovering only the CNT layer by being diffused by combustion. CNTs are bonded to the endless belt of the twelfth form and the collection roll of the fourteenth form, and it is necessary to separate and collect the CNTs. A CNT layer is bonded to both the substrate belts through a carbonized layer. For these belts, for example, a CNT with a carbonized layer (CNT layer with a carbonized layer attached) is mechanically separated by a separating means such as a scraper. By this separation, the carbonized carbon nanotubes are collected in a container. Since the carbonized layer-attached CNT is easily peeled off from the substrate belt, the substrate belt is recovered as an excellent substrate belt without being damaged and reused for the next CNT synthesis. When the CNT with a carbonized layer is burned in an oxidizing atmosphere, for example, in the air, the carbonized layer is diffused as CO2 gas, and only the CNT layer remains in the container finally, and the recovery of the CNT is completed. The carbonized layer combustion means may be considered as a container communicating with the atmosphere provided with heating means, for example. If the separation device of the fifteenth embodiment and the carbonized layer combustion means are disposed close to the endless belt of the twelfth embodiment or close to the belt of the fourteenth embodiment, the CNTs are continuously collected and recovered. Purification and recovery can be realized, and at the same time, reuse of the substrate belt can be realized.
以下、本発明の実施形態を添付図面に基づいて詳細に説明する。
図１は、本発明に係る四層型触媒基体の構成図である。（１Ａ）には、本発明の四層型触媒基体の基本構成が示されている。基板層２の上に耐熱性樹脂層４が形成され、耐熱性樹脂層４の上にＡｌ層６が形成され、更にＡｌ層６の上に触媒層８が形成されて四層型触媒基体１が完成される。基板層２は各種材料で形成されるが、（１Ｂ）には可撓性基板層の代表例としてＳＵＳ基板層２が開示されている。ＳＵＳ基板層はＣＮＴ合成温度である６００℃〜９００℃で耐熱性且つ耐食性を有し、しかも平板状のみならずロール状に形成できるから大面積化が容易である。勿論、ＳＵＳ以外にも、例えばニッケル、チタン、ジルコニウム、タンタルなどがあり、また鉄基合金としてインコロイ、ニッケル基合金としてインコネル、ハステロイ、コバルト基合金としてＳ８１６、ニッケル銅合金としてモネルなどが利用できる。また、（１Ｃ）には非可撓性基板層の代表例としてシリコン基板層２が開示されている。シリコン基板層２はＣＮＴ合成温度である６００℃〜９００℃で耐熱性且つ耐食性を有し、平板状に形成できる。またシリコン以外にも、セラミックス材の一例として金属酸化物、石英板、サファイヤ板などの剛体素材、無機非金属化合物の一例として水晶板、溶融シリカ板などの剛体素材、無機非金属の一例としては、シリコン板、グラファイト板などの剛体素材があり、これらの材料は非可撓性素材として纏められる。
Embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
FIG. 1 is a configuration diagram of a four-layer type catalyst substrate according to the present invention. (1A) shows the basic structure of the four-layer catalyst substrate of the present invention. A heat-resistant resin layer 4 is formed on the substrate layer 2, an Al layer 6 is formed on the heat-resistant resin layer 4, and a catalyst layer 8 is further formed on the Al layer 6. Is completed. The substrate layer 2 is formed of various materials. In (1B), a SUS substrate layer 2 is disclosed as a representative example of the flexible substrate layer. The SUS substrate layer has heat resistance and corrosion resistance at a CNT synthesis temperature of 600 ° C. to 900 ° C., and can be formed not only in a flat plate shape but also in a roll shape, so that the area can be easily increased. Of course, in addition to SUS, for example, nickel, titanium, zirconium, tantalum, and the like can be used. Incoloy as an iron-based alloy, Inconel, Hastelloy as a nickel-based alloy, S816 as a cobalt-based alloy, and Monel as a nickel-copper alloy can be used. In (1C), a silicon substrate layer 2 is disclosed as a representative example of an inflexible substrate layer. The silicon substrate layer 2 has heat resistance and corrosion resistance at a CNT synthesis temperature of 600 ° C. to 900 ° C., and can be formed in a flat plate shape. In addition to silicon, examples of ceramic materials include rigid materials such as metal oxides, quartz plates, and sapphire plates, examples of inorganic non-metallic compounds such as quartz plates and fused silica plates, and examples of inorganic non-metals. There are rigid materials such as silicon plates and graphite plates, and these materials are collected as inflexible materials.
前記耐熱性樹脂層４としては、ポリイミド樹脂、ポリアミドイミド樹脂、全芳香族ポリエステル系樹脂、その他の有機樹脂を含む材料からなり、４００℃以上の耐熱温度を有した耐熱性樹脂が選択される。ＣＮＴ合成温度が、６００℃〜９００℃と高温であるため、合成時間に依存するが、耐熱温度としては、４００℃以上、好ましくは４５０℃以上、更に好ましくは５００℃以上がよい。ポリイミド樹脂の耐熱温度は一般に４００℃以上であり、現在５５０℃の耐熱温度が提供される素材がある。ポリアミドイミド樹脂も熱分解開始温度が４００℃以上であり、４００℃以上の耐熱温度を有すると云える。全芳香族ポリエステル系樹脂でも４００℃で溶融変形しない材料が開発されている。しかもこれらの耐熱性樹脂は有機樹脂であるから、ＣＮＴ合成温度且つ炭化水素などの原料ガスといった還元性雰囲気中では、炭化して炭化層に変化する。ＣＮＴ合成温度が６００℃以上であるから、現在最も耐熱温度の高いポリイミド樹脂が好適である。
前記触媒層はＦｅ、Ｃｏ、Ｎｉ、Ｍｏ、Ｐｔを含む遷移金属の一種以上から形成される。例えば、Ｆｅ層、Ｃｏ層、Ｎｉ層、Ｍｏ層、Ｐｔ層が最も簡単であるが、Ｆｅ−Ｃｏ層や、Ｆｅ−Ｎｉ層、Ｆｅ−Ｍｏ層などの複合金属層や合金層としてもよい。
Ａｌ層６は、触媒層８がＣＮＴ合成温度で微粒子化するときに、樹脂層との隔たりを作り、微細化と同時に粒径の均一化を促進するために配置される。
The heat resistant resin layer 4 is made of a material containing polyimide resin, polyamideimide resin, wholly aromatic polyester resin, or other organic resin and having a heat resistant temperature of 400 ° C. or higher. Since the CNT synthesis temperature is as high as 600 ° C. to 900 ° C., depending on the synthesis time, the heat resistant temperature is 400 ° C. or higher, preferably 450 ° C. or higher, more preferably 500 ° C. or higher. The heat resistance temperature of the polyimide resin is generally 400 ° C. or higher, and there is a material that currently provides a heat resistance temperature of 550 ° C. Polyamideimide resin also has a thermal decomposition starting temperature of 400 ° C. or higher, and has a heat resistant temperature of 400 ° C. or higher. A material that does not melt and deform at 400 ° C. even with wholly aromatic polyester resins has been developed. Moreover, since these heat-resistant resins are organic resins, they are carbonized and changed into a carbonized layer in a reducing atmosphere such as a CNT synthesis temperature and a raw material gas such as hydrocarbon. Since the CNT synthesis temperature is 600 ° C. or higher, a polyimide resin having the highest heat-resistant temperature is suitable at present.
The catalyst layer is formed of one or more transition metals including Fe, Co, Ni, Mo, and Pt. For example, the Fe layer, the Co layer, the Ni layer, the Mo layer, and the Pt layer are the simplest, but a composite metal layer such as an Fe—Co layer, an Fe—Ni layer, or an Fe—Mo layer, or an alloy layer may be used.
The Al layer 6 is disposed in order to make a separation from the resin layer when the catalyst layer 8 is atomized at the CNT synthesis temperature, and to promote the uniformization of the particle size simultaneously with the miniaturization.
