JP4351120B2 - Method for producing metal particles - Google Patents
Method for producing metal particles Download PDFInfo
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- JP4351120B2 JP4351120B2 JP2004239040A JP2004239040A JP4351120B2 JP 4351120 B2 JP4351120 B2 JP 4351120B2 JP 2004239040 A JP2004239040 A JP 2004239040A JP 2004239040 A JP2004239040 A JP 2004239040A JP 4351120 B2 JP4351120 B2 JP 4351120B2
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- 239000002923 metal particle Substances 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000002041 carbon nanotube Substances 0.000 claims description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 54
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 description 53
- 239000002184 metal Substances 0.000 description 53
- 239000002131 composite material Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
本発明は、電気接点、電池、電磁波シールド、導電材、摩擦材接点、摺動材等の材料として好適に用いることのできる金属材料の製造方法に関する。 The present invention relates to a method for producing a metal material that can be suitably used as a material such as an electrical contact, a battery, an electromagnetic wave shield, a conductive material, a friction material contact, and a sliding material.
金属内にカーボンナノチューブを分散させた複合金属体が知られている。
特許文献１（特開２０００−２２３００４号）に示される複合金属体は、カーボンナノチューブと金属粉とを混合し、焼結してブロック状となしたものである。
A composite metal body in which carbon nanotubes are dispersed in a metal is known.
A composite metal body disclosed in Patent Document 1 (Japanese Patent Application Laid-Open No. 2000-220304) is obtained by mixing carbon nanotubes and metal powder and sintering them into a block shape.
また、特許文献２（特開２００４−１８６１０２号）に示すように、複合金属体に用いるカーボンナノチューブとしてはある特定の種類のものを用いるのが一般的である。
しかしながら、上述した従来の技術のように特定の種類のカーボンナノチューブを混入させた複合金属体では、その電気伝導性や熱伝導性等の性能は混入させたカーボンナノチューブの性能に依存しているので、性能に限界があるという課題がある。 However, in the composite metal body in which a specific type of carbon nanotube is mixed as in the conventional technique described above, the performance such as electric conductivity and thermal conductivity depends on the performance of the mixed carbon nanotube. There is a problem that performance is limited.
そこで、本発明は上記課題を解決すべくなされたものであり、その目的とするところは従来よりも電気伝導性や熱伝導性等の性能を向上させた複合金属体の材料となる金属粒子の製造方法を提供することにある。 Therefore, the present invention has been made to solve the above-mentioned problems, and the object of the present invention is to provide a metal particle that is a material of a composite metal body with improved performance such as electrical conductivity and thermal conductivity than before. It is to provide a manufacturing method .
本発明にかかる金属粒子の製造方法によれば、２種類以上のカーボンナノチューブを分散した電解液を電解して、カソード電極上に、カーボンナノチューブが混入した金属粒子を析出させる工程と、該析出した金属粒子をカソード電極上から分離する工程とを含むことを特徴とする。According to the method for producing metal particles according to the present invention, the step of electrolyzing an electrolytic solution in which two or more types of carbon nanotubes are dispersed to deposit metal particles mixed with carbon nanotubes on the cathode electrode, and the deposition Separating the metal particles from the cathode electrode.
この方法によれば、性能の向上を図った複合金属体の材料として、カーボンナノチューブが均一に分散した金属粒子が得られる。 According to this method, metal particles in which carbon nanotubes are uniformly dispersed can be obtained as a composite metal body material with improved performance.
なお、本明細書中においてはカーボンナノチューブをＣＮＴと省略して称する場合がある。また、カーボンナノチューブの種類とは、構造的に違うもの、および同一構造であっても直径や線長さが異なるものを含めた概念である。In the present specification, the carbon nanotube may be abbreviated as CNT. Further, the type of carbon nanotube is a concept that includes structurally different ones and those that have the same structure but different diameters and line lengths.
