JP2007016262A - Carbon nanotube-containing composite material, and method for producing the same - Google Patents
Carbon nanotube-containing composite material, and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、カーボンナノチューブ含有複合材及びその製造方法に係り、更に詳細には、カーボンナノチューブ含有金属粉末、その製造方法、カーボンナノチューブ含有複合材、その製造方法、積層型カーボンナノチューブ含有複合材及びその製造方法に関する。
特に、自動車用部品などの高い性能を必要とする部品に適したカーボンナノチューブ含有複合材及び積層型カーボンナノチューブ含有複合材に関する。
The present invention relates to a carbon nanotube-containing composite material and a method for producing the same, and more specifically, a carbon nanotube-containing metal powder, a method for producing the same, a carbon nanotube-containing composite material, a method for producing the same, a laminated carbon nanotube-containing composite material, and the method thereof It relates to a manufacturing method.
In particular, the present invention relates to a carbon nanotube-containing composite material and a laminated carbon nanotube-containing composite material suitable for parts that require high performance such as automobile parts.
従来からカーボンナノチューブ（以下、「ＣＮＴ」と略記する。）は、その特徴的な構造から、機械的性質だけでなく、電気的性質や熱的性質についても優れていることが知られている。
そして、ＣＮＴ含有複合材は、自動車用部品だけでなく、広くその応用が期待されている。
特に、マトリックスを金属とした複合材は、マトリックスが樹脂である複合材と比較して耐熱性や耐摩耗性、熱膨張特性などが優れていることから、これらの性能が必要とされる自動車用部品として広く応用が期待できる。
Conventionally, carbon nanotubes (hereinafter abbreviated as “CNT”) are known to be excellent not only in mechanical properties but also in electrical properties and thermal properties due to their characteristic structures.
The CNT-containing composite material is expected to be widely applied not only to automobile parts.
In particular, composite materials with a matrix metal are superior in heat resistance, wear resistance, thermal expansion characteristics, etc. compared to composite materials in which the matrix is a resin. Wide application as a part can be expected.
これまでに、アルミニウム粉末とＣＮＴを混合して、金属シース中に詰め、線引きして複合材としたものが提案されている（非特許文献１参照。）。
また、ニッケルめっき層中にＣＮＴを添加して耐摩耗性を向上させたものが提案されている（非特許文献２参照。）。
So far, a composite material in which aluminum powder and CNT are mixed, packed in a metal sheath, and drawn into a composite material has been proposed (see Non-Patent Document 1).
In addition, a material in which CNT is added to a nickel plating layer to improve wear resistance has been proposed (see Non-Patent Document 2).
一方、自動車のエンジンシリンダヘッドには、バルブシートが圧入され、バルブとのシールを保っていることが知られており、この部品には強度だけでなく、バルブの熱をシリンダヘッドのウォータジャケットへ逃がすという機能が要求されている。
そして、これまでの鉄系合金からなるバルブシートを圧入する代わりに、レーザによって銅合金粉末を肉盛し、仕上げ加工することにより、基材との熱伝導性能を高めてバルブの温度を低下させたものが提案されている（特許文献１参照。）。
And instead of press-fitting a conventional valve seat made of an iron-based alloy, the copper alloy powder is built up by laser and finished, thereby improving the heat conduction performance with the base material and lowering the valve temperature. Have been proposed (see Patent Document 1).
しかしながら、ＣＮＴは金属に対して濡れ性が良くなく、また、非常に微細であるため、マトリックス金属中に分散・配合させることが極めて困難であり、未だ部材・部品として使用に耐えるものが得られていない。 However, CNTs do not have good wettability to metals, and are very fine, so it is extremely difficult to disperse and mix them in matrix metals, and those that can still be used as members and parts are obtained. Not.
例えば、上記非特許文献１に記載の複合材は、ＣＮＴが凝集しているために、その性能が十分に発揮されていないという問題点があった。 For example, the composite material described in Non-Patent Document 1 has a problem that its performance is not sufficiently exhibited because CNTs are aggregated.
これは、ＣＮＴを強化材としてマトリックス金属中に添加する場合には、その凝集を解き、均一に分散させた状態とすることが重要であるが、原料としてマトリックス金属の粉末とＣＮＴとを混合して焼結させる場合には、その成形は可能であっても凝集が十分には解けないためである。 When adding CNT as a reinforcing material to a matrix metal, it is important to break up the agglomeration and make it uniformly dispersed. However, as a raw material, a matrix metal powder and CNT are mixed. In the case of sintering, the aggregation is not sufficiently solved even if the molding is possible.
また、上記非特許文献２に記載の複合材は、薄い皮膜しか得られないという寸法上の制約がある。そして、マトリックス金属の材質についても制約がある。 Further, the composite material described in Non-Patent Document 2 has a dimensional limitation that only a thin film can be obtained. There are also restrictions on the material of the matrix metal.
これは、めっき層中にＣＮＴを混合させる場合には、現実にはめっき層の厚さに限度があるためである。
そして、そのために低面圧下での摩擦摩耗性能が要求される部材に用途が限定されるという問題点がある。
また、マトリックス金属としてアルミニウムの適用が困難であり、軽量化を目的とする場合には利用できない、更には処理速度が遅く生産性が低いといった問題点もある。
This is because when the CNT is mixed in the plating layer, the thickness of the plating layer is actually limited.
For this reason, there is a problem in that the use is limited to members that require friction and wear performance under low surface pressure.
In addition, it is difficult to apply aluminum as a matrix metal, and there is a problem that it cannot be used for the purpose of weight reduction, and further, the processing speed is slow and the productivity is low.
本発明は、このような従来技術の有する課題に鑑みてなされたものであり、その目的とするところは、ＣＮＴを分散・配合させ、機械的性質や電気的性質、熱的性質などに優れ、部材や部品として使用に適したＣＮＴ含有複合材及びその製造方法を提供することにある。 The present invention has been made in view of such problems of the prior art, and the object is to disperse and blend CNTs, which are excellent in mechanical properties, electrical properties, thermal properties, An object of the present invention is to provide a CNT-containing composite material suitable for use as a member or component and a method for producing the same.
本発明者らは、上記目的を達成するため鋭意研究を重ねた結果、金属粉末の内部及び表面の一方又は双方にＣＮＴを保持して成るＣＮＴ含有金属粉末を得、それを出発原料とすることなどにより、上記目的が達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained a CNT-containing metal powder comprising CNTs held on one or both of the inside and the surface of the metal powder, and using it as a starting material. As a result, the inventors have found that the above object can be achieved, and have completed the present invention.