図２は、本発明に係る四層型触媒基体の製造手順図である。以下では、各層の層厚が一例として例示されている。まず５０μｍの基板層が２が配置され、この基板層２の上面に耐熱性樹脂層４がスピンコート法により５μｍの厚さで塗布され、その後乾燥される。次に、耐熱性樹脂層４の上面にＡｌ層６がスパッタリング法により１０ｎｍの膜厚で形成される。更に、Ａｌ層６の上面に触媒層８としてＦｅ層がスパッタリング法により４ｎｍの膜厚で形成され、最終的に四層型触媒基体１が完成される。
膜厚に関しては、種々に変更可能である。例えば、触媒層の膜厚は、合成されるＣＮＴの断面直径を決める因子であり、１ｎｍ〜１００ｎｍ、好適には１ｎｍ〜２０ｎｍがよい。Ａｌ層の厚みは、樹脂層との隔たり及び触媒層の微粒子化を促進する意味から、触媒層の厚みと相関関係を有し、触媒層の厚みと同程度に調整される。従って、Ａｌ層の厚みとしては、１ｎｍ〜１００ｎｍ、好適には１ｎｍ〜２０ｎｍがよい。耐熱性樹脂層の厚みとして０．１μｍ〜１００μｍ、好ましくは１μｍ〜２０μｍが好ましい。基板層の厚みは形態保持性と耐熱性の観点から、非可撓性基板では１０μｍ以上で、特に３０μｍ以上が好ましい。また、非可撓性基板では市販状況から１０μｍ以上で、再利用し易いためには４０μｍ以上が好ましい。耐熱性樹脂層を基板層に形成するには、耐熱性樹脂の溶液やペーストを塗布する方法、印刷する方法、具体的にはスピンコート法、スクリーン印刷法、インクジェット法、その他の公知の塗布方法が利用でき、塗布後乾燥して耐熱性樹脂層とする。Ａｌ層と触媒層は薄膜形成するため、物理的蒸着法、化学的蒸着法、スパッタリング法、溶液塗布法などその他の公知の塗布方法が利用できる。
FIG. 2 is a production procedure diagram of a four-layer type catalyst substrate according to the present invention. Below, the layer thickness of each layer is illustrated as an example. First, a 50 μm substrate layer 2 is disposed, and a heat resistant resin layer 4 is applied to the upper surface of the substrate layer 2 by a spin coating method to a thickness of 5 μm, and then dried. Next, an Al layer 6 is formed with a thickness of 10 nm on the upper surface of the heat resistant resin layer 4 by sputtering. Further, an Fe layer is formed as a catalyst layer 8 with a film thickness of 4 nm on the upper surface of the Al layer 6 by sputtering, and the four-layer catalyst substrate 1 is finally completed.
Various changes can be made to the film thickness. For example, the film thickness of the catalyst layer is a factor that determines the cross-sectional diameter of the synthesized CNT, and is 1 nm to 100 nm, preferably 1 nm to 20 nm. The thickness of the Al layer has a correlation with the thickness of the catalyst layer and is adjusted to be approximately the same as the thickness of the catalyst layer in order to promote separation from the resin layer and atomization of the catalyst layer. Therefore, the thickness of the Al layer is 1 nm to 100 nm, preferably 1 nm to 20 nm. The thickness of the heat resistant resin layer is 0.1 μm to 100 μm, preferably 1 μm to 20 μm. From the viewpoint of shape retention and heat resistance, the thickness of the substrate layer is preferably 10 μm or more, particularly preferably 30 μm or more, for non-flexible substrates. In addition, in the case of an inflexible substrate, it is 10 μm or more from the market situation, and 40 μm or more is preferable for easy reuse. In order to form the heat-resistant resin layer on the substrate layer, a method of applying a heat-resistant resin solution or paste, a method of printing, specifically, a spin coating method, a screen printing method, an inkjet method, or other known application methods Can be used and dried after application to form a heat-resistant resin layer. Since the Al layer and the catalyst layer are formed into thin films, other known coating methods such as physical vapor deposition, chemical vapor deposition, sputtering, and solution coating can be used.
図３は、本発明に係る四層型触媒基体を用いてＣＮＴを製造する概略手順と、得られた基板炭化層付きＣＮＴの概略構成図である。四層型触媒基体１は、図示しないベルト面上に載置され、前記四層型触媒基体１を上方から覆うように反応室が配置されており、反応室とベルト面とは接触しないように隙間が開けら、外気と大気圧で連通している。従って、反応圧力は大気圧である。四層型触媒基体１の基板層２の大きさは２０ｍｍ×２０ｍｍの平板である。反応室に収容された四層型触媒基体１は６８０℃で１０分間だけ予熱される。予熱時間の１０分が経過してから、６８０℃に保持された反応室中に、キャリアガスとしてＨｅを２４５ｓｃｃｍの流量で流通させ、原料ガスとしてＣ２Ｈ２を１４ｓｃｃｍの流量で流通させる。反応時間は１０分間であり、この１０分間でＣＮＴが触媒層８の上面に合成される。反応時間が経過するとキャリアガスと原料ガスの供給は遮断され、ＣＮＴ合成は停止される。ＣＮＴ合成反応の結果、基板層２の上には炭化層１０を介してＣＮＴ層１２が形成されており、この全体を基板炭化層付きＣＮＴ１４と称する。触媒層８はＦe層であり、合成温度でＦｅ層はＡｌの微粒子化促進作用によりＡｌに包まれて均一なＦｅ触媒微粒子に変化する。この触媒微粒子はＣＮＴの根元に残ってＣＮＴは上方へ伸長する。触媒層８はＣＮＴに組み込まれながらＣＮＴ層へと変化する。ＡｌはＣＮＴに組み込まれずにＣＮＴ根元の外に残る。また、耐熱性樹脂層４は高温環境により分解気散しながら炭化層１０へと変化する。この炭化層１０は炭素だけからなる層で、Ｃ層といってもよいし、炭素膜といってもよい。 FIG. 3 is a schematic diagram illustrating a schematic procedure for producing CNTs using the four-layer catalyst substrate according to the present invention, and the obtained CNTs with a substrate carbonized layer. The four-layer type catalyst substrate 1 is placed on a belt surface (not shown), and a reaction chamber is disposed so as to cover the four-layer catalyst substrate 1 from above, so that the reaction chamber and the belt surface do not come into contact with each other. If there is a gap, it communicates with the outside air at atmospheric pressure. Therefore, the reaction pressure is atmospheric pressure. The size of the substrate layer 2 of the four-layer type catalyst base 1 is a flat plate of 20 mm × 20 mm. The four-layer catalyst substrate 1 accommodated in the reaction chamber is preheated at 680 ° C. for only 10 minutes. After 10 minutes of preheating time, He is circulated at a flow rate of 245 sccm as a carrier gas and C2H2 is circulated at a flow rate of 14 sccm as a source gas in a reaction chamber maintained at 680 ° C. The reaction time is 10 minutes, and CNTs are synthesized on the upper surface of the catalyst layer 8 in this 10 minutes. When the reaction time elapses, the supply of the carrier gas and the raw material gas is cut off, and the CNT synthesis is stopped. As a result of the CNT synthesis reaction, a CNT layer 12 is formed on the substrate layer 2 via a carbonized layer 10, and this whole is called CNT 14 with a substrate carbonized layer. The catalyst layer 8 is an Fe layer, and at the synthesis temperature, the Fe layer is encased in Al by the Al atomization promoting action and changes to uniform Fe catalyst particles. The catalyst fine particles remain at the base of the CNT, and the CNT extends upward. The catalyst layer 8 changes to a CNT layer while being incorporated in the CNT. Al remains outside the CNT root without being incorporated into the CNT. Further, the heat resistant resin layer 4 changes into the carbonized layer 10 while being decomposed and diffused by a high temperature environment. The carbonized layer 10 is a layer made of only carbon, and may be referred to as a C layer or a carbon film.
図４は、本発明に係る四層型触媒ＳＵＳ基体上に生成されたＣＮＴ層の断面ＳＥＭ写真図である。この写真は、基板層２として５０μｍ厚のＳＵＳ基板を使用してＣＮＴ合成された写真であるから、四層型触媒基体１を四層型触媒ＳＵＳ基体と称する。左側写真では、ＳＵＳ基板層２の上に３８μｍの高さの配向ＣＮＴが成長したＣＮＴ層１２が合成されている。右側写真は、ＣＮＴ層１２の一部の拡大写真であり、多少ジグザグしているが、ＣＮＴ層全体としては配向ＣＮＴが合成されている。 FIG. 4 is a cross-sectional SEM photograph of the CNT layer produced on the four-layer catalyst SUS substrate according to the present invention. Since this photograph is a photograph of CNT synthesis using a 50 μm thick SUS substrate as the substrate layer 2, the four-layer catalyst substrate 1 is referred to as a four-layer catalyst SUS substrate. In the left photograph, a CNT layer 12 in which oriented CNTs having a height of 38 μm are grown on the SUS substrate layer 2 is synthesized. The right-side photo is an enlarged photo of a part of the CNT layer 12 and is slightly zigzag, but oriented CNT is synthesized as the entire CNT layer.
