JP2010001569A - Granulated substance and method of manufacturing the same - Google Patents
Granulated substance and method of manufacturing the same Download PDFInfo
- Publication number
- JP2010001569A JP2010001569A JP2009222004A JP2009222004A JP2010001569A JP 2010001569 A JP2010001569 A JP 2010001569A JP 2009222004 A JP2009222004 A JP 2009222004A JP 2009222004 A JP2009222004 A JP 2009222004A JP 2010001569 A JP2010001569 A JP 2010001569A
- Authority
- JP
- Japan
- Prior art keywords
- granular material
- metal layer
- plated metal
- electrolytic plating
- carbon nanotube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
本発明は粒状物及びその製造方法に関し、更に詳細にはカーボンナノチューブから成る粒状物及びその製造方法に関する。 The present invention relates to a granular material and a manufacturing method thereof, and more particularly to a granular material made of carbon nanotubes and a manufacturing method thereof .
カーボンナノチューブ（以下、単にＣＮＴと称することがある）は、その剛性、電気伝導性及び伝熱性に優れている。このため、一般的に剛性、電気伝導性及び伝熱性に劣る樹脂等の材料に均一に分散配合できれば、樹脂等の材料の剛性、電気伝導性及び伝熱性を格段に改善できる。
しかし、ＣＮＴは凝集し易いため、単に樹脂等の材料に投入して混練したのみでは分散配合することは至難のことである。
一方、下記非特許文献１には、図９に示すＣＮＴと金属とから成り、ＣＮＴの端部がウニ状に突出した粒状物を、ＣＮＴを特殊な分散剤により分散した金属イオンを含有するめっき液に電流を流すことによって得ることができ、かかる粒状物を熱圧着して部品材料を形成することが提案されている。
Carbon nanotubes (hereinafter sometimes simply referred to as CNT) are excellent in rigidity, electrical conductivity, and heat conductivity. For this reason, if it can disperse and mix | blend uniformly with materials, such as resin generally inferior to rigidity, electrical conductivity, and heat conductivity, the rigidity, electrical conductivity, and heat conductivity of materials, such as resin, can be improved markedly.
However, since CNTs easily aggregate, it is very difficult to disperse and mix them simply by putting them into a material such as a resin and kneading them.
On the other hand, the following Non-Patent Document 1 includes a CNT and a metal shown in FIG. 9, and a granular material in which the end of the CNT protrudes in a sea urchin shape, containing metal ions obtained by dispersing CNT with a special dispersant. It can be obtained by passing an electric current through the liquid, and it has been proposed to thermocompress such a granular material to form a component material.
図９に示す粒状物を熱圧着して形成した部品材料をモータ軸や軸受に用いることによって、耐摩擦性及び放熱性を著しく向上でき、部品寿命の延長が期待できる。
しかし、図９に示す粒状物は、ＣＮＴの端部が金属層に覆われることなく露出状態でウニ状に突出しているものであり、粒状物自体の分散性が劣る。更に、ウニ状に突出したＣＮＴが露出状態であるため、樹脂との濡れ性が劣るものと考えられる。
このため、図９に示す粒状物を樹脂に均一分散しようとすると、粒状物の分散性が劣るものと考えられる。
そこで、本発明の課題は、粒状物自体の分散性が改善されたカーボンナノチューブから成る粒状物及びその製造方法を提案することにある。
By using the component material formed by thermocompression bonding of the granular material shown in FIG. 9 for the motor shaft and the bearing, it is possible to remarkably improve the friction resistance and the heat dissipation, and to expect an extension of the component life.
However, the granular material shown in FIG. 9 protrudes like a sea urchin in an exposed state without being covered with a metal layer, and the dispersibility of the granular material itself is inferior. Furthermore, since the CNT protruding in the shape of a sea urchin is in an exposed state, it is considered that the wettability with the resin is inferior.
For this reason, when it is going to disperse | distribute the granular material shown in FIG. 9 to resin uniformly, it is thought that the dispersibility of a granular material is inferior.
Accordingly, an object of the present invention is to propose a granular material composed of carbon nanotubes in which the dispersibility of the granular material itself is improved and a method for producing the same.
本発明者等は、前記課題を解決すべく、先ず、無電解めっきによってＣＮＴにめっき金属を形成せんと試みたところ、周面全面が薄層のめっき金属層で覆われた薄層ＣＮＴを得ることができた。
しかしながら、ＣＮＴの全周面を薄層のめっき金属層で覆うための時間は長時間かかり、形成された薄層のめっき金属層は均一層であって、その表面は平滑面であるため、樹脂に配合した薄層ＣＮＴは樹脂から剥離し易い。
次に、本発明者は、電解めっきによってＣＮＴにめっき金属を形成せんと試みたところ、ＣＮＴの端部が露出状態でウニ状に突出することなく粒状物を形成できること、電解めっき条件を変更することによって粒状物の形状を変更できることを見出し、本発明に到達した。
In order to solve the above-mentioned problems, the present inventors first tried to form a plating metal on the CNTs by electroless plating. As a result, thin CNTs whose entire peripheral surface was covered with a thin plating metal layer were obtained. I was able to.