即ち、本発明のＣＮＴ含有金属粉末は、金属粉末の内部及び表面の一方又は双方にＣＮＴを保持して成るものである。 That is, the CNT-containing metal powder of the present invention is obtained by holding CNTs in one or both of the inside and the surface of the metal powder.
また、本発明のＣＮＴ含有複合材は、上記本発明のＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末を焼結して成るものである。
更に、本発明の積層型ＣＮＴ含有複合材は、上記本発明のＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末を基材表面に肉盛して成るものである。
The CNT-containing composite material of the present invention is obtained by sintering the CNT-containing metal powder using the CNT-containing metal powder of the present invention.
Furthermore, the laminated CNT-containing composite material of the present invention is formed by depositing the CNT-containing metal powder on the surface of the substrate using the CNT-containing metal powder of the present invention.
更にまた、本発明のバルブフェース部材、シリンダヘッドバルブシート部材、シリンダヘッド弁間部材及び成形用金型部材は、上記本発明の積層型ＣＮＴ含有複合材を適用したものである。 Furthermore, the valve face member, the cylinder head valve seat member, the cylinder head inter-valve member, and the molding die member of the present invention are obtained by applying the laminated CNT-containing composite material of the present invention.
また、本発明のＣＮＴ含有金属粉末の製造方法は、上記本発明のＣＮＴ含有金属粉末を製造する方法であって、金属粉末とＣＮＴに衝撃力、圧縮力、摩擦力及び剪断力から成る群より選ばれた少なくとも１種の機械的作用を繰り返し加えて、一体化させる方法である。
そして、金属粉末とカーボンナノチューブを一体化させるに当たり、好ましくはその雰囲気を不活性ガス雰囲気とする方法である。
Further, the method for producing a CNT-containing metal powder of the present invention is a method for producing the CNT-containing metal powder of the present invention, wherein the metal powder and CNT are made of a group consisting of impact force, compressive force, friction force and shear force. In this method, at least one selected mechanical action is repeatedly added and integrated.
In integrating the metal powder and the carbon nanotube, the atmosphere is preferably an inert gas atmosphere.
更に、本発明のＣＮＴ含有複合材の製造方法は、上記本発明のＣＮＴ含有複合材を製造する方法であって、金属粉末とＣＮＴに衝撃力、圧縮力、摩擦力及び剪断力から成る群より選ばれた少なくとも１種の機械的作用を繰り返し加えて、一体化させてＣＮＴ含有金属粉末を得、得られたＣＮＴ含有金属粉末を非酸化性雰囲気下で加熱して、焼結させる方法である。
そして、金属粉末とカーボンナノチューブを一体化させるに当たり、好ましくはその雰囲気を不活性ガス雰囲気とする方法である。
Furthermore, the method for producing a CNT-containing composite material according to the present invention is a method for producing the above-described CNT-containing composite material according to the present invention, wherein the metal powder and CNT are made of a group consisting of impact force, compressive force, friction force and shear force. It is a method in which at least one selected mechanical action is repeatedly applied and integrated to obtain a CNT-containing metal powder, and the obtained CNT-containing metal powder is heated and sintered in a non-oxidizing atmosphere. .
In integrating the metal powder and the carbon nanotube, the atmosphere is preferably an inert gas atmosphere.
更にまた、本発明の積層型ＣＮＴ含有複合材の製造方法は、上記本発明の積層型ＣＮＴ含有複合材を製造する方法であって、金属粉末とＣＮＴに衝撃力、圧縮力、摩擦力及び剪断力から成る群より選ばれた少なくとも１種の機械的作用を繰り返し加えて、一体化させてＣＮＴ含有金属粉末を得、得られたＣＮＴ含有金属粉末を非酸化性雰囲気下で加熱して、溶融または半溶融状態にし、基材表面に積層させる方法である。
そして、金属粉末とカーボンナノチューブを一体化させるに当たり、好ましくはその雰囲気を不活性ガス雰囲気とする方法である。
Furthermore, the method for producing a laminated CNT-containing composite material according to the present invention is a method for producing the above-mentioned laminated CNT-containing composite material according to the present invention, wherein impact force, compressive force, frictional force and shear force are applied to metal powder and CNT. At least one mechanical action selected from the group consisting of forces is repeatedly added and integrated to obtain a CNT-containing metal powder, and the obtained CNT-containing metal powder is heated and melted in a non-oxidizing atmosphere. Or it is the method of making it a semi-molten state and laminating | stacking on the base-material surface.
In integrating the metal powder and the carbon nanotube, the atmosphere is preferably an inert gas atmosphere.
本発明によれば、金属粉末の内部及び表面の一方又は双方にＣＮＴを保持して成るＣＮＴ含有金属粉末を得、それを出発原料とすることなどとしたため、ＣＮＴを分散・配合させ、機械的性質や電気的性質、熱的性質などに優れ、部材や部品として使用に適したＣＮＴ含有複合材及びその製造方法を提供することができる。 According to the present invention, since a CNT-containing metal powder obtained by holding CNT inside and / or on the surface of the metal powder is obtained and used as a starting material, CNT is dispersed and blended, It is possible to provide a CNT-containing composite material excellent in properties, electrical properties, thermal properties, etc., and suitable for use as a member or component, and a method for producing the same.
以下、本発明のＣＮＴ含有金属粉末について詳細に説明する。
上述の如く、本発明のＣＮＴ含有金属粉末は、金属粉末の内部及び表面の一方又は双方にＣＮＴを保持して成るものである。
このようなＣＮＴ含有金属粉末は、詳しくは後述する本発明のＣＮＴ含有複合材や積層型ＣＮＴ含有複合材を製造する際の出発原料として好適に用いることができる。
Hereinafter, the CNT-containing metal powder of the present invention will be described in detail.
As described above, the CNT-containing metal powder of the present invention is obtained by holding CNTs in one or both of the inside and the surface of the metal powder.
Such a CNT-containing metal powder can be suitably used as a starting material when producing the CNT-containing composite material or laminated CNT-containing composite material of the present invention described later in detail.
また、本発明のＣＮＴ含有金属粉末において、そのＣＮＴ含有率は２〜２０体積％であることが望ましい。
ＣＮＴ含有率が２体積％より小さいと、複合材とした際に、その性能が十分に発揮されない可能性がある。一方、２０体積％を超えると、ＣＮＴの凝集が完全に解けず、複合材を成形した際に、欠陥となり、かえって機械的強度やその他の性能が低下するおそれがある。
In the CNT-containing metal powder of the present invention, the CNT content is preferably 2 to 20% by volume.