図５は、本発明に係る四層型触媒ＳＵＳ基体上に生成されたＣＮＴのＴＥＭ写真と直径分布図である。左側写真から分かるように、合成されたＣＮＴは多層ＣＮＴ(写真中ではＭＷＮＴと表記)であり、断面直径は約２０ｎｍである。右側写真は、多数のＣＮＴの断面直径を計測して得られたＣＮＴの直径分布図である。平均直径は１１．６ｎｍであった。良質のＣＮＴが得られることが実証された。 FIG. 5 is a TEM photograph and a diameter distribution diagram of the CNT produced on the four-layer catalyst SUS substrate according to the present invention. As can be seen from the left photograph, the synthesized CNT is a multi-layer CNT (denoted as MWNT in the photograph) and has a cross-sectional diameter of about 20 nm. The right-side photo is a CNT diameter distribution diagram obtained by measuring the cross-sectional diameters of many CNTs. The average diameter was 11.6 nm. It has been demonstrated that good quality CNTs can be obtained.
[実施例１〜９：ポリイミド樹脂]
表１は、基板の材質・厚さ及び耐熱性樹脂層（ポリイミド樹脂）の厚さを変えたときに生成されたＣＮＴの評価を与えている。基板の材質は、ＳＵＳ、チタン、ニッケル、インコネル、ハステロイ、アロイ、シリコン及びセラミックの８種類で、２０ｍｍ×２０ｍｍの正方形基板である。基板厚さは表１の通りである。耐熱性樹脂として耐熱温度が５５０℃のポリイミド樹脂が使用された。耐熱性樹脂層厚は５μｍと１０μｍの２種類に設定され、スピンコート法が使用された。Ａｌ層厚は１０ｎｍで、スパッタリング法で蒸着された。Ｆｅ層からなる触媒層厚は４ｎｍに設定され、スパッタリング法で蒸着された。反応条件は、図３で説明された条件と全く同様である。即ち、四層型触媒基体１は、予熱温度６８０℃で１０分間保持され、その後に、Ｈｅ流量が２４５ｓｃｃｍ、Ｃ２Ｈ２流量が１５ｓｃｃｍ、合成温度６８０℃、大気圧条件下で１０分間だけＣＮＴ合成を行った。合成されたＣＮＴの評価は４段階で行われた。◎は良質、○は普通、△はやや不十分、×は不十分である。表１に示す通り、全て普通以上の評価が得られる結果となった。従って、基板の種類を変更してもポリイミド樹脂を使用した場合には、良好なＣＮＴ合成が行われることが分かった。
[Examples 1 to 9: Polyimide resin]
Table 1 gives the evaluation of the CNT produced when the material / thickness of the substrate and the thickness of the heat resistant resin layer (polyimide resin) are changed. There are eight types of substrates, SUS, titanium, nickel, inconel, hastelloy, alloy, silicon and ceramic, which are 20 mm × 20 mm square substrates. The substrate thickness is as shown in Table 1. A polyimide resin having a heat resistant temperature of 550 ° C. was used as the heat resistant resin. The heat-resistant resin layer thickness was set to two types of 5 μm and 10 μm, and a spin coating method was used. The Al layer thickness was 10 nm and was deposited by sputtering. The thickness of the catalyst layer composed of the Fe layer was set to 4 nm and was deposited by sputtering. The reaction conditions are exactly the same as those described in FIG. That is, the four-layer type catalyst substrate 1 is held at a preheating temperature of 680 ° C. for 10 minutes, and thereafter, CNT synthesis is performed only for 10 minutes at a He flow rate of 245 sccm, a C 2 H 2 flow rate of 15 sccm, a synthesis temperature of 680 ° C., and atmospheric pressure conditions. It was. The synthesized CNT was evaluated in four stages. ◎ is good quality, ○ is normal, Δ is slightly insufficient, and × is insufficient. As shown in Table 1, all of the results were evaluated as normal or higher. Therefore, it was found that even when the type of substrate was changed, good CNT synthesis was performed when polyimide resin was used.
[実施例１０〜１８：全芳香族ポリエステルとポリアミドイミド]
表２は、基板の材質・厚さ及び耐熱性樹脂層の厚さを変えたときに生成されたＣＮＴの評価を与えている。使用された樹脂は、全芳香族ポリエステル樹脂とポリアミドイミド樹脂の二通りである。基板の材質は表１と同様に、ＳＵＳ、チタン、ニッケル、インコネル、ハステロイ、アロイ、シリコン及びセラミックの８種類で、２０ｍｍ×２０ｍｍの正方形基板である。基板厚さは表２の通りである。耐熱性樹脂として耐熱温度が４００℃の全芳香族ポリエステル樹脂とポリアミドイミド樹脂が使用された。耐熱温度がポリイミド樹脂より１５０℃低いため、耐熱性樹脂層厚はやや大きめに１０μｍと１５μｍの２種類に設定され、スピンコート法が使用された。Ａｌ層厚は１０ｎｍで、スパッタリング法で蒸着された。Ｆｅ層からなる触媒層厚は４ｎｍに設定され、スパッタリング法で蒸着された。反応条件は、樹脂の耐熱温度が低いため、予熱温度及び反応温度ともに６００℃に設定された。四層型触媒基体１は、予熱温度６００℃で１０分間保持された。合成温度が低いため、Ｈｅ流量が３００ｓｃｃｍ、Ｃ２Ｈ２流量が２０ｓｃｃｍと流量を増加した。合成温度６００℃、大気圧条件下で１３分間だけＣＮＴ合成を行った。合成温度がやや低いために合成時間は１３分間と増加された。合成されたＣＮＴの評価は４段階で行われた。◎は良質、○は普通、△はやや不十分、×は不十分である。表２に示す通り、普通が６例で、やや不十分が３例であった。表１と比較して全体的に評価が低下したのは、樹脂の耐熱温度が４００℃と低く、それに応じて合成温度を６００℃と低下させたことが主たる理由と考えられる。
[Examples 10 to 18: wholly aromatic polyester and polyamideimide]
Table 2 gives an evaluation of the CNTs produced when the substrate material / thickness and the thickness of the heat-resistant resin layer are changed. There are two types of resins used, wholly aromatic polyester resins and polyamideimide resins. As in Table 1, the materials of the substrate are SUS, titanium, nickel, Inconel, Hastelloy, alloy, silicon and ceramic, and are 20 mm × 20 mm square substrates. The substrate thickness is as shown in Table 2. As the heat resistant resin, a wholly aromatic polyester resin having a heat resistant temperature of 400 ° C. and a polyamideimide resin were used. Since the heat-resistant temperature is 150 ° C. lower than that of the polyimide resin, the heat-resistant resin layer thickness was set to be slightly larger, two types of 10 μm and 15 μm, and the spin coating method was used. The Al layer thickness was 10 nm and was deposited by sputtering. The thickness of the catalyst layer composed of the Fe layer was set to 4 nm and was deposited by sputtering. The reaction conditions were set to 600 ° C. for both the preheating temperature and the reaction temperature because the heat resistant temperature of the resin was low. The four-layer type catalyst substrate 1 was held at a preheating temperature of 600 ° C. for 10 minutes. Since the synthesis temperature was low, the He flow rate was increased to 300 sccm and the C2H2 flow rate was increased to 20 sccm. CNT synthesis was performed for 13 minutes at a synthesis temperature of 600 ° C. and atmospheric pressure. The synthesis time was increased to 13 minutes due to the slightly lower synthesis temperature. The synthesized CNT was evaluated in four stages. ◎ is good quality, ○ is normal, Δ is slightly insufficient, and × is insufficient. As shown in Table 2, there were 6 normal cases and 3 cases that were slightly insufficient. The overall decrease in evaluation compared to Table 1 is considered to be mainly due to the fact that the heat-resistant temperature of the resin is as low as 400 ° C. and the synthesis temperature is accordingly reduced to 600 ° C.
図６は、本発明に係る基板炭化層付きＣＮＴから炭化層付きＣＮＴを製造する製造手順図である。図３によって製造された基板炭化層付きＣＮＴ１４から基板層２を分離することによって、基板層２と炭化層付きＣＮＴ１６に２分割される。分離方法には機械的分離方法が最も効率がよく、例えばスクレイパーで炭化層付きＣＮＴ１６を基板層２から剥離する。炭化層１０と基板層２との接合力は弱く、簡単に剥離することができる。従って、分離された基板層２の表面は秀麗であり、再度のＣＮＴ合成に利用できる長所を有している。本発明は、基板の再利用を初めて可能にしたもので、今後のＣＮＴ合成の価格低下を招来することが可能になった。また、炭化層１０はＣＮＴ層の土台になり、ＣＮＴ層がバラけることを防止する作用をする。 FIG. 6 is a production procedure diagram for producing CNTs with a carbonized layer from CNTs with a substrate carbonized layer according to the present invention. By separating the substrate layer 2 from the CNTs 14 with carbonized substrate produced according to FIG. 3, the substrate layer 2 and the CNTs 16 with carbonized layer are divided into two. A mechanical separation method is the most efficient separation method. For example, the carbonized CNT 16 with a scraper is peeled off from the substrate layer 2. The bonding force between the carbonized layer 10 and the substrate layer 2 is weak and can be easily peeled off. Therefore, the surface of the separated substrate layer 2 is excellent, and has an advantage that it can be used for another CNT synthesis. The present invention makes it possible to reuse a substrate for the first time, and it is possible to bring about a future price reduction of CNT synthesis. In addition, the carbonized layer 10 serves as a base of the CNT layer and functions to prevent the CNT layer from being broken.