また、前記カーボンナノチューブとしては、互いの直径比が５以上である少なくとも２種類のカーボンナノチューブを含むことを特徴としてもよく、前記カーボンナノチューブとしては、互いの線長さ比が２以上である少なくとも２種類のカーボンナノチューブを含むことを特徴としてもよい。The carbon nanotubes may include at least two types of carbon nanotubes having a diameter ratio of 5 or more. The carbon nanotubes have at least a line length ratio of 2 or more. Two types of carbon nanotubes may be included.
本発明によれば、従来の単一種類のカーボンナノチューブが混入した複合金属体よりも、電気伝導性や熱伝導性といった性能の向上を図ることができる。また２種類以上のカーボンナノチューブの相互作用により、さらなる性能の向上も期待できる。 According to the present invention, performances such as electrical conductivity and thermal conductivity can be improved as compared with the conventional composite metal body mixed with a single type of carbon nanotube. Further, further improvement in performance can be expected due to the interaction of two or more types of carbon nanotubes.
（複合金属体）
以下、本発明の好適な実施の形態について説明する。
複合金属体の概略説明図を図１に示す。
複合金属体１０は、銅などの金属に2種類のカーボンナノチューブ（ＣＮＴ）が混入して構成されている。
図１に示すＣＮＴは、大径且つ線方向の長さが長いＣＮＴ１２（以下、長大ＣＮＴと称する）と、小径且つ線方向の長さが短いＣＮＴ１３（以下、短小ＣＮＴと称する）の２種類である。
このため、複合金属体１０全体としては、長大ＣＮＴ１２の性能と短小ＣＮＴの性能の双方の性能を有することとなり、単一のＣＮＴが混入した複合金属体と比較して高性能の金属材料とすることができる
(Composite metal)
Hereinafter, preferred embodiments of the present invention will be described.
A schematic illustration of the composite metal body is shown in FIG.
The composite metal body 10 is configured by mixing two types of carbon nanotubes (CNT) in a metal such as copper.
The CNTs shown in FIG. 1 are of two types: CNTs 12 having a large diameter and a long linear direction (hereinafter referred to as long CNTs) and CNTs 13 having a small diameter and a short length in the linear direction (hereinafter referred to as short CNTs). is there.
For this reason, the composite metal body 10 as a whole has both the performance of long CNTs 12 and the performance of short CNTs, and is a high-performance metal material compared to a composite metal body mixed with a single CNT. be able to
また、複合金属体１０では、長大ＣＮＴ１２の間の金属マトリクス１４中に、短小ＣＮＴ１３が介在する。このため、短小ＣＮＴ１３は、長大ＣＮＴ１２のどうしの間を接続し長大ＣＮＴのネットワークも形成する。このネットワークの形成によって、長大ＣＮＴ１２が本来有している性能をさらに上回る性能が引き出されることが期待される。 In the composite metal body 10, short and small CNTs 13 are interposed in the metal matrix 14 between the long and large CNTs 12. For this reason, the short CNTs 13 connect the long CNTs 12 to form a network of long CNTs. With the formation of this network, it is expected that performance that exceeds the performance inherent in the long CNT 12 will be derived.
なお、ここでは複合金属体に混入されているＣＮＴの種類として、直径や長さの違いによるものを例として説明したが、種類の違いとしては直径や長さの違いに限られることはなく、構造の違いであってもよい。例えば年輪状のＣＮＴ、シングルウォールＣＮＴ、カップスタック状のＣＮＴ等の形状が異なるＣＮＴを複数種類混入させたものであってもよい。
また、ＣＮＴは2種類に限定されることはなく、２種類以上混入されていればよい。
In addition, here, as a type of CNT mixed in the composite metal body, as described as an example due to the difference in diameter and length, the difference in type is not limited to the difference in diameter and length, It may be a difference in structure. For example, a plurality of CNTs having different shapes such as annual ring-shaped CNT, single-wall CNT, and cup-stacked CNT may be mixed.