When the CNT content is less than 2% by volume, there is a possibility that the performance is not sufficiently exhibited when a composite material is obtained. On the other hand, when it exceeds 20% by volume, the aggregation of CNTs is not completely solved, and when the composite material is molded, it becomes a defect, which may lower the mechanical strength and other performances.
更に、本発明のＣＮＴ含有金属粉末において、用いる金属粉末については特に限定されるものではないが、代表的なものとして、銅（Ｃｕ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、鉄（Ｆｅ）又はアルミニウム（Ａｌ）、及びこれらの任意の組合わせに係る金属を含む合金などを挙げることができる。
このような金属粉末の大きさとしては、特に限定されるものではないが、平均粒径が３０〜３００μｍ程度のものを利用することが望ましい。
Furthermore, in the CNT-containing metal powder of the present invention, the metal powder to be used is not particularly limited, but representative examples include copper (Cu), cobalt (Co), nickel (Ni), iron (Fe). Alternatively, aluminum (Al), and an alloy containing a metal related to any combination thereof can be given.
The size of the metal powder is not particularly limited, but it is desirable to use a metal powder having an average particle size of about 30 to 300 μm.
更にまた、本発明のＣＮＴ含有金属粉末において、用いるＣＮＴは、その種類について特に限定されるものではなく、単層（ＳＷ−ＣＮＴ）であっても多層（ＭＷ−ＣＮＴ）であっても構わないが、焼結や肉盛などの製造工程において高温に曝されるので、耐熱性の高いものが望ましい。例えば、５００℃以上の耐熱性を有すればよく、７００℃以上の耐熱性を有することが好ましい。 Furthermore, in the CNT-containing metal powder of the present invention, the type of CNT to be used is not particularly limited, and may be a single layer (SW-CNT) or a multilayer (MW-CNT). However, since it is exposed to high temperature in manufacturing processes, such as sintering and overlaying, a thing with high heat resistance is desirable. For example, it should just have heat resistance of 500 degreeC or more, and it is preferable to have heat resistance of 700 degreeC or more.
次に、本発明のＣＮＴ含有金属粉末の製造方法について詳細に説明する。
上述の如く、本発明のＣＮＴ含有金属粉末の製造方法は、上記本発明のＣＮＴ含有金属粉末を製造するに当たり、金属粉末とカーボンナノチューブに衝撃力、圧縮力、摩擦力又は剪断力、及びこれらの任意の組合せに係る機械的作用を繰り返し加えて、一体化させて、所望のＣＮＴ含有金属粉末を得る方法である。
そして、金属粉末とカーボンナノチューブを一体化させるに当たり、その雰囲気を不活性ガス雰囲気とすることが好ましい。
なお、不活性ガスとしては、例えば窒素（Ｎ２）やアルゴン（Ａｒ）を用いことができるが、詳しくは後述する雰囲気とＣＮＴ含有金属粉末との反応を考慮するとより安定なアルゴンが好ましい。
Next, the manufacturing method of the CNT containing metal powder of this invention is demonstrated in detail.
As described above, the method for producing the CNT-containing metal powder of the present invention provides the impact force, compressive force, frictional force or shear force applied to the metal powder and the carbon nanotube, In this method, mechanical actions related to any combination are repeatedly added and integrated to obtain a desired CNT-containing metal powder.
And when integrating a metal powder and a carbon nanotube, it is preferable to make the atmosphere into an inert gas atmosphere.
As the inert gas, for example, nitrogen (N 2 ) or argon (Ar) can be used, but more stable argon is preferable in consideration of the reaction between the atmosphere described later and the CNT-containing metal powder.
より具体的には、例えば高速気流中で金属粉末とＣＮＴとを衝突させて、これらに衝撃力や圧縮力、摩擦力、剪断力等の機械的作用を繰り返し加えることによって、ＣＮＴの凝集が解かれながら、金属粉末の表面にＣＮＴが固着したり、金属粉末同士が合体する際に、その内部にＣＮＴが取り込まれることにより、ＣＮＴと金属粉末とが一体化したＣＮＴ含有金属粉末を得ることができる。 More specifically, for example, by colliding metal powder with CNTs in a high-speed air current and repeatedly applying mechanical actions such as impact force, compression force, friction force, shear force, etc., the aggregation of CNTs is solved. As it is, when CNTs adhere to the surface of the metal powder or when the metal powders coalesce, the CNTs are taken into the interior, thereby obtaining a CNT-containing metal powder in which the CNTs and the metal powder are integrated. it can.
なお、このように作製することにより、ＣＮＴ含有金属粉末は生産性良く得られ、更に本発明のＣＮＴ含有複合材や積層型ＣＮＴ含有複合材を作製する際の原料として特に望ましいものとなるが、本発明のＣＮＴ含有金属粉末は、かかる方法により作製されたものに限定されないことは言うまでもない。 In addition, by producing in this way, the CNT-containing metal powder can be obtained with high productivity, and it is particularly desirable as a raw material for producing the CNT-containing composite material and the laminated CNT-containing composite material of the present invention. It goes without saying that the CNT-containing metal powder of the present invention is not limited to those produced by such a method.
更に、この際には、金属粉末やＣＮＴの表面は、その微細な構造のため（金属粉末は代表的には、平均粒径が３０〜３００μｍ程度であり、ＣＮＴは代表的には、直径が数１０ｎｍ程度であり、かつ長さが数μｍ程度である。）、かなり活性化された状態であり、製造工程における雰囲気と反応し易くなる。
具体的には、酸化や窒化が起こり易くなる。そのため、部分的に酸化や窒化されたような反応生成物を必要とする場合を除いて、上述したように不活性ガス雰囲気中で、上記工程を実施することが望ましい。
Further, at this time, the surface of the metal powder or CNT has a fine structure (the metal powder typically has an average particle size of about 30 to 300 μm, and the CNT typically has a diameter of about 30 to 300 μm. It is about several tens of nm and the length is about several μm.) It is in a considerably activated state and easily reacts with the atmosphere in the manufacturing process.
Specifically, oxidation and nitridation are likely to occur. Therefore, it is desirable to carry out the above steps in an inert gas atmosphere as described above, except when a reaction product that is partially oxidized or nitrided is required.