図７は、本発明に係る炭化層付きＣＮＴからＣＮＴを製造する製造手順図である。基板層２を分離して得られる炭化層付きＣＮＴ１６はＣＮＴ層１２の根元に土台となる炭化層１０が存在する構成を有する。この炭化層付きＣＮＴ１６を大量に回収して大気に開放された燃焼容器内に堆積する。燃焼容器の外周に加熱装置を配置し、この加熱によってエッジの多い炭化層１２は燃焼し、ＣＯ２になって気散する。その結果、燃焼容器内には炭化層１０を消失したＣＮＴ層１２だけが残留し、ＣＮＴを簡単に精製回収することが可能になった。ＣＮＴ層の耐熱性は極めて高いから、燃焼温度が４００℃〜５００℃程度であれば、ＣＮＴへの影響は全くないことが実証された。 FIG. 7 is a production procedure diagram for producing CNTs from the carbonized carbon nanotubes according to the present invention. The carbonized layer-attached CNT 16 obtained by separating the substrate layer 2 has a structure in which the carbonized layer 10 serving as a base exists at the base of the CNT layer 12. A large amount of the carbonized layer-attached CNTs 16 are collected and deposited in a combustion container opened to the atmosphere. A heating device is arranged on the outer periphery of the combustion container, and the carbonized layer 12 with many edges is combusted by this heating, and becomes CO2 and diffuses. As a result, only the CNT layer 12 from which the carbonized layer 10 disappeared remained in the combustion container, and it became possible to easily purify and recover the CNT. Since the heat resistance of the CNT layer is extremely high, it has been demonstrated that there is no influence on the CNTs when the combustion temperature is about 400 ° C. to 500 ° C.
[実施例２０〜２８：ＣＮＴ評価、ポリイミド]
表３は、表１の実施例１〜９から得られるＣＮＴの評価の表である。表１は、耐熱性樹脂としてポリイミドを使用した場合の実施例を示すことは前述した通りである。表３は３種類のＣＮＴの評価を与えている。即ち、基板炭化層付きＣＮＴ１４、炭化層付きＣＮＴ１６及び分離されたＣＮＴ層１２におけるＣＮＴの評価を示している。基板炭化層付きＣＮＴ１４の評価とは、表１の評価と同一である。炭化層付きＣＮＴ１６の評価とは、基板炭化層付きＣＮＴ１４から基板層２を分離した際にＣＮＴへの影響を考慮した評価である。ＣＮＴ層１２の評価とは、炭化層付きＣＮＴ１６から炭化層を燃焼気散させて得られるＣＮＴ層１２の評価であり、燃焼によるＣＮＴ層への影響を考慮した評価である。結果として、炭化層付きＣＮＴの評価と燃焼分離ＣＮＴの評価は、基板炭化層付きＣＮＴの評価とほぼ同様であった。このことは、基板の分離や炭化層の燃焼気散がＣＮＴに与える影響はほとんどないということを示している。
[Examples 20 to 28: CNT evaluation, polyimide]
Table 3 is a table of evaluation of CNTs obtained from Examples 1 to 9 in Table 1. As described above, Table 1 shows an example in which polyimide is used as the heat resistant resin. Table 3 gives an evaluation of three types of CNTs. That is, the evaluation of CNT in the CNT 14 with the substrate carbonized layer, the CNT 16 with the carbonized layer, and the separated CNT layer 12 is shown. The evaluation of CNT 14 with a substrate carbonized layer is the same as the evaluation in Table 1. The evaluation of the carbonized layer-attached CNT 16 is an evaluation in consideration of the influence on the CNT when the substrate layer 2 is separated from the substrate carbonized layer-attached CNT 14. The evaluation of the CNT layer 12 is an evaluation of the CNT layer 12 obtained by burning and dispersing the carbonized layer from the CNTs 16 with the carbonized layer, and is an evaluation in consideration of the influence of the combustion on the CNT layer. As a result, the evaluation of the CNT with a carbonized layer and the evaluation of the combustion-separated CNT were substantially the same as the evaluation of the CNT with a substrate carbonized layer. This indicates that the separation of the substrate and the combustion diffusion of the carbonized layer have almost no influence on the CNT.
[実施例２９〜３７：ＣＮＴ評価：全芳香族ホ゜リエステル、ホ゜リアミト゛イミト゛]
表４は、表２の実施例１０〜１８から得られるＣＮＴの評価の表である。表２は、耐熱性樹脂として全芳香族ポリエステル及びポリアミドイミドを使用した場合の実施例を示すことは前述した通りである。表４は３種類のＣＮＴの評価を与えている。即ち、基板炭化層付きＣＮＴ１４、炭化層付きＣＮＴ１６及び分離されたＣＮＴ層１２におけるＣＮＴの評価を示している。基板炭化層付きＣＮＴ１４の評価とは、表１の評価と同一である。炭化層付きＣＮＴ１６の評価とは、基板炭化層付きＣＮＴ１４から基板層２を分離した際にＣＮＴへの影響を考慮した評価である。ＣＮＴ層１２の評価とは、炭化層付きＣＮＴ１６から炭化層を燃焼気散させて得られるＣＮＴ層１２の評価であり、燃焼によるＣＮＴ層への影響を考慮した評価である。結果として、炭化層付きＣＮＴの評価と燃焼分離ＣＮＴの評価は、基板炭化層付きＣＮＴの評価とほぼ同様であった。従って、基板の分離や炭化層の燃焼気散がＣＮＴに与える影響はほとんどないということができる。
[Examples 29 to 37: Evaluation of CNT: wholly aromatic polyester, polyamidimide]
Table 4 is a table of evaluation of CNTs obtained from Examples 10 to 18 in Table 2. As described above, Table 2 shows an example in which a wholly aromatic polyester and polyamideimide are used as the heat resistant resin. Table 4 gives an evaluation of three types of CNTs. That is, the evaluation of CNT in the CNT 14 with the substrate carbonized layer, the CNT 16 with the carbonized layer, and the separated CNT layer 12 is shown. The evaluation of CNT 14 with a substrate carbonized layer is the same as the evaluation in Table 1. The evaluation of the carbonized layer-attached CNT 16 is an evaluation in consideration of the influence on the CNT when the substrate layer 2 is separated from the substrate carbonized layer-attached CNT 14. The evaluation of the CNT layer 12 is an evaluation of the CNT layer 12 obtained by burning and dispersing the carbonized layer from the CNTs 16 with the carbonized layer, and is an evaluation in consideration of the influence of the combustion on the CNT layer. As a result, the evaluation of the CNT with a carbonized layer and the evaluation of the combustion-separated CNT were substantially the same as the evaluation of the CNT with a substrate carbonized layer. Therefore, it can be said that there is almost no influence on the CNTs by the separation of the substrate and the combustion diffusion of the carbonized layer.
図８は、本発明に係る耐熱性樹脂層（ポリイミド層）の有無に依存したＣＮＴの断面ＳＥＭ写真図であり、基板層としてＳＵＳ基板層を使用した。耐熱性樹脂層の典型例であるポリイミド層を使用した場合（四層型触媒基体）と、全く耐熱性樹脂層を形成しない場合（三層型触媒基体）を比較検討した。上側の写真が、ポリイミド層有りでＣＮＴ合成した四層型触媒基体の断面ＳＥＭ像で、下側の写真が、ポリイミド層無しでＣＮＴ合成した三層型触媒基体の断面ＳＥＭ像である。ポリイミド層有りの場合には、配向ＣＮＴが秀麗に直立成長していることが分かる。他方、ポリイミド層無しの場合には、短いＣＮＴがランダムに形成されてはいるが、配向ＣＮＴは全く合成されていないことが分かる。この結果から、ポリイミド層を典型例として示したが、耐熱性樹脂層がＳＵＳ基板層への配向ＣＮＴ合成に有効であることが実証された。 FIG. 8 is a cross-sectional SEM photograph of CNT depending on the presence or absence of the heat-resistant resin layer (polyimide layer) according to the present invention, and a SUS substrate layer was used as the substrate layer. A case where a polyimide layer, which is a typical example of a heat-resistant resin layer, was used (four-layer catalyst substrate) and a case where no heat-resistant resin layer was formed (three-layer catalyst substrate) were compared. The upper photograph is a cross-sectional SEM image of a four-layer catalyst substrate synthesized with CNTs with a polyimide layer, and the lower photograph is a cross-sectional SEM image of a three-layer catalyst substrate synthesized with CNTs without a polyimide layer. When the polyimide layer is present, it can be seen that the aligned CNTs are excellently grown upright. On the other hand, in the case of no polyimide layer, short CNTs are randomly formed, but it can be seen that oriented CNTs are not synthesized at all. From this result, although the polyimide layer was shown as a typical example, it was demonstrated that the heat resistant resin layer is effective for the synthesis of oriented CNTs on the SUS substrate layer.