Moreover, CNT is not limited to two types, What is necessary is just to mix two or more types.
（複合金属体の製造方法）
上述したような、2種類以上のＣＮＴが混入された複合金属体を製造する製造方法について説明する。製造方法については、いくつかの方法が考えられる。
(Production method of composite metal body)
A manufacturing method for manufacturing a composite metal body mixed with two or more kinds of CNTs as described above will be described. Several methods can be considered for the manufacturing method.
（製造方法１）
図２に複合金属体の製造方法１について示す。
まず、2種類以上のＣＮＴと、金属粉とを混合する（ステップＳ１００）。
次に、2種類以上のＣＮＴと金属粉とを混合して成る混合物を所定の型に充填して成形する（ステップＳ１０２）。
成形した成形物を焼成または溶融する（ステップＳ１０４）。これにより、金属粉が結着し、2種類以上のＣＮＴが混入した複合金属体を得ることができる。
(Manufacturing method 1)
FIG. 2 shows a method 1 for producing a composite metal body.
First, two or more types of CNT and metal powder are mixed (step S100).
Next, a mixture obtained by mixing two or more types of CNTs and metal powder is filled into a predetermined mold and molded (step S102).
The molded product is fired or melted (step S104). Thereby, the metal powder is bound and a composite metal body in which two or more kinds of CNTs are mixed can be obtained.
場合によっては、２種類以上のＣＮＴと金属粉に加え、ステップＳ１００においてバインダーを混合させてもよい。バインダーを用いることにより、ステップＳ１０２の成形時にＣＮＴと金属粉との間の隙間を十分に埋めることができる。
バインダーとしては、樹脂バインダーまたは金属バインダーを用いることができる。樹脂バインダーを用いた場合には、ステップＳ１０４の焼成または溶融時に樹脂バインダーは飛散して消失する。
In some cases, a binder may be mixed in step S100 in addition to two or more types of CNT and metal powder. By using the binder, the gap between the CNT and the metal powder can be sufficiently filled at the time of molding in step S102.
As the binder, a resin binder or a metal binder can be used. When a resin binder is used, the resin binder scatters and disappears during firing or melting in step S104.
（製造方法２）
図３に複合金属体の製造方法２について示す。
この方法によれば、2種類以上のＣＮＴを用意しておき、これと溶融した金属とを混合させる（ステップＳ２００）だけで、複合金属体を得ることができる。
ただし、この方法によればＣＮＴをどのようにして均一に分散させるかが課題になると考えられる。
(Manufacturing method 2)
FIG. 3 shows a method 2 for producing a composite metal body.
According to this method, a composite metal body can be obtained simply by preparing two or more types of CNTs and mixing them with molten metal (step S200).
However, according to this method, it is considered how to uniformly disperse CNTs.
（製造方法３）
図４に複合金属体の製造方法３について示す。
本方法は、2種類以上のＣＮＴで修飾された金属粒子を用いて複合金属体を得る方法である。
まず、2種類以上のＣＮＴで修飾された金属粒子を所定の型に充填して成形する（ステップＳ３００）。
次いで、成形した成形物を焼成または溶融する（ステップＳ３０２）。これにより、金属粒子が結着し、2種類以上のＣＮＴが混入した複合金属体を得ることができる。
この方法によれば、ＣＮＴが均一に行き渡った複合金属体を製造できる。
なお、2種類以上のＣＮＴで修飾された金属粒子の製造方法については、後述する。
(Manufacturing method 3)
FIG. 4 shows a method 3 for producing a composite metal body.
This method is a method of obtaining a composite metal body using metal particles modified with two or more types of CNTs.
First, metal particles modified with two or more types of CNTs are filled into a predetermined mold and molded (step S300).
Next, the molded product is fired or melted (step S302). Thereby, the metal particle is bound and a composite metal body in which two or more kinds of CNTs are mixed can be obtained.
According to this method, a composite metal body in which CNTs are uniformly distributed can be manufactured.