図１は、本発明のＣＮＴ含有金属粉末の製造方法により得られるＣＮＴ含有金属粉末の概念図である。
同図に示すように、金属粉末とＣＮＴは、上述したような処理を経ることにより、ＣＮＴ含有複合材等の出発原料として好適なＣＮＴ含有金属粉末となる。
FIG. 1 is a conceptual diagram of a CNT-containing metal powder obtained by the method for producing a CNT-containing metal powder of the present invention.
As shown in the figure, the metal powder and CNT become a CNT-containing metal powder suitable as a starting material for a CNT-containing composite material and the like by undergoing the above-described treatment.
次に、本発明のＣＮＴ含有複合材について詳細に説明する。
上述の如く、本発明のＣＮＴ含有複合材は、上記本発明のＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末を焼結して成るものである。
このようにＣＮＴ含有複合材は、所望する形状に適宜成形し、加熱・焼結してバルク化することができ、機械的性質や電気的性質、熱的性質などに優れ、部材や部品の使用に適したものを得ることができる。
Next, the CNT-containing composite material of the present invention will be described in detail.
As described above, the CNT-containing composite material of the present invention is obtained by sintering the CNT-containing metal powder using the CNT-containing metal powder of the present invention.
In this way, CNT-containing composites can be appropriately shaped into the desired shape, heated and sintered to be bulked, and have excellent mechanical properties, electrical properties, thermal properties, etc., and use of members and parts Can be obtained.
また、ＣＮＴの含有量は、上述したような理由により２〜２０体積％であることが好ましく、ＣＮＴ含有複合材のマトリックス金属についても、特に限定されるものではないが、例えば、代表的なものとして、Ｃｕ、Ｃｏ、Ｎｉ、Ｆｅ又はＡｌ、及びこれらの任意の組合わせに係る金属を含む合金などを挙げることができる。 Further, the content of CNT is preferably 2 to 20% by volume for the reasons described above, and the matrix metal of the CNT-containing composite material is not particularly limited. Examples thereof include Cu, Co, Ni, Fe, Al, and alloys containing metals according to any combination thereof.
次に、本発明のＣＮＴ含有複合材の製造方法について詳細に説明する。
上述の如く、本発明のＣＮＴ複合材の製造方法は、上記本発明のＣＮＴ含有複合材を製造するに当たり、上述したように金属粉末とＣＮＴに衝撃力、圧縮力、摩擦力又は剪断力、及びこれらの任意の組合せに係る機械的作用を繰り返し加えて、好ましくは不活性ガス雰囲気中で、一体化させてＣＮＴ含有金属粉末を得、得られたＣＮＴ含有金属粉末を非酸化性雰囲気下で加熱して、焼結させて、所望のＣＮＴ含有複合材を得る方法である。
このように、上記本発明のＣＮＴ含有金属粉末を用いることにより、機械的性質や電気的性質、熱的性質などに優れ、部材や部品として使用に適したＣＮＴ含有複合材を効率よく得ることができる。
なお、非酸化性雰囲気を得るために、真空中、又はアルゴン（Ａｒ）、ヘリウム（Ｈｅ）等の不活性ガス中、又は窒素（Ｎ２）若しくは水素（Ｈ２）などの還元性雰囲気中で処理すればよい。真空中であることが好ましいが、上記雰囲気でも特に支障はない。
Next, the manufacturing method of the CNT containing composite material of this invention is demonstrated in detail.
As described above, the manufacturing method of the CNT composite material according to the present invention, in manufacturing the CNT-containing composite material according to the present invention, as described above, impact force, compressive force, frictional force or shear force on the metal powder and CNT, and A mechanical action related to any combination of these is repeatedly applied, and preferably integrated in an inert gas atmosphere to obtain a CNT-containing metal powder, and the obtained CNT-containing metal powder is heated in a non-oxidizing atmosphere. Then, the desired CNT-containing composite material is obtained by sintering.
Thus, by using the CNT-containing metal powder of the present invention, it is possible to efficiently obtain a CNT-containing composite material that is excellent in mechanical properties, electrical properties, thermal properties, etc. and suitable for use as a member or component. it can.
In order to obtain a non-oxidizing atmosphere, in a vacuum, or in an inert gas such as argon (Ar) or helium (He), or in a reducing atmosphere such as nitrogen (N 2 ) or hydrogen (H 2 ). What is necessary is just to process. Although it is preferably in a vacuum, there is no particular problem in the above atmosphere.
但し、金属粉末の表面に固着したＣＮＴは、ＣＮＴ含有金属粉末同士の焼結を若干ではあるが阻害するので、その場合には、ＣＮＴ含有金属粉末を成形用の型中で圧縮・加熱するだけでなく、塑性加工工程を付加することにより、より健全なバルクが得られやすくなる。
また、圧延や押出しなどの塑性加工工程を付加することにより、方向性のあるＣＮＴ含有複合材を製造することができ、積極的に異方性を利用したＣＮＴ含有複合材を得ることもできる。
なお、このような製造方法は、生産性に優れたものであるが、所望する性能を有するものが得られれば、本発明のＣＮＴ含有複合材は、かかる方法により作製されたものに限定されないことは言うまでもない。
However, since the CNTs fixed on the surface of the metal powder slightly inhibit the sintering of the CNT-containing metal powders, in that case, the CNT-containing metal powder is simply compressed and heated in a molding die. Instead, by adding a plastic working step, a more sound bulk can be easily obtained.
Further, by adding a plastic working step such as rolling or extrusion, a directional CNT-containing composite material can be produced, and a CNT-containing composite material that actively utilizes anisotropy can also be obtained.
In addition, although such a manufacturing method is excellent in productivity, if a material having desired performance is obtained, the CNT-containing composite material of the present invention is not limited to that produced by such a method. Needless to say.
次に、本発明の積層型ＣＮＴ含有複合材について詳細に説明する。
上述の如く、本発明の積層型ＣＮＴ含有複合材は、上記本発明のＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末を基材表面に肉盛して成るものである。
このように、上記本発明のＣＮＴ含有金属粉末を用いることにより、機械的性質や電気的性質、熱的性質などに優れ、部材や部品として使用に適した積層型ＣＮＴ複合材を得ることができる。
なお、用いる基材の材質については、例えば耐熱鋼、より具体的にはアルミニウム合金や鉄基合金などを適用することができるがこれに限定されるものではない。
また、用いる基材の形状についても、例えば板状や円筒状、円柱状などのものに適用することができ、部品の形状にしたものに適用することもできる。
Next, the laminated CNT-containing composite material of the present invention will be described in detail.