図９は、本発明に係る四層型触媒ＳＵＳ基体の加熱時間に依存した断面ＳＥＭ写真図である。ここで四層型触媒ＳＵＳ基体とは、基板層としてＳＵＳ基板層を使用した四層型触媒基体を意味する。まず、右上の図から分かるように、ＳＵＳ基板層にポリイミド層とＡｌ層と触媒層を積層した四層型触媒ＳＵＳ基体を（１）及び（２）の２個用意する。この実験では、Ｈｅガスだけを流通させ、原料ガスであるＣ２Ｈ２ガスは流通させないから、ＣＮＴは合成されない。パターン（１）では、四層型触媒ＳＵＳ基体を合成温度である６８０℃まで加熱して１０分間保持した後に室温にまで冷却する。前述したＣＮＴ合成実験では、四層型触媒ＳＵＳ基体を６８０℃まで加熱して１０分間だけ予熱し、その後にＣ２Ｈ２ガスを流通させたから、パターン（１）は合成開始直前の四層型触媒ＳＵＳ基体の状態を確認するために作成した。他方、パターン（２）では、基体を６８０℃まで加熱して３０分間保持した後、室温まで冷却した。パターン（１）、（２）の温度制御で、ポリイミド層がどのように変化するかを確認した。 FIG. 9 is a cross-sectional SEM photograph of the four-layer catalyst SUS substrate according to the present invention depending on the heating time. Here, the four-layer type catalyst SUS base means a four-layer type catalyst base using a SUS substrate layer as a substrate layer. First, as can be seen from the upper right figure, two four-layer catalyst SUS substrates (1) and (2) are prepared in which a polyimide layer, an Al layer, and a catalyst layer are laminated on a SUS substrate layer. In this experiment, only He gas is circulated and C2H2 gas, which is a raw material gas, is not circulated, so that CNT is not synthesized. In pattern (1), the four-layer catalyst SUS substrate is heated to 680 ° C., which is the synthesis temperature, held for 10 minutes, and then cooled to room temperature. In the CNT synthesis experiment described above, the four-layer catalyst SUS substrate was heated to 680 ° C. and preheated for 10 minutes, and then C2H2 gas was circulated. Created to check the status of. On the other hand, in the pattern (2), the substrate was heated to 680 ° C. and held for 30 minutes, and then cooled to room temperature. It was confirmed how the polyimide layer changed by the temperature control of the patterns (1) and (2).
図９において、左上の写真は、加熱する前の（１）、（２）の四層型触媒ＳＵＳ基体の断面ＳＥＭ像である。５０μｍのＳＵＳ基板層の上に５μｍのポリイミド層が形成されている。１０ｎｍのＡｌ層と４ｎｍの触媒層は薄層のため写真には現れていない。左下写真はパターン（１）の６８０℃・１０分保持した断面ＳＥＭ像、右下写真はパターン（２）の６８０℃・３０分保持した断面ＳＥＭ像を示している。加熱前に５μｍの厚さを有したポリイミド層は、パターン（１）では加熱分解により減少しているが、１０分経過後でも少し残留している。他方、パターン（２）のポリイミド層は３０分間の加熱分解により完全に消失している。但し、パターン（２）では、Ｃ２Ｈ２ガスは通気していないから、ポリイミド層は炭化層には変化せず、ほぼ完全にポリイミド層は消失している。但し、実際には、１０分間の予熱後に、Ｃ２Ｈ２という還元性ガスを通気するから、薄く残留したポリイミド層が炭化され、炭化層へと変化する。この炭化層の出現が本発明では極めて重要であることは上述した通りである。従って、予熱直後の時点でポリイミド層が存在することが本発明の重要点である。
前述したＣＮＴ合成実験では、６８０℃・１０分間予熱、その後の１０分間合成により秀麗な配向ＣＮＴが製造できた事実があるから、１０分間予熱直後の時点で、ポリイミド層で代表される耐熱性樹脂層が残留していることが、基板層と触媒層間の断熱及び配向ＣＮＴ合成に極めて重要であることが判明した。また、耐熱性樹脂の種類により耐熱温度は変化するから、耐熱温度が低い場合には耐熱樹脂層厚さを厚くし、耐熱温度が高い場合には耐熱樹脂層厚さを薄くすることができることを意味している。つまり、耐熱樹脂層厚さは耐熱温度の減少関数と考えてよい。
In FIG. 9, the upper left photograph is a cross-sectional SEM image of the four-layer catalyst SUS substrate of (1) and (2) before heating. A 5 μm polyimide layer is formed on a 50 μm SUS substrate layer. Since the 10 nm Al layer and the 4 nm catalyst layer are thin layers, they do not appear in the photograph. The lower left photograph shows a cross-sectional SEM image of pattern (1) held at 680 ° C. for 10 minutes, and the lower right photograph shows a cross-sectional SEM image of pattern (2) held at 680 ° C. for 30 minutes. The polyimide layer having a thickness of 5 μm before heating is reduced by thermal decomposition in the pattern (1), but remains slightly even after 10 minutes. On the other hand, the polyimide layer of the pattern (2) has completely disappeared by the thermal decomposition for 30 minutes. However, in the pattern (2), since the C2H2 gas is not ventilated, the polyimide layer does not change to the carbonized layer, and the polyimide layer disappears almost completely. However, in practice, after the preheating for 10 minutes, a reducing gas called C2H2 is vented, so that the thinly remaining polyimide layer is carbonized and changed to a carbonized layer. As described above, the appearance of the carbonized layer is extremely important in the present invention. Therefore, it is an important point of the present invention that the polyimide layer exists immediately after preheating.
In the CNT synthesis experiment described above, there is a fact that excellent aligned CNTs can be produced by preheating at 680 ° C. for 10 minutes and then synthesizing for 10 minutes. Therefore, at the time immediately after preheating for 10 minutes, a heat resistant resin represented by a polyimide layer is used. It has been found that the remaining layer is extremely important for the thermal insulation between the substrate layer and the catalyst layer and the synthesis of oriented CNTs. Also, the heat-resistant temperature varies depending on the type of heat-resistant resin, so that the heat-resistant resin layer thickness can be increased when the heat-resistant temperature is low, and the heat-resistant resin layer thickness can be decreased when the heat-resistant temperature is high. I mean. That is, the heat-resistant resin layer thickness may be considered as a decreasing function of the heat-resistant temperature.
図１０は、本発明に係る四層型触媒ＳＵＳ基体の加熱時間に依存した断面ＳＥＭ写真と表面ＡＦＭ像の比較説明図である。図１０の左上のＳＥＭ写真と右上のＳＥＭ写真は、図９の左下のＳＥＭ写真と右下のＳＥＭ写真と夫々同一である。図１０の左下のＡＦＭ像は図９のパターン（１）の表面ＡＦＭ像であり、図１０の右下のＡＦＭ像は図９のパターン（２）の表面ＡＦＭ像である。左下及び右下のＡＦＭ像は、共に１μｍ×１μｍの領域を示している。パターン（１）では、ポリイミド層が薄く残留しているため、表面が凹凸のある多孔質状になっていることが分かる。他方、パターン（２）では、ポリイミド層が消失しているため、鉄触媒と考えられる微小触媒粒子が均一な大きさで存在していることが分かる。即ち、１０分間の加熱ではポリイミド層の残留により表面凹凸状になり、１０分間以上の加熱により、いずれかの時点でポリイミド層は完全に消失し、表面凹凸形状は次第に均一な触媒微粒子状へと変化する。この均一触媒微粒子が配向ＣＮＴの合成に重要である。 FIG. 10 is a comparative explanatory view of a cross-sectional SEM photograph and a surface AFM image depending on the heating time of the four-layer catalyst SUS substrate according to the present invention. The upper left SEM photograph and the upper right SEM photograph in FIG. 10 are the same as the lower left SEM photograph and the lower right SEM photograph in FIG. 9, respectively. The lower left AFM image in FIG. 10 is the surface AFM image of the pattern (1) in FIG. 9, and the lower right AFM image in FIG. 10 is the surface AFM image in the pattern (2) in FIG. Both the lower left and lower right AFM images show an area of 1 μm × 1 μm. In pattern (1), since the polyimide layer remains thin, it can be seen that the surface is porous with irregularities. On the other hand, in the pattern (2), since the polyimide layer has disappeared, it can be seen that the fine catalyst particles considered to be an iron catalyst are present in a uniform size. That is, when heated for 10 minutes, the surface of the polyimide layer remains uneven, and when heated for 10 minutes or longer, the polyimide layer disappears completely at any point in time, and the surface uneven shape gradually becomes uniform catalyst fine particles. Change. This uniform catalyst fine particle is important for the synthesis of oriented CNTs.