A method for producing metal particles modified with two or more types of CNTs will be described later.
（製造方法４）
図５に複合金属体の製造方法４について示す。
まず、1種類のＣＮＴで修飾された金属粒子と、該金属粒子とは異なる種類のＣＮＴで修飾された金属粒子とを混合する（ステップＳ４００）。
次に、金属粒子が混合されて成る混合物を所定の型に充填して成形する（ステップＳ４０２）。
成形した成形物を焼成または溶融する（ステップＳ４０４）。これで、２種類以上のＣＮＴが混入した複合金属体を得ることができる。
この方法によっても、ＣＮＴが均一に行き渡った複合金属体を製造できる。
(Manufacturing method 4)
FIG. 5 shows a method 4 for producing a composite metal body.
First, metal particles modified with one type of CNT and metal particles modified with a type of CNT different from the metal particles are mixed (step S400).
Next, the mixture obtained by mixing the metal particles is filled into a predetermined mold and molded (step S402).
The molded product is fired or melted (step S404). Thus, a composite metal body in which two or more kinds of CNTs are mixed can be obtained.
This method can also produce a composite metal body in which CNTs are uniformly distributed.
（金属粒子およびその製造方法）
上述した複合金属体の製造方法３と製造方法４では、ＣＮＴが修飾された金属粒子を用いて複合金属体を製造することを説明したが、以下に2種類以上のＣＮＴで修飾された金属粒子とその製造方法について説明する。
なお、単一種類のＣＮＴで修飾された金属粒子とその製造方法については従来から特願２００３−４０３０８等で本発明者等が提案しているので、ここでは2種類以上のＣＮＴで修飾された金属粒子についてのみ説明する。
(Metal particles and manufacturing method thereof)
In the manufacturing method 3 and manufacturing method 4 of the composite metal body described above, it has been described that a composite metal body is manufactured using metal particles modified with CNTs. The metal particles modified with two or more types of CNTs are described below. The manufacturing method will be described.
In addition, since the present inventors have proposed in Japanese Patent Application No. 2003-40308 etc. about the metal particle modified with a single type of CNT and the method for producing the same, here it was modified with two or more types of CNT. Only the metal particles will be described.
本発明の金属粒子の製造方法は、２種類以上のＣＮＴを分散した電解液を電解して、カソード電極上に、ＣＮＴが混入した金属粒子を析出させる工程と、析出した金属粒子をカソード電極上から分離する工程を含んでいる。
分離した金属粒子を回収、洗浄、乾燥することによって所要の金属粒子を得ることができる。
The method for producing metal particles of the present invention includes a step of electrolyzing an electrolytic solution in which two or more types of CNTs are dispersed to deposit metal particles mixed with CNTs on the cathode electrode, and the deposited metal particles on the cathode electrode. A step of separating from.
The required metal particles can be obtained by collecting, washing and drying the separated metal particles.
電流密度や電解時間などの電解条件を調節することによって平均粒径数百ｎｍ〜数十μｍの範囲の金属粒子を析出させることができる。電流密度は粒径や生産性を考慮して最適値を選択する。
例えば銅の電解液の場合、電解槽に硫酸銅水溶液と硫酸を主成分とする電解液を入れ、2種類以上のカーボンナノチューブを電解液に入れる。
電解槽中ではアノード電極として電気銅を使用し、電解中の銅イオンの補給を行う。電解液への銅イオンの補給は、銅以外の金属、例えば鉛をアノード電極として使用し、外部から銅イオンを補給しても構わない。
場合によっては、電解中の電解液は撹拌装置により撹拌されると同時に、電解液濃度および成分量も所定の比率となるように制御する。
By adjusting electrolysis conditions such as current density and electrolysis time, metal particles having an average particle size in the range of several hundred nm to several tens of μm can be deposited. The optimum current density is selected in consideration of the particle size and productivity.