As described above, the multilayer CNT-containing composite material of the present invention is formed by depositing the CNT-containing metal powder on the surface of the substrate using the CNT-containing metal powder of the present invention.
Thus, by using the CNT-containing metal powder of the present invention, it is possible to obtain a multilayer CNT composite material that is excellent in mechanical properties, electrical properties, thermal properties, etc. and suitable for use as a member or component. .
In addition, as a material of the base material to be used, for example, heat-resistant steel, more specifically, an aluminum alloy or an iron-based alloy can be applied, but the material is not limited thereto.
Further, the shape of the base material used can be applied to, for example, a plate shape, a cylindrical shape, a columnar shape, etc., and can also be applied to a component shape.
また、肉盛部位のＣＮＴの含有量は、上述したような理由により２〜２０体積％であることが好ましく、ＣＮＴを含有する複合材層のマトリックス金属についても、特に限定されるものではないが、例えば、代表的なものとして、Ｃｕ、Ｃｏ、Ｎｉ、Ｆｅ又はＡｌ、及びこれらの任意の組合わせに係る金属を含む合金などを挙げることができる。 Further, the content of the CNT in the build-up site is preferably 2 to 20% by volume for the reason described above, and the matrix metal of the composite material layer containing CNT is not particularly limited. For example, typical examples include Cu, Co, Ni, Fe, Al, and alloys containing metals according to any combination thereof.
また、上述した本発明のＣＮＴ含有複合材のように、全体がＣＮＴを含有する複合材となっているわけではないが、部材や部品とする際に必要な部位にだけ肉盛をし、ＣＮＴを含有する複合材層を形成することができ、また、めっき層と異なり厚膜を形成することもできるため、適宜性能を向上させることができ、部材・部品の設計も容易となる。 In addition, unlike the CNT-containing composite material of the present invention described above, the entire CNT-containing composite material is not a CNT-containing composite material. Since a composite material layer containing can be formed, and a thick film can be formed unlike a plating layer, the performance can be appropriately improved, and the design of members and parts is facilitated.
次に、本発明のバルブフェース部材、シリンダヘッドバルブシート部材、シリンダヘッド弁間部材及び成形用金型について詳細に説明する。
まず、本発明の積層型ＣＮＴ含有複合材を自動車用部品に適用した例について説明する。
本発明のバルブフェース部材は、上記本発明の積層型ＣＮＴ含有複合材を用いた部材であって、Ｃｏ及びＮｉの一方又は双方を含むＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末を耐熱鋼の基材表面に肉盛して成るものである。
このような構成とすることにより、耐熱性や伝熱性が更に向上し、動力性能を高めることができる。
なお、基材表面に形成されるＣＮＴを含有する複合材層に含まれる金属は、上記のものに特に限定されるものではなく、例えば現行よく用いられているニッケル基やコバルト基、鉄基などの合金も用いることができる。
Next, the valve face member, cylinder head valve seat member, cylinder head inter-valve member, and molding die of the present invention will be described in detail.
First, an example in which the laminated CNT-containing composite material of the present invention is applied to an automotive part will be described.
The valve face member of the present invention is a member using the laminated CNT-containing composite material of the present invention, and a CNT-containing metal powder containing one or both of Co and Ni is used. It is built up on the surface of the substrate.
By setting it as such a structure, heat resistance and heat conductivity can further improve and power performance can be improved.
In addition, the metal contained in the composite material layer containing CNTs formed on the substrate surface is not particularly limited to the above, and for example, nickel base, cobalt base, iron base, etc. that are often used at present These alloys can also be used.
また、本発明のシリンダヘッドバルブシート部材は、上記本発明の積層型ＣＮＴ含有複合材を用いた部材であって、Ｃｕを含むＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末をアルミニウム合金の基材表面に肉盛して成るものである。
このような構成とすることにより、強度だけでなく、熱伝導特性を更に向上させることができる。また、低熱膨張性のものとすることもできる。
なお、基材表面に形成されるＣＮＴを含有する複合材層に含まれる金属としては、特に限定されるものではないが、耐熱・高強度合金であることが望ましく、例えばＮｉやケイ素（Ｓｉ）、モリブデン（Ｍｏ）などの合金元素を添加した銅合金などを挙げることができる。
The cylinder head valve seat member of the present invention is a member using the multilayer CNT-containing composite material of the present invention, wherein the CNT-containing metal powder containing Cu is used as a base material of an aluminum alloy. It is built up on the surface of the material.
By adopting such a configuration, not only strength but also heat conduction characteristics can be further improved. It can also be of low thermal expansion.
The metal contained in the composite material layer containing CNT formed on the substrate surface is not particularly limited, but is preferably a heat-resistant and high-strength alloy such as Ni or silicon (Si). And a copper alloy to which an alloy element such as molybdenum (Mo) is added.
更に、本発明のシリンダベッド弁間部材は、上記本発明の積層型ＣＮＴ含有複合材を用いた部材であって、Ａｌを含むＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末をアルミニウム合金の基材表面に肉盛して成るものである。
シリンダヘッド弁間部は、使用中の熱応力による亀裂を防がねばならず、近年のエンジンの高出力化やコンパクト化に伴い、この部位の使用環境は益々厳しくなっている。
そこで、この部位に開先を設け、基材とＣＮＴを含有する複合材層とを同じＡｌを含むような構成とすることにより、耐熱性や低熱膨張性を更に向上させることができる。
Further, the cylinder bed valve member of the present invention is a member using the above-mentioned laminated CNT-containing composite material of the present invention, and uses a CNT-containing metal powder containing Al, and the CNT-containing metal powder is based on an aluminum alloy. It is built up on the surface of the material.
The portion between the cylinder head valves must be prevented from cracking due to thermal stress during use, and the use environment of this part has become increasingly severe with the recent increase in output and compactness of the engine.
Therefore, by providing a groove at this site and making the base material and the composite material layer containing CNTs contain the same Al, heat resistance and low thermal expansion can be further improved.
更にまた、本発明の積層型ＣＮＴ含有複合材を自動車部品以外に適用した例について説明する。
従来から鍛造や鋳造する際の金型として、鉄系の合金のものが使用されているが、使用中に厳しい熱環境に曝され表面にヒートクラックが発生するため、損傷が小さい場合にはその都度補修して再使用すること、損傷が著しい場合には新規に作り直すことが行われている。
Furthermore, an example in which the laminated CNT-containing composite material of the present invention is applied to other than automobile parts will be described.