図１１は、本発明に係る耐熱性樹脂層（ポリイミド層）の有無と加熱時間に依存した表面ＡＦＭ像図である。ポリイミド層がある場合とポリイミド層が無い場合について、パターン（１）とパターン（２）を比較する実験を行った。勿論、Ｈｅガスを通気させるだけで、還元性ガスであるＣ２Ｈ２ガスは通気させていない。上側がポリイミド層有りの場合で、下側がポリイミド層無しの場合である。ポリイミド層有りの場合には、ポリイミド層が消失した後に、鉄触媒が均一で小さな触媒微粒子の状態を維持していることが分かる。他方、ポリイミド層が無い場合には、６８０℃で１０分間保持しただけで粒子径が不均一に比較的に大きくなり、３０分間保持すると不均一度が急激に高まり、触媒粒子は急激に増大していることが分かった。ポリイミド層有りと無しの両者を対比すると、その違いは明らかである。ポリイミド無しの場合において、触媒粒子は不均一性と団子状の凹凸を示しているから、配向ＣＮＴは到底合成できないことを物語る。 FIG. 11 is a surface AFM image diagram depending on the presence / absence of the heat-resistant resin layer (polyimide layer) and the heating time according to the present invention. An experiment was conducted to compare the pattern (1) and the pattern (2) with and without the polyimide layer. Of course, only the He gas is ventilated, and the reducing gas C2H2 gas is not vented. The upper side is a case with a polyimide layer, and the lower side is a case without a polyimide layer. When the polyimide layer is present, it can be seen that after the polyimide layer disappears, the iron catalyst maintains the state of uniform and small catalyst fine particles. On the other hand, when there is no polyimide layer, the particle size becomes non-uniform and relatively large just by holding at 680 ° C. for 10 minutes, and when held for 30 minutes, the non-uniformity increases rapidly and the catalyst particles increase rapidly. I found out. The difference is obvious when comparing the polyimide layer with and without the polyimide layer. In the case of no polyimide, the catalyst particles show non-uniformity and dumpling-like irregularities, which means that oriented CNT cannot be synthesized at all.
図１２は、本発明に係る耐熱性樹脂層（ポリイミド層）の有無に依存したＣＮＴ成長の比較モデル説明図である。ここでは、図８〜図１１の実験結果から得られる耐熱性触媒層の配向ＣＮＴ合成に与える作用効果をまとめる。図１２の上側はポリイミド層がある場合、下側はポリイミド層が無い場合の説明図である。まず上側図において、ポリイミド層を典型例とする耐熱性触媒層は強力な耐熱性を示し、加熱によって触媒層が微粒子となる高温でも凹凸のある多孔性の触媒微粒子構造を与える。この多孔質構造が四層型触媒基体の表面エネルギーを調整することで触媒微粒子の凝集を防ぎ、均一な触媒微粒子を形成する。Ｃ２Ｈ２を流通させる直前時点でも、まだポリイミド層は残留している。その後、炭素源となるＣ２Ｈ２を触媒微粒子に供給すると、触媒微粒子をもとにＣＮＴが合成される。残留していたポリイミド層は炭化層へと変化する。他方、図１２の下側図のポリイミド層が無い場合には、加熱すると、触媒の凝集作用が強く、触媒粒子径がどんどん大きくなり、また大きさや粒子間隔も不均一になる。そのため、炭素源となるＣ２Ｈ２を供給しても全ての触媒が活性ではなくなり、配向ＣＮＴが合成されないと考えられる。以上の説明は、耐熱性樹脂としてポリイミドを例にとって説明したが、他の耐熱性樹脂でも同様の作用効果を奏することが、本発明において確認されている。耐熱温度が４００℃以上であればよく、５００℃以上であれば更に好適であることは言うまでもない。 FIG. 12 is a comparative model explanatory diagram of CNT growth depending on the presence or absence of the heat resistant resin layer (polyimide layer) according to the present invention. Here, the effects of the heat resistant catalyst layer obtained from the experimental results of FIGS. The upper side of FIG. 12 is an explanatory diagram when the polyimide layer is present, and the lower side is an explanatory diagram when the polyimide layer is absent. First, in the upper view, a heat-resistant catalyst layer having a polyimide layer as a typical example exhibits strong heat resistance, and gives a porous catalyst fine particle structure having irregularities even at a high temperature at which the catalyst layer becomes fine particles by heating. This porous structure adjusts the surface energy of the four-layer catalyst substrate to prevent the aggregation of the catalyst fine particles and form uniform catalyst fine particles. Even immediately before C2H2 is distributed, the polyimide layer still remains. Thereafter, when C2H2 serving as a carbon source is supplied to the catalyst fine particles, CNTs are synthesized based on the catalyst fine particles. The remaining polyimide layer turns into a carbonized layer. On the other hand, in the absence of the polyimide layer in the lower diagram of FIG. 12, when heated, the agglomeration effect of the catalyst is strong, the catalyst particle diameter increases steadily, and the size and particle spacing become nonuniform. Therefore, it is considered that even when C2H2 serving as a carbon source is supplied, all the catalysts are not active and aligned CNTs are not synthesized. In the above description, polyimide is used as an example of the heat-resistant resin, but it has been confirmed in the present invention that other heat-resistant resins have the same effects. Needless to say, the heat resistant temperature should be 400 ° C. or higher, and more preferably 500 ° C. or higher.
図１３は、本発明に係る四層型触媒基体ベルトの製造説明図とこれを用いたＣＮＴ連続製造装置の構成図である。（１３Ａ）は四層型触媒基体ベルト製造装置の説明図であり、（１３Ｂ）はＣＮＴ連続製造装置の説明図である。まず、（１３Ａ）において、１９は四層型触媒基体ベルト製造装置、２８は耐熱性樹脂層形成手段、３０はＡｌ層形成手段、３２は触媒層形成手段、４３は金属製の基板ベルト、４４は四層型触媒基体ロール、４５は四層型触媒基体ベルト、４６は基板ロールである。より具体的には、耐熱性樹脂層形成手段２８は耐熱性樹脂溶液を基板ベルト表面に薄膜形成する手段で、例えばスプレー手段、スピンコート手段等である。Ａｌ層形成手段３０は蒸着装置で、物理的蒸着装置や化学的蒸着装置などである。触媒層形成手段３２は触媒物質の蒸着装置で、物理的蒸着装置や化学的蒸着装置などである。基板ベルト４６はＳＵＳ基板ベルトのように薄い金属製フィルムで、基板ロール４６に卷回されている。基板ベルト４３を基板ロール４６から四層型触媒基体ロール４４に張設し、四層型触媒基体ロール４４を駆動ロールとして矢印ｅ方向に回転させると、基板ロール４６も矢印ｅ方向に回転する。この回転により基板ベルト４３は矢印ｄ方向に走行する。基板ベルト４３の表面に耐熱性樹脂層形成手段２８により耐熱性樹脂層を形成して乾燥させ、この耐熱性樹脂層の上にＡｌ層形成手段３０によりＡｌ層を形成し、最後に前記Ａｌ層の上に触媒層形成手段３２により触媒層を形成して、四層型触媒基体ベルト４５が完成する。この四層型触媒基体ベルト４５は四層型触媒基体ロール４４により卷回してロール状に回収される。従って、長尺の四層型触媒基体ベルト４５からなる四層型触媒基体ロール４４が製造される。 FIG. 13 is an explanatory view of the production of a four-layer type catalyst substrate belt according to the present invention and a configuration diagram of a CNT continuous production apparatus using the same. (13A) is an explanatory view of a four-layer catalyst base belt manufacturing apparatus, and (13B) is an explanatory view of a CNT continuous manufacturing apparatus. First, in (13A), 19 is a four-layer catalyst substrate belt manufacturing apparatus, 28 is a heat-resistant resin layer forming means, 30 is an Al layer forming means, 32 is a catalyst layer forming means, 43 is a metal substrate belt, 44 Is a four-layer catalyst substrate roll, 45 is a four-layer catalyst substrate belt, and 46 is a substrate roll. More specifically, the heat resistant resin layer forming means 28 is a means for forming a thin film of the heat resistant resin solution on the surface of the substrate belt, and is, for example, a spray means or a spin coat means. The Al layer forming means 30 is a vapor deposition apparatus, such as a physical vapor deposition apparatus or a chemical vapor deposition apparatus. The catalyst layer forming means 32 is a catalyst material vapor deposition device, such as a physical vapor deposition device or a chemical vapor deposition device. The substrate belt 46 is a thin metal film like a SUS substrate belt, and is wound around a substrate roll 46. When the substrate belt 43 is stretched from the substrate roll 46 to the four-layer type catalyst base roll 44 and is rotated in the direction of arrow e using the four-layer type catalyst base roll 44 as a drive roll, the substrate roll 46 is also rotated in the direction of arrow e. By this rotation, the substrate belt 43 travels in the direction of arrow d. A heat resistant resin layer is formed on the surface of the substrate belt 43 by the heat resistant resin layer forming means 28 and dried. An Al layer is formed on the heat resistant resin layer by the Al layer forming means 30, and finally the Al layer is formed. A catalyst layer is formed thereon by the catalyst layer forming means 32, and the four-layer type catalyst substrate belt 45 is completed. The four-layer type catalyst base belt 45 is wound by a four-layer type catalyst base roll 44 and collected in a roll shape. Therefore, a four-layer catalyst substrate roll 44 composed of a long four-layer catalyst substrate belt 45 is manufactured.