However, it takes a long time to cover the entire circumferential surface of the CNT with the thin plated metal layer, and the formed thin plated metal layer is a uniform layer and the surface thereof is a smooth surface. The thin-walled CNT blended in is easily peeled from the resin.
Next, the present inventor tried to form a plating metal on the CNTs by electrolytic plating. As a result, the end of the CNTs can be formed in an exposed state without protruding into a sea urchin, and the electrolytic plating conditions are changed. As a result, the inventors have found that the shape of the granular material can be changed, and have reached the present invention.
すなわち、本発明は、表面の少なくとも一部が電解めっき金属層によって被覆された一本又は複数本のカーボンナノチューブによって形成されていることを特徴とする粒状物にある。
かかる本発明において、カーボンナノチューブの長手方向に、間欠的に電解めっき金属層を形成することによって、カーボンナノチューブ同士がめっき金属を介することなく直接接触することができ、電解めっき金属を介して接触する場合に比較して、電気伝導性や伝熱性を向上できる。
しかも、このカーボンナノチューブ間に隙間が形成されるため、粒状物を樹脂に含浸する際に、かかる隙間に樹脂が入り込みアンカー効果を奏することも期待できる。この間欠的に形成されている電解めっき金属層としては、球形であることが好ましい。
一方、カーボンナノチューブの全表面を電解めっき金属層によって被覆することによって、粒状物と樹脂との親和性を向上でき、樹脂に対する耐剥離性を向上できる。このカーボンナノチューブを覆う電解めっき金属層の表面を凹凸状に形成すること、或いはカーボンナノチューブの端部の少なくとも一方を被覆する電解めっき金属層を、他の部分を被覆する電解めっき金属層よりも厚く形成することが好ましい。
かかる電解めっき金属層を、磁性を有する金属とすることによって、粒状物を磁石によって容易に回収できる。
尚、複数本のカーボンナノチューブを、電解めっき金属層によって相互に固着することによって、粒状物の粒径を大きくできる。
That is, the present invention is particle-like material you characterized in that at least a part is formed by one or a plurality of carbon nanotubes coated with electroless plated metal layer on the surface.
In the present invention, by intermittently forming the electroplated metal layer in the longitudinal direction of the carbon nanotubes, the carbon nanotubes can directly contact each other without interposing the plated metal, and contact through the electroplated metal. Compared to the case, electrical conductivity and heat transfer can be improved.
In addition, since a gap is formed between the carbon nanotubes, when the granular material is impregnated with the resin, it can be expected that the resin enters the gap and has an anchor effect. The intermittently formed electroplated metal layer is preferably spherical.
On the other hand, by covering the entire surface of the carbon nanotube with the electroplated metal layer, the affinity between the granular material and the resin can be improved, and the peel resistance to the resin can be improved. The surface of the electroplating metal layer covering the carbon nanotubes is formed in an uneven shape, or the electroplating metal layer covering at least one of the ends of the carbon nanotubes is thicker than the electroplating metal layer covering the other part. It is preferable to form.
By making the electroplated metal layer a metal having magnetism, the particulate matter can be easily recovered with a magnet.
In addition, the particle size of a granular material can be enlarged by mutually adhering a plurality of carbon nanotubes with an electroplating metal layer.
また、本発明は、分散剤を添加した電解めっき液中に複数本のカーボンナノチューブを分散させた後、前記カーボンナノチューブに電解めっきを施し、表面の少なくとも一部を電解めっき金属層によって被覆したカーボンナノチューブから成る粒状物を得ることを特徴とする粒状物の製造方法にある。
かかる本発明において、分散剤として、アルキンジオール分子中にオキシエチレン側鎖を有するアルキンジオール化合物又はカチオン活性剤を好適に用いることができる。
更に、電解めっきを電解めっき液中に浸漬した陽極と陰極とに電流を流して施し、その際に、前記陰極面にカーボンナノチューブを付着して、前記カーボンナノチューブの表面に電解めっき金属を析出させることによって、カーボンナノチューブの表面に電解めっきによる金属層の被覆を形成できる。
また、複数本のカーボンナノチューブ同士を、電解めっきによる金属層によって相互に固着して粒状物とすることによって、得られた粒状物の粒径を大きくできる。
Further, the present invention provides a carbon in which a plurality of carbon nanotubes are dispersed in an electrolytic plating solution to which a dispersant is added, and then the carbon nanotubes are subjected to electrolytic plating, and at least a part of the surface is covered with an electrolytic plating metal layer. The present invention resides in a method for producing a granular material characterized by obtaining a granular material comprising nanotubes .
In the present invention, an alkynediol compound having a oxyethylene side chain in the alkynediol molecule or a cationic activator can be suitably used as the dispersant.