Conventionally, iron-based alloys are used as molds for forging and casting. However, since heat cracks occur on the surface due to exposure to severe thermal environments during use, if the damage is small, It is repaired and reused each time, and when damage is significant, it is remade.
そして、本発明の成形用金型部材は、上記本発明の積層型ＣＮＴ含有複合材を用いた部材であって、Ｆｅを含むＣＮＴ含有金属粉末を用い、該ＣＮＴ含有金属粉末を鉄基合金の基材表面に肉盛して成るものである。
このような構成とすることにより、耐熱性や熱伝導性を更に向上させることができ、寿命をより長くすることができる。
また、成形用金型の一例であるプレス型でも同様に、強度や熱伝導性を向上させることができ、耐摩耗性やかじり性を改善して、寿命を長くすることができる。
更に、成形用金型の一例である射出成形型では、熱伝導性を向上させることができるため、その使用に際し、成形サイクルを速めることができる。
なお、基材表面に形成されるＣＮＴを含有する複合材層に含まれる金属としては、特に限定されるものではないが、耐熱性を有する金属であることが望ましく、例えば鉄系金属やニッケル基の耐熱合金などを挙げることができる。
The molding die member of the present invention is a member using the multilayer CNT-containing composite material of the present invention, using a CNT-containing metal powder containing Fe, and using the CNT-containing metal powder of an iron-based alloy. It is built up on the substrate surface.
By setting it as such a structure, heat resistance and heat conductivity can further be improved and a lifetime can be lengthened more.
Similarly, a press die, which is an example of a molding die, can improve strength and thermal conductivity, can improve wear resistance and galling property, and can extend the life.
Furthermore, in an injection mold that is an example of a mold for molding, the thermal conductivity can be improved, so that the molding cycle can be accelerated when used.
The metal contained in the composite material layer containing CNTs formed on the substrate surface is not particularly limited, but is preferably a metal having heat resistance, such as an iron-based metal or nickel-based metal. And heat-resistant alloys.
次に、本発明の積層型ＣＮＴ含有複合材の製造方法について詳細に説明する。
上述の如く、本発明の積層型ＣＮＴ含有複合材の製造方法は、上記本発明の積層型ＣＮＴ含有複合材を製造するに当たり、上述したように金属粉末とＣＮＴに衝撃力、圧縮力、摩擦力又は剪断力、及びこれらの任意の組合わせに係る機械的作用を繰り返し加えて、好ましくは不活性ガス雰囲気中で、一体化させてＣＮＴ含有金属粉末を得、得られたＣＮＴ含有金属粉末を非酸化性雰囲気下で加熱して、溶融または半溶融状態にし、基材表面に積層させて、所望の積層型ＣＮＴ含有複合材を得る方法である。
このように、上記本発明のＣＮＴ含有金属粉末と、基材を用いることにより、機械的性質や電気的性質、熱的性質などに優れ、部材や部品として使用に適した積層型ＣＮＴ含有複合材を効率よく得ることができる。
Next, the manufacturing method of the laminated CNT-containing composite material of the present invention will be described in detail.
As described above, the method for producing a laminated CNT-containing composite material according to the present invention provides the impact force, compressive force, and frictional force applied to the metal powder and CNT as described above in producing the laminated CNT-containing composite material according to the present invention. Alternatively, a shearing force and a mechanical action relating to any combination thereof are repeatedly added, and preferably integrated in an inert gas atmosphere to obtain a CNT-containing metal powder. This is a method of obtaining a desired laminated CNT-containing composite material by heating in an oxidizing atmosphere to be in a molten or semi-molten state and laminated on the surface of the substrate.
As described above, by using the CNT-containing metal powder of the present invention and a base material, a laminated CNT-containing composite material excellent in mechanical properties, electrical properties, thermal properties, etc. and suitable for use as a member or component. Can be obtained efficiently.
より具体的には、例えば本発明のＣＮＴ含有金属粉末と、基材とを用いて積層型ＣＮＴ含有複合材を製造するに当たり、基材と非消耗電極との間に発生させたプラズマアーク中（代表的には数万℃程度。）に、本発明のＣＮＴ含有金属粉末を供給し、溶融させて基材表面に肉盛するプラズマ粉体肉盛や、プラズマジェット中（代表的には数万℃程度。）に、本発明のＣＮＴ含有金属粉末を供給し、溶融させて高速気流（代表的には気流速度はノズル近傍では数千ｍ／秒程度。）で基材に吹き付け肉盛（積層）するプラズマ溶射、より好ましくは火炎中（代表的には２５００〜２８００℃程度。）にＣＮＴ含有金属粉末を投入し、半溶融状態にして超音速気流（代表的には気流速度１３００〜２４００ｍ／秒程度。）で基材表面に吹き付け肉盛（積層）するＨＶＯＦ（Ｈｉｇｈ Ｖｅｌｏｃｉｔｙ Ｏｘｙｇｅｎ Ｆｕｅｌ ｓｐｒａｙ ｐｒｏｃｅｓｓ）又はＨＶＡＦ（Ｈｉｇｈ Ｖｅｌｏｃｉｔｙ Ａｉｒ Ｆｕｅｌ ｓｐｒａｙ ｐｒｏｃｅｓｓ）という高速フレーム溶射によってＣＮＴを含有する複合材層を基材表面に形成することができる。肉盛りはプラズマ粉体肉盛りに限らず、他の方法、例えばレーザ肉盛りでもかまわない。 More specifically, for example, in producing a laminated CNT-containing composite material using the CNT-containing metal powder of the present invention and a base material, in a plasma arc generated between the base material and a non-consumable electrode ( (Typically about several tens of thousands of degrees C.) The CNT-containing metal powder of the present invention is supplied and melted to build up on the surface of the substrate, and in a plasma jet (typically tens of thousands). The CNT-containing metal powder of the present invention is supplied to and melted and sprayed on the substrate with a high-speed airflow (typically, the airflow speed is about several thousand m / sec near the nozzle). ) Plasma spraying, more preferably in a flame (typically about 2500 to 2800 ° C.), a CNT-containing metal powder is put into a semi-molten state and a supersonic airflow (typically an air velocity of 1300 to 2400 m / second). Sprayed on the substrate surface in about seconds) The composite material layer containing a CNT by high-velocity flame spraying of the laminated) to HVOF (High Velocity Oxygen Fuel spray process) or HVAF (High Velocity Air Fuel spray process) can be formed on the substrate surface. The build-up is not limited to plasma powder build-up, and other methods such as laser build-up may be used.