次に、ＣＮＴ連続製造装置２０を示す図１３の（１３Ｂ）を説明する。１０は炭化層、１２はＣＮＴ層、１４は基板炭化層付きＣＮＴ、１６は炭化層付きＣＮＴ、３４はＣＶＤ反応手段、３６はＣＮＴ分離手段、３８はＣＮＴ回収手段、４０は炭化層燃焼手段、４４は四層型触媒基体ロール、４５は四層型触媒基体ベルト、４８は回収ロールである。まず、（１３Ａ）で完成した四層型触媒基体ロール４４から四層型触媒基体ベルト４５を引き出して回収ロール４８に卷回して張設する。回収ロール４８を駆動軸にして矢印ｇ方向に回転させると、四層型触媒基体ロール４４も矢印ｇ方向に回転し、四層型触媒基体ベルト４５は矢印ｆ方向に走行する。ＣＶＤ反応手段３４により、四層型触媒基体ベルト４５の表面にＣＮＴ層１２を合成し、ＣＮＴ層１２が形成された四層型触媒基体ベルト４５が基板炭化層付きＣＮＴ１４として形成される。ＣＮＴ分離手段３６により基板炭化層付きＣＮＴ１４から炭化層付きＣＮＴ１６を剥離し、基板ベルト４３が回収ロール４８に卷回回収されて、（１３Ａ）の基板ロール４６として再利用される。炭化層付きＣＮＴ１６は簡単に分離するから、基板ベルト４３の表面は秀麗であり、そのまま再利用することができる。他方、分離された炭化層付きＣＮＴ１６はＣＮＴ回収手段３８に落下し、炭化層燃焼手段４０の中に堆積回収される。炭化層燃焼手段４０は大気に開放されており、図示しない加熱手段により炭化層付きＣＮＴ１６は加熱される。この加熱により耐熱性の高いＣＮＴ層１２は変化しないが、炭化層１０はＣＯ２になってガス化し、大気中に気散してゆく。その結果、炭化層燃焼手段４０の中には、炭化層１０の無い純粋の高配向したＣＮＴ層が大量に収容されることになる。 Next, (13B) of FIG. 13 which shows the CNT continuous manufacturing apparatus 20 is demonstrated. 10 is a carbonized layer, 12 is a CNT layer, 14 is a CNT with a substrate carbonized layer, 16 is a CNT with a carbonized layer, 34 is a CVD reaction means, 36 is a CNT separation means, 38 is a CNT recovery means, 40 is a carbonized layer combustion means, 44 is a four-layer catalyst substrate roll, 45 is a four-layer catalyst substrate belt, and 48 is a recovery roll. First, the four-layer catalyst substrate belt 45 is pulled out from the four-layer catalyst substrate roll 44 completed in (13A), wound around the collection roller 48 and stretched. When the collection roll 48 is rotated in the direction of arrow g with the recovery roll 48 as the drive shaft, the four-layer type catalyst substrate roll 44 is also rotated in the direction of arrow g, and the four-layer type catalyst substrate belt 45 travels in the direction of arrow f. The CVD reaction means 34 synthesizes the CNT layer 12 on the surface of the four-layer catalyst substrate belt 45, and the four-layer catalyst substrate belt 45 on which the CNT layer 12 is formed is formed as the CNT 14 with the substrate carbonized layer. The carbonized layer-attached CNT 16 is peeled from the substrate carbonized layer-attached CNTs 14 by the CNT separating means 36, and the substrate belt 43 is wound around the collecting roll 48 and reused as the substrate roll 46 of (13A). Since the CNTs 16 with the carbonized layer are easily separated, the surface of the substrate belt 43 is excellent and can be reused as it is. On the other hand, the separated carbonized layer-attached CNT 16 falls to the CNT collecting means 38 and is collected and collected in the carbonized layer combustion means 40. The carbonized layer combustion means 40 is open to the atmosphere, and the CNTs 16 with the carbonized layer are heated by a heating means (not shown). Although the CNT layer 12 having high heat resistance does not change by this heating, the carbonized layer 10 becomes CO2 and gasifies and diffuses into the atmosphere. As a result, a large amount of pure highly oriented CNT layers without the carbonized layer 10 are accommodated in the carbonized layer combustion means 40.
[実施例４１、４２：図１３の燃焼分離法によるＣＮＴ評価]
表５は、図１３により製造されたＳＵＳベルト製造法による燃焼分離されたＣＮＴの評価表である。ＣＶＤ反応手段３４のＣＶＤ条件は、６８０℃・１０分間の予熱過程と、Ｈｅガスが２４５ｓｃｃｍ、Ｃ２Ｈ２ガスが１５ｓｃｃｍで１０分間のＣＮＴ合成過程である。ＳＵＳベルト走行速度は１０ｃｍ／ｍｉｎであり、合成は大気圧下で実施された。更に、炭化層燃焼手段４０内では、燃焼温度５００℃、大気中燃焼で、燃焼時間は１０分間であった。使用触媒構成とＳＵＳベルト厚は実施例１と実施例２で示された条件と同一である。その結果、基板炭化層付きＣＮＴ１４、炭化層付きＣＮＴ１６及び最終分離されたＣＮＴ層１２の品質評価は全て良質であった。本発明の装置方法の優秀性が実証された。
[Examples 41 and 42: CNT evaluation by the combustion separation method of FIG. 13]
Table 5 is an evaluation table of CNT separated by combustion by the SUS belt manufacturing method manufactured according to FIG. The CVD conditions of the CVD reaction means 34 are a preheating process at 680 ° C. for 10 minutes and a CNT synthesis process at 245 sccm for He gas and 15 sccm for C2H2 gas for 10 minutes. The SUS belt running speed was 10 cm / min, and the synthesis was performed under atmospheric pressure. Further, in the carbonized layer combustion means 40, the combustion temperature was 500 ° C., the combustion in the atmosphere, and the combustion time was 10 minutes. The catalyst composition and SUS belt thickness are the same as the conditions shown in Example 1 and Example 2. As a result, the quality evaluation of the CNT 14 with the substrate carbonized layer, the CNT 16 with the carbonized layer, and the finally separated CNT layer 12 was good. The superiority of the device method of the present invention was demonstrated.