For example, in the case of a copper electrolytic solution, an electrolytic solution containing a copper sulfate aqueous solution and sulfuric acid as main components is placed in an electrolytic bath, and two or more types of carbon nanotubes are placed in the electrolytic solution.
In the electrolytic bath, electrolytic copper is used as the anode electrode to replenish copper ions during electrolysis. For supplying copper ions to the electrolytic solution, a metal other than copper, for example, lead may be used as the anode electrode, and copper ions may be supplied from the outside.
In some cases, the electrolytic solution being electrolyzed is stirred by the stirring device, and at the same time, the electrolytic solution concentration and the component amount are controlled to have a predetermined ratio.
また、２種類以上のＣＮＴを電解液中に分散させるために、有機化合物からなる分散剤を添加するか、あるいは超音波による振動を与えるとよい。分散剤としてはポリアクリル酸等を用いることができる。 Further, in order to disperse two or more types of CNTs in the electrolytic solution, it is preferable to add a dispersant made of an organic compound or to apply vibration by ultrasonic waves. A polyacrylic acid etc. can be used as a dispersing agent.
析出した金属粒子をカソード電極上から分離する場合、金属粒子が析出したカソード電極よりブレード等を用いて機械的に分離できる。 When the deposited metal particles are separated from the cathode electrode, they can be mechanically separated from the cathode electrode on which the metal particles are deposited using a blade or the like.
析出粒子の粒径や強度、およびカソード電極からの分離性を調整するため、電解液にチオ尿素、ゼラチン、タングステン、塩化物等の有機、無機化合物を添加してもよい。
カソード電極には、析出する金属（本実施例では銅）の密着性が悪く、析出粒子を分離しやすいニオブを使用すると好適である。カソード電極としてはニオブに限られることはなく、ステンレス鋼、チタン、タンタル、白金等を使用することができる。
またカソード電極の表面は析出する金属を粒子化するため表面を粗面化しておくことが望ましい。例えば、カソード電極の表面にカソード電極とは異なる金属材料から成る微小突起を形成するとよい。
In order to adjust the particle size and strength of the deposited particles and the separability from the cathode electrode, an organic or inorganic compound such as thiourea, gelatin, tungsten, or chloride may be added to the electrolytic solution.
For the cathode electrode, it is preferable to use niobium which has poor adhesion to the deposited metal (copper in this embodiment) and can easily separate the deposited particles. The cathode electrode is not limited to niobium, and stainless steel, titanium, tantalum, platinum or the like can be used.
Further, it is desirable that the surface of the cathode electrode is roughened in order to make the deposited metal into particles. For example, microprotrusions made of a metal material different from the cathode electrode may be formed on the surface of the cathode electrode.
生産される、2種類以上のＣＮＴで修飾された金属粒子の粒径は、カソード表面の微小突起の大きさと形状、電解電流密度などが相互に関連して決まる。
なお、金属粒子の金属の種類は銅に限定されるものではない。
The particle size of the metal particles modified with two or more types of CNTs to be produced is determined in relation to the size and shape of the microprojections on the cathode surface, the electrolytic current density, and the like.
Note that the metal type of the metal particles is not limited to copper.
上記のようにして得られる金属粒子は数百ｎｍ〜数十μｍの極めて微細なものであり、しかも各金属粒子に２種類以上のＣＮＴが混入している。したがって、これら金属粒子の集合体を焼成または溶融して得られる複合材料中には、２種類以上のＣＮＴが均一に混入されたものとなる。 The metal particles obtained as described above are extremely fine particles of several hundred nm to several tens of μm, and two or more kinds of CNTs are mixed in each metal particle. Therefore, two or more types of CNTs are uniformly mixed in the composite material obtained by firing or melting these aggregates of metal particles.