なお、このような製造方法は、生産性に優れたものであるが、所望する性能を有するものが得られれば、本発明の積層型ＣＮＴ複合材は、かかる方法により作製されたものに限定されないことは言うまでもない。 In addition, although such a manufacturing method is excellent in productivity, as long as what has the desired performance is obtained, the multilayer CNT composite material of the present invention is not limited to that manufactured by such a method. Needless to say.
ここで、本発明の積層型ＣＮＴ含有複合材を製造する様子を図面を用いて詳細に説明する。
図２は、積層型ＣＮＴ含有複合材をプラズマ粉体肉盛装置により製造する様子を示す概念説明図である。なお、同図は、非消耗電極の軸を通り、肉盛方向に平行な面で切断した断面を示すものである。
同図に示すように、プラズマ粉体肉盛装置１００は、トーチ１１０（水冷機構は図示せず。）と溶接電源１２０を備え、トーチ１１０内には、非消耗電極１１２と、センターガス流路１１４と、原料粉末供給路１１６と、シールドガス流路１１８を有している。
また、トーチ１１０内の非消耗電極１１２と用いる基材１２とは溶接電源１２０を介して接続されている。
Here, how to manufacture the multilayer CNT-containing composite material of the present invention will be described in detail with reference to the drawings.
FIG. 2 is a conceptual explanatory view showing a state in which a laminated CNT-containing composite material is manufactured by a plasma powder cladding apparatus. The figure shows a cross section cut along a plane passing through the axis of the non-consumable electrode and parallel to the build-up direction.
As shown in the figure, the plasma
Further, the
センターガス流路１１４に矢印で示すように例えばＡｒ又はＨｅなどのガスを通じ、原料粉末供給路１１６からＣＮＴ含有金属粉末１４ａを供給し、シールドガス流路１１８に矢印で示すように例えばＡｒ又はＨｅなどのガスを通じながら、非消耗電極１１２と用いる基材１２との間にプラズマアークＡを発生させ、その中にＣＮＴ含有金属粉末１４ａを供給することにより、ＣＮＴ含有金属粉末１４ａがプラズマアークＡ中で溶融され、基材１２の表面にＣＮＴ含有金属粉末１４ａが肉盛され、肉盛層（ＣＮＴを含有する複合材層）１４が形成された積層型ＣＮＴ複合材１０が得られる。
なお、図において左側に基材１２を移動することにより、矢印Ｆの肉盛方向に肉盛層が形成されていく。
As shown by an arrow in the center
In addition, a build-up layer is formed in the build-up direction of the arrow F by moving the
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
（実施例１）
強化材として、直径が２０〜５０ｎｍの多層型ＣＮＴと平均粒径が３０μｍのＡｌ−Ｓｉ合金粉末をＡｒ気流にのせてロータが回転する容器中で衝撃力を付加してＣＮＴ含有金属粉末を作製した。
得られたＣＮＴ含有金属粉末のＣＮＴ含有率は４体積％であった。
使用した装置は、（株）奈良機械製作所製、ハイブリダイゼーヨン装置で、処理時間は３分であった。
Example 1
As a reinforcing material, a multi-wall CNT having a diameter of 20 to 50 nm and an Al-Si alloy powder having an average particle diameter of 30 μm are placed in an Ar air stream and an impact force is applied in a container in which a rotor rotates to produce a CNT-containing metal powder. did.
The CNT content of the obtained CNT-containing metal powder was 4% by volume.
The apparatus used was a hybridization apparatus manufactured by Nara Machinery Co., Ltd., and the treatment time was 3 minutes.
得られたＣＮＴ含有金属粉末を用いて、プラズマ粉体肉盛装置（日鐵溶接工業社製）によって、純アルミニウム板（厚さ：５ｍｍ）上に厚さ３〜４ｍｍの肉盛層（ＣＮＴを含有する複合材層）を形成し、本例の積層型ＣＮＴ含有複合材を得た。
得られた積層型ＣＮＴ含有複合材は、割れや大きなポロシティの観察されない健全な肉盛層を有していた。
Using the obtained CNT-containing metal powder, a 3 to 4 mm thick build-up layer (CNT is formed on a pure aluminum plate (thickness: 5 mm) by a plasma powder build-up device (manufactured by Nippon Steel Welding Co., Ltd.). Composite layer containing) to form a laminated CNT-containing composite material of this example.
The obtained laminated CNT-containing composite material had a sound build-up layer in which no cracks or large porosity was observed.
（実施例２）
強化材として、直径が２０〜５０ｎｍの多層型ＣＮＴと平均粒径が３０μｍの純Ｃｕ粉末をＡｒ気流にのせてロータが回転する容器中で衝撃力を付加してＣＮＴ含有金属粉末を作製した。
得られたＣＮＴ含有金属粉末のＣＮＴ含有率は３．５体積％であった。
(Example 2)
As a reinforcing material, a multi-walled CNT having a diameter of 20 to 50 nm and a pure Cu powder having an average particle diameter of 30 μm were placed on an Ar air stream, and an impact force was applied in a container in which a rotor was rotated to produce a CNT-containing metal powder.
The CNT content of the obtained CNT-containing metal powder was 3.5% by volume.
得られたＣＮＴ含有金属粉末を用いて、ＨＶＯＦによって、純アルミニウム板（厚さ：５ｍｍ）上に厚さ３〜４ｍｍの肉盛層（ＣＮＴを含有する複合材層）を形成し、本例の積層型ＣＮＴ含有複合材を得た。
得られた積層型ＣＮＴ含有複合材は、割れや大きなポロシティの観察されない健全な肉盛層を有していた。
Using the obtained CNT-containing metal powder, an overlay layer (composite layer containing CNT) having a thickness of 3 to 4 mm is formed on a pure aluminum plate (thickness: 5 mm) by HVOF. A laminated CNT-containing composite material was obtained.
The obtained laminated CNT-containing composite material had a sound build-up layer in which no cracks or large porosity was observed.
（実施例３）
実施例１で得られたＣＮＴ含有金属粉末を用いて、コンテナに挿入し、脱気し、シールした状態で、熱間で押出しして、本例のＣＮＴ含有複合材（焼結体）を得た。
得られたＣＮＴ含有複合材は、相対密度が１００％の健全なバルクであった。
本実施例では、押出し温度４００℃、押出し速度１０ｍｍ／分、押出し比１５とした。
(Example 3)
Using the CNT-containing metal powder obtained in Example 1, the CNT-containing composite material (sintered body) of this example was obtained by inserting into a container, degassing, and extruding hot in a sealed state. It was.