図１４は、本発明に係る四層型触媒基体を無端ベルトに適用したＣＮＴ連続製造装置の説明図である。符号説明は図１３と同様であるから、ここでは図符号の説明は省略する。基板ベルト４３からなる無端ベルト２６は駆動ローラ２２と従動ローラ２４の間に卷設されている。駆動ローラ２２が矢印ａ方向に回転すると、従動ローラ―２４も矢印ａ方向に回転し、無端ベルト２６は矢印ｂ方向に走行する。矢印ｂ方向に走行する過程で、無端ベルト２６は耐熱性樹脂層形成手段２８により耐熱性樹脂層を形成され、次に前記耐熱性樹脂層の上にＡｌ層形成手段３０によりＡｌ層が形成され、更に前記Ａｌ層の上に触媒層形成手段３２により触媒層が形成され、無端ベルトが四層型触媒基体ベルト４５に変化する。四層型触媒基体ベルト４５が矢印ｃ方向に走行する過程で、ＣＶＤ反応手段３４により触媒層の表面にＣＮＴ層１２が合成され、四層型触媒基体ベルト４５は基板炭化層付きＣＮＴ１４に変化する。ＣＮＴ分離手段３６は、前記基板炭化層付きＣＮＴ１４から炭化層付きＣＮＴ１６を剥離し、基板炭化層付きＣＮＴ１４は基板ベルト４３と炭化層付きＣＮＴ１６に分離する。基板ベルト４３は矢印ｂ方向に走行して前記ＣＮＴ製造工程に入るために再利用される。他方、分離された炭化層付きＣＮＴ１６はＣＮＴ回収手段３８に落下し、炭化層燃焼手段４０の中に堆積回収される。炭化層燃焼手段４０は大気に開放されており、図示しない加熱手段により炭化層付きＣＮＴ１６は加熱される。この加熱により耐熱性の高いＣＮＴ層１２は変化しないが、炭化層１０はＣＯ２になってガス化し、大気中に気散してゆく。その結果、炭化層燃焼手段４０の中には、炭化層１０の無い純粋の高配向したＣＮＴ層が大量に収容されることになる。 FIG. 14 is an explanatory view of a continuous CNT manufacturing apparatus in which the four-layer catalyst base according to the present invention is applied to an endless belt. The explanation of the reference numerals is the same as that of FIG. 13, so the explanation of the reference numerals is omitted here. An endless belt 26 formed of a substrate belt 43 is provided between the driving roller 22 and the driven roller 24. When the driving roller 22 rotates in the direction of arrow a, the driven roller 24 also rotates in the direction of arrow a, and the endless belt 26 travels in the direction of arrow b. In the process of traveling in the direction of arrow b, the endless belt 26 is formed with a heat resistant resin layer by the heat resistant resin layer forming means 28, and then an Al layer is formed on the heat resistant resin layer by the Al layer forming means 30. Further, a catalyst layer is formed on the Al layer by the catalyst layer forming means 32, and the endless belt is changed to a four-layer type catalyst base belt 45. In the process in which the four-layer type catalyst substrate belt 45 travels in the direction of arrow c, the CNT layer 12 is synthesized on the surface of the catalyst layer by the CVD reaction means 34, and the four-layer catalyst substrate belt 45 is changed to the CNT 14 with the substrate carbonized layer. . The CNT separation means 36 peels the CNTs 16 with the carbonized layer from the CNTs 14 with the carbonized substrate, and the CNTs 14 with the carbonized substrate are separated into the substrate belt 43 and the CNTs 16 with the carbonized layer. The substrate belt 43 is reused for traveling in the direction of arrow b and entering the CNT manufacturing process. On the other hand, the separated carbonized layer-attached CNT 16 falls to the CNT collecting means 38 and is collected and collected in the carbonized layer combustion means 40. The carbonized layer combustion means 40 is open to the atmosphere, and the CNTs 16 with the carbonized layer are heated by a heating means (not shown). Although the CNT layer 12 having high heat resistance does not change by this heating, the carbonized layer 10 becomes CO2 and gasifies and diffuses into the atmosphere. As a result, a large amount of pure highly oriented CNT layers without the carbonized layer 10 are accommodated in the carbonized layer combustion means 40.
[実施例４３、４４：図１４の燃焼分離法によるＣＮＴ評価]
表６は、図１４により製造された無端ＳＵＳベルト製造法による燃焼分離されたＣＮＴの評価表である。ＣＶＤ反応装置３４のＣＶＤ条件は、図１３と全く同様で、６８０℃・１０分間の予熱過程と、Ｈｅガスが２４５ｓｃｃｍ、Ｃ２Ｈ２ガスが１５ｓｃｃｍで１０分間のＣＮＴ合成過程である。ＳＵＳベルト走行速度は１０ｃｍ／ｍｉｎであり、合成は大気圧化で実施された。更に、炭化層燃焼手段４０内では、燃焼温度５００℃、大気中燃焼で、燃焼時間は１０分間であった。使用触媒構成とＳＵＳベルト厚は実施例１と実施例２で示された条件と同一である。
[Examples 43 and 44: CNT evaluation by combustion separation method of FIG. 14]
Table 6 is an evaluation table of CNTs separated by combustion by the endless SUS belt manufacturing method manufactured according to FIG. The CVD conditions of the CVD reactor 34 are exactly the same as in FIG. 13, a preheating process at 680 ° C. for 10 minutes and a CNT synthesis process at 245 sccm for He gas and 15 sccm for C2H2 gas for 10 minutes. The SUS belt running speed was 10 cm / min, and the synthesis was performed at atmospheric pressure. Further, in the carbonized layer combustion means 40, the combustion temperature was 500 ° C., the combustion in the atmosphere, and the combustion time was 10 minutes. The catalyst composition and SUS belt thickness are the same as the conditions shown in Example 1 and Example 2.
表６に示すように、基板炭化層付きＣＮＴ１４、炭化層付きＣＮＴ１６及び最終分離されたＣＮＴ層１２の品質評価は全て良質であった。本発明の無端ベルト装置方法の優秀性が実証された。 As shown in Table 6, the quality evaluation of the CNTs 14 with the substrate carbonized layer, the CNTs 16 with the carbonized layer, and the finally separated CNT layer 12 was high. The superiority of the endless belt device method of the present invention was demonstrated.
本発明においては、基板層の上に耐熱性樹脂層を形成し、この耐熱性樹脂層の上にＡｌ層と触媒層を形成した四層型触媒基体を提案し、特に４００℃以上の耐熱温度を有した耐熱性樹脂層を形成することによって、ＣＮＴ合成時に耐熱性樹脂層が基板層を熱的に保護しながら、触媒層上に秀麗な配向ＣＮＴを合成でき、しかもＣＮＴを分離回収しても基板層表面は合成前の状態を保持できるから、基板層の再利用を実現することができる。 In the present invention, a four-layer catalyst substrate is proposed in which a heat-resistant resin layer is formed on a substrate layer, and an Al layer and a catalyst layer are formed on the heat-resistant resin layer. By forming a heat-resistant resin layer having CNTs, it is possible to synthesize excellent oriented CNTs on the catalyst layer while the heat-resistant resin layer thermally protects the substrate layer during CNT synthesis, and separates and recovers CNTs. In addition, since the surface of the substrate layer can maintain the state before synthesis, the reuse of the substrate layer can be realized.
１ 四層型触媒基体
２ 基板層
４ 耐熱性樹脂層
６ Ａｌ層
８ 触媒層
１０ 炭化層
１２ ＣＮＴ層
１４ 基板炭化層付きＣＮＴ
１６ 炭化層付きＣＮＴ
１９ 四層型触媒基体ベルト製造装置
２０ ＣＮＴ連続製造装置
２２ 駆動ローラ
２４ 従動ローラ
２６ 無端ベルト
２８ 耐熱性樹脂層形成手段
３０ Ａｌ層形成手段
３２ 触媒層形成手段
３４ ＣＶＤ反応手段
３６ ＣＮＴ分離手段
３８ ＣＮＴ回収手段
４０ 炭化層燃焼手段
４３ 基板ベルト
４４ 四層型触媒基体ロール
４５ 四層型触媒基体ベルト
４６ 基板ロール
４８ 回収ロール
１０１ 触媒基体
１０２ シリコン基板層、ＳＵＳ基板層
１０４ エポキシ樹脂層
１０５ Ａｌ２Ｏ３層
１０６ Ａｌ層
１０８ 触媒層
DESCRIPTION OF SYMBOLS 1 Four-layer type catalyst base 2 Substrate layer 4 Heat resistant resin layer 6 Al layer 8 Catalyst layer 10 Carbonized layer 12 CNT layer 14 CNT with substrate carbonized layer
16 CNT with carbonized layer
DESCRIPTION OF SYMBOLS 19 Four-layer type catalyst base belt manufacturing apparatus 20 CNT continuous manufacturing apparatus 22 Drive roller 24 Driven roller 26 Endless belt 28 Heat resistant resin layer forming means 30 Al layer forming means 32 Catalyst layer forming means 34 CVD reaction means 36 CNT separation means 38 CNT Collection means 40 Carbonized layer combustion means 43 Substrate belt 44 Four-layer type catalyst substrate roll 45 Four-layer type catalyst substrate belt 46 Substrate roll 48 Collection roll 101 Catalyst substrate 102 Silicon substrate layer, SUS substrate layer 104 Epoxy resin layer 105 Al2O3 layer 106 Al Layer 108 Catalyst layer
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