また、電解液へのＣＮＴの分散量、電解条件などを変えることによって、種々のＣＮＴの混入量、粒径の金属粒子が得られるから、これら金属粒子を焼成または溶融することによって得られる複合金属体中の各ＣＮＴ量も任意にコントロールすることが可能となる。
このような複合金属体は、２種類以上の各ＣＮＴの特質を生かして、摺動性が必要な軸受、高い電気伝導率が必要な電極や電気接点、高い熱伝導率の必要な放熱機構など、多様な用途に利用可能である。
In addition, by changing the amount of CNT dispersed in the electrolytic solution, electrolysis conditions, etc., various CNT mixing amounts and metal particles with particle sizes can be obtained, so composite metals obtained by firing or melting these metal particles The amount of each CNT in the body can also be arbitrarily controlled.
Such composite metal bodies make use of the characteristics of each of two or more types of CNTs, such as bearings that require slidability, electrodes and electrical contacts that require high electrical conductivity, and heat dissipation mechanisms that require high thermal conductivity. It can be used for various purposes.
以下、金属粒子の製造方法の実施例について説明する。
電解液
ＣｕＳＯ4・５Ｈ2Ｏ ４０ｇ／Ｌ
Ｈ2ＳＯ4 １００ｇ／Ｌ
ＣＮＴ（Ａ） ２．５ｇ／Ｌ
ＣＮＴ（Ｂ） ２．５ｇ／Ｌ
ポリアクリル酸分子量５０００ ０．０５ｇ／Ｌ
上記電解液を用いて、撹拌下、液温２５℃、２０Ａ／ｄｍ2の電流密度で１５分間電解を行った場合に、カソード電極の表面に析出した皮膜の走査型電子顕微鏡写真を図６に示す。
なお、ＣＮＴ（Ａ）とは、年輪状のもの（ＭＷＣＮＴ）で直径が１００〜３００ｎｍのものであり、ＣＮＴ（Ｂ）とは、カップスタック状のもので直径が１００〜２００ｎｍのものである。
図６に見られるように、粒径約１０μｍ程度の微細な球状の銅粒に2種類のＣＮＴが多数取り込まれた、Ｃｕ-ＣＮＴ複合物が形成されている。
これら複合物は、安定してカソード電極から分離し、粒子化できた。
Hereinafter, the Example of the manufacturing method of a metal particle is described.
Electrolyte CuSO 4 · 5H 2 O 40g / L
H 2 SO 4 100 g / L
CNT (A) 2.5g / L
CNT (B) 2.5g / L
Polyacrylic acid molecular weight 5000 0.05g / L
FIG. 6 shows a scanning electron micrograph of the film deposited on the surface of the cathode electrode when electrolysis is performed for 15 minutes with stirring at a liquid temperature of 25 ° C. and a current density of 20 A / dm 2 using the above electrolytic solution. Show.
The CNT (A) is an annual ring (MWCNT) having a diameter of 100 to 300 nm, and the CNT (B) is a cup stack having a diameter of 100 to 200 nm.
As seen in FIG. 6, a Cu—CNT composite is formed in which a large number of two types of CNTs are incorporated into fine spherical copper particles having a particle diameter of about 10 μm.
These composites could be stably separated from the cathode electrode and granulated.