The obtained CNT-containing composite was a healthy bulk with a relative density of 100%.
In this example, the extrusion temperature was 400 ° C., the extrusion speed was 10 mm / min, and the extrusion ratio was 15.
（比較例１）
ＣＮＴ複合粉末の代わりに、平均粒径３０μｍのＡｌ−Ｓｉ合金粉末のみを使用した以外は、実施例１と同様の操作を繰り返し、本例の部材を得た。
(Comparative Example 1)
The same operation as in Example 1 was repeated except that only the Al—Si alloy powder having an average particle size of 30 μm was used in place of the CNT composite powder to obtain a member of this example.
（比較例２）
ＣＮＴ複合粉末の代わりに、平均粒径３０μｍの純Ｃｕ粉末のみを使用した以外は、実施例２と同様の操作を繰り返し、本例の部材を得た。
(Comparative Example 2)
A member of this example was obtained by repeating the same operation as in Example 2 except that only pure Cu powder having an average particle size of 30 μm was used instead of the CNT composite powder.
（比較例３）
ＣＮＴ複合粉末の代わりに、平均粒径３０μｍのＡｌ−Ｓｉ合金粉末のみを使用した以外は、実施例３と同様の操作を繰り返し、本例の部材を得た。
(Comparative Example 3)
The same operation as in Example 3 was repeated except that only the Al—Si alloy powder having an average particle size of 30 μm was used in place of the CNT composite powder to obtain a member of this example.
［性能評価］
上記各例の部材から試料を切り出し、各種評価試験に供した。
[Performance evaluation]
Samples were cut out from the members of the above examples and subjected to various evaluation tests.
（引張り強度試験）
実施例１及び比較例１の試料について、下記条件のもとで引張り強度を測定したところ、比較例１に対して実施例１の引張り強度が２６％向上していた。
また、実施例３及び比較例３の試料について、同様に引張り強度を測定したところ、比較例３に対して実施例３の引張り強度がおよそ２５％向上していた。
(Tensile strength test)
When the tensile strength of the samples of Example 1 and Comparative Example 1 was measured under the following conditions, the tensile strength of Example 1 was improved by 26% with respect to Comparative Example 1.
Moreover, when the tensile strength was similarly measured about the sample of Example 3 and the comparative example 3, the tensile strength of Example 3 improved about 25% with respect to the comparative example 3. FIG.
（試験条件）
肉盛層から厚さ２ｍｍの短冊状試験片を切り出し、室温で引張り試験を行った。
(Test conditions)
A strip-shaped test piece having a thickness of 2 mm was cut out from the built-up layer, and a tensile test was performed at room temperature.
（熱伝導性試験）
実施例２及び比較例２の試料について、下記条件のもとで熱伝導率を測定したところ、比較例２に対して実施例２の熱伝導率が１５％向上していた。
(Thermal conductivity test)
When the thermal conductivity of the samples of Example 2 and Comparative Example 2 was measured under the following conditions, the thermal conductivity of Example 2 was improved by 15% with respect to Comparative Example 2.
（試験条件）
肉盛層から厚さ１ｍｍの円板状試験片を切り出し、レーザフラッシュ法にて測定を行なった。
(Test conditions)
A disk-shaped test piece having a thickness of 1 mm was cut out from the built-up layer and measured by a laser flash method.
このような結果から、優れた性能を有するＣＮＴ含有複合材や積層型ＣＮＴ含有複合材が得られていることが分かる。 From these results, it can be seen that CNT-containing composite materials and laminated CNT-containing composite materials having excellent performance are obtained.
１０ 積層型ＣＮＴ含有複合材
１２ 基材
１４ 肉盛層（ＣＮＴを含有する複合材層）
１４ａ ＣＮＴ含有金属粉末
１００ プラズマ粉体肉盛装置
１１０ トーチ
１１２ 非消耗電極
１１４ センターガス流路
１１６ 原料粉末供給路
１１８ シールドガス流路
１２０ 溶接電源
10 Stacked CNT-containing
14a CNT-containing
Claims (18)
金属粉末とカーボンナノチューブに衝撃力、圧縮力、摩擦力及び剪断力から成る群より選ばれた少なくとも１種の機械的作用を繰り返し加えて、一体化させることを特徴とするカーボンナノチューブ含有金属粉末の製造方法。 A method for producing the carbon nanotube-containing metal powder according to any one of claims 1 to 3,
What is claimed is: 1. A carbon nanotube-containing metal powder comprising a metal powder and a carbon nanotube, wherein at least one mechanical action selected from the group consisting of impact force, compressive force, friction force and shear force is repeatedly applied and integrated. Production method.
金属粉末とカーボンナノチューブに衝撃力、圧縮力、摩擦力及び剪断力から成る群より選ばれた少なくとも１種の機械的作用を繰り返し加えて、一体化させてカーボンナノチューブ含有金属粉末を得、得られたカーボンナノチューブ含有金属粉末を非酸化性雰囲気下で加熱して、焼結させることを特徴とするカーボンナノチューブ含有複合材の製造方法。 A method for producing the carbon nanotube-containing composite material according to claim 4,
At least one mechanical action selected from the group consisting of impact force, compression force, friction force and shear force is repeatedly applied to the metal powder and the carbon nanotube, and integrated to obtain a metal powder containing carbon nanotube. A method for producing a carbon nanotube-containing composite material, comprising heating and sintering a carbon nanotube-containing metal powder in a non-oxidizing atmosphere.
金属粉末とカーボンナノチューブに衝撃力、圧縮力、摩擦力及び剪断力から成る群より選ばれた少なくとも１種の機械的作用を繰り返し加えて、一体化させてカーボンナノチューブ含有金属粉末を得、得られたカーボンナノチューブ含有金属粉末を非酸化性雰囲気下で加熱して、溶融または半溶融状態にし、基材表面に積層させることを特徴とする積層型カーボンナノチューブ含有複合材の製造方法。 A method for producing a laminated carbon nanotube-containing composite material according to any one of claims 5 to 8,
At least one mechanical action selected from the group consisting of impact force, compression force, friction force and shear force is repeatedly applied to the metal powder and the carbon nanotube, and integrated to obtain a metal powder containing carbon nanotube. A method for producing a laminated carbon nanotube-containing composite material, characterized in that the carbon nanotube-containing metal powder is heated in a non-oxidizing atmosphere to be melted or semi-molten and laminated on the substrate surface.
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2005
- 2005-07-06 JP JP2005197218A patent/JP2007016262A/en active Pending
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