電解液
ＣｕＳＯ4・５Ｈ2Ｏ ４０ｇ／Ｌ
Ｈ2ＳＯ4 １００ｇ／Ｌ
ＣＮＴ（Ｃ） ０．８ｇ／Ｌ
ＣＮＴ（Ｄ） ０．５ｇ／Ｌ
上記電解液を用いて、撹拌下、超音波発生器により超音波振動を与えつつ液温２５℃、４０Ａ／ｄｍ2の電流密度で１５分間電解を行った場合に、カソード電極の表面に析出した皮膜の走査型電子顕微鏡写真を図７に示す。超音波発生器として、超音波洗浄機（アズワン株式会社：ＵＳ−１）を使用した。
なお、ＣＮＴ（Ｃ）とは、シングルウォールカーボンナノチューブ（ＳＷＣＮＴ）で直径が１００〜３００ｎｍのものであり、ＣＮＴ（Ｄ）とは、カップスタック状のもので直径が１００〜２００ｎｍのものである。
図７に見られるように、粒径数十μｍ程度の微細な球状の銅粒に2種類のＣＮＴが多数取り込まれた、Ｃｕ-ＣＮＴ複合物が形成されている。
これら複合物は、安定してカソード電極から分離し、粒子化できた。
Electrolyte CuSO 4 · 5H 2 O 40g / L
H 2 SO 4 100 g / L
CNT (C) 0.8g / L
CNT (D) 0.5g / L
When electrolysis was performed for 15 minutes at a liquid temperature of 25 ° C. and a current density of 40 A / dm 2 while applying ultrasonic vibration with an ultrasonic generator with stirring using the above electrolytic solution, it was deposited on the surface of the cathode electrode. A scanning electron micrograph of the film is shown in FIG. As an ultrasonic generator, an ultrasonic cleaning machine (As One Corporation: US-1) was used.
CNT (C) is a single-wall carbon nanotube (SWCNT) having a diameter of 100 to 300 nm, and CNT (D) is a cup-stacked one having a diameter of 100 to 200 nm.
As can be seen in FIG. 7, a Cu—CNT composite is formed in which a large number of two types of CNTs are incorporated into fine spherical copper particles having a particle size of several tens of μm.
These composites could be stably separated from the cathode electrode and granulated.
以上本発明につき好適な実施例を挙げて種々説明したが、本発明はこの実施例に限定されるものではなく、発明の精神を逸脱しない範囲内で多くの改変を施し得るのはもちろんである。 While the present invention has been described in detail with reference to a preferred embodiment, the present invention is not limited to this embodiment, and it goes without saying that many modifications can be made without departing from the spirit of the invention. .
１０ 複合金属体
１２ 長大ＣＮＴ
１３ 短小ＣＮＴ
１４ 金属マトリクス
10 Composite metal body 12 Long CNT
13 Short CNT
14 Metal matrix
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| US8628746B2 (en) | 2007-04-12 | 2014-01-14 | Raytheon Company | System and method for dispersing nanostructures in a composite material |
| CN100463745C (en) * | 2007-06-13 | 2009-02-25 | 湖南大学 | Method for preparing copper-base composite particles of internal carbon-inlaid nano pipe |
| US8491292B1 (en) | 2007-07-31 | 2013-07-23 | Raytheon Company | Aligning nanomaterial in a nanomaterial composite |
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| DE102009054427B4 (en) * | 2009-11-25 | 2014-02-13 | Kme Germany Ag & Co. Kg | Method for applying mixtures of carbon and metal particles to a substrate, substrate obtainable by the method and its use |
| BR112012012525A2 (en) * | 2009-12-01 | 2019-09-24 | Applied Nanostructured Sols | electrical matrix composite materials containing carbon nanotube infused fiber materials and methods for their production |
| WO2011146151A2 (en) | 2010-02-02 | 2011-11-24 | Applied Nanostructured Solutions, Llc | Fiber containing parallel-aligned carbon nanotubes |
| US9017854B2 (en) | 2010-08-30 | 2015-04-28 | Applied Nanostructured Solutions, Llc | Structural energy storage assemblies and methods for production thereof |
| JP6118540B2 (en) | 2012-11-08 | 2017-04-19 | 新光電気工業株式会社 | Heat dissipation component and manufacturing method thereof |
| JP5876817B2 (en) * | 2012-12-04 | 2016-03-02 | 日信工業株式会社 | Heat resistant seal |
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| WO2016013219A1 (en) * | 2014-07-23 | 2016-01-28 | 日本ゼオン株式会社 | Plating solution and method for producing same, composite material, copper composite material, and method for producing same |
| JP6066007B1 (en) | 2016-05-10 | 2017-01-25 | 日立金属株式会社 | Method for producing purified copper and method for producing electric wire |
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