Further, the electroplating is applied by passing an electric current through an anode and a cathode immersed in an electroplating solution. At this time, carbon nanotubes are attached to the cathode surface, and an electroplating metal is deposited on the surface of the carbon nanotubes. As a result, the coating of the metal layer by electrolytic plating can be formed on the surface of the carbon nanotube.
Moreover, the particle diameter of the obtained granular material can be enlarged by mutually adhering a plurality of carbon nanotubes by the metal layer by electroplating, and making it a granular material.
本発明に係る粒状物は、特定の分散剤を用いてＣＮＴを分散した電解めっき液を用いた電解めっきによって容易に得ることができ、電解めっき条件を調整することによって、種々の粒状物を得ることができる。
得られた粒状物は、ＣＮＴの各端部が粒状物の外方に露出状態でウニ状に突出することなく形成され、その分散性はいずれも良好である。
このため、得られた粒状物を樹脂に添加して攪拌や混練によって、樹脂中に容易に分散可能である。
The granular material according to the present invention can be easily obtained by electrolytic plating using an electrolytic plating solution in which CNTs are dispersed using a specific dispersant, and various granular materials are obtained by adjusting the electrolytic plating conditions. be able to.
The resulting particle Jobutsu is formed without the end portions of the CNT protrudes sea urchin shape in exposed state to the outside of the particle, the dispersibility of that are both good.
For this reason, it can disperse | distribute easily in resin by adding the obtained granular material to resin and stirring and kneading | mixing.
本発明において用いるカーボンナノチューブは、公知のカーボンナノチューブを用いることができ、具体的にはシングルウォールカーボンナノチューブ又はマルチウォールカーボンナノチューブを用いることができる。
かかるカーボンナノチューブ（ＣＮＴ）から成る本発明に係る粒状物の一例を図１に示す。図１は、複数本のＣＮＴから成る塊状の粒状物の電子顕微鏡写真である。図１において、線状物がＣＮＴであって、ＣＮＴの所々に形成された白い球状物がめっき金属層としてのニッケル層である。
図１から明らかな様に、図１に示す粒状物は、金属層で覆われていないＣＮＴの端部が粒状物の外方にウニ状に突出することなく形成されており、ＣＮＴの各表面に間欠的に形成された球状のニッケル層によってＣＮＴ同士が相互に固着されていると共に、ＣＮＴ間には隙間が形成されている。
As the carbon nanotube used in the present invention, a known carbon nanotube can be used, and specifically, a single wall carbon nanotube or a multi-wall carbon nanotube can be used.
An example of the granular material according to the present invention comprising such carbon nanotubes (CNT) is shown in FIG. Figure 1 is an electron microscopic photograph of granules of bulk comprising a plurality of CNT. In FIG. 1, the linear object is CNT, and the white spherical object formed in the CNT is a nickel layer as a plating metal layer.
As is apparent from FIG. 1, shown to particle Jobutsu 1 is formed without the end of the CNT not covered with the metal layer projects into sea urchin-like outside the granules, the CNT The CNTs are fixed to each other by a spherical nickel layer intermittently formed on each surface, and a gap is formed between the CNTs.
これに対し、図２に示すＣＮＴから成る塊状の粒状物も、金属層で覆われていないＣＮＴの端部が粒状物の外方にウニ状に突出することなく形成されているが、粒状物の外周面は、めっき金属層としてのニッケル層によって覆われている。
更に、かかる図２に示す粒状物の外周面を観察すると、外周面近傍のＣＮＴは、その実質的全面が凹凸状表面のニッケル層によって覆われており、このＣＮＴの端部の少なくとも一方を覆うニッケル層がＣＮＴの側面を覆うニッケル層よりも厚く形成されている。
この様に、図１及び図２に示す粒状物は、ＣＮＴの端部が粒状物の外方に露出状態でウニ状に突出することなく形成されているため、粒状物自体の分散性は良好である。
また、かかる粒状物を樹脂に含浸させることによって、剛性に優れたＣＮＴを樹脂中に分散して配設できるため、樹脂の剛性や電気特性を改善できる。
In contrast, granules bulk consisting CNT shown in FIG. 2 also have been formed without the end portions of the CNT not covered with the metal layer projects into sea urchin-like outside the granules, the particle shape The outer peripheral surface of the object is covered with a nickel layer as a plating metal layer.
Furthermore, when observing the outer peripheral surface of the take 2 shown to the grain-like material, CNT of the outer peripheral surface near its substantially entire surface is covered by a nickel layer of uneven surfaces, at least one end of the CNT The nickel layer covering the CNTs is formed thicker than the nickel layer covering the side surfaces of the CNTs.
Thus, shown to particle Jobutsu in FIGS. 1 and 2, since it is formed without the end of the CNT protrudes sea urchin shape in exposed state to the outside of the particle, dispersion of the grain-like material itself The property is good.
Further, a particle-like material that written by impregnating the resin, the CNT has excellent rigidity because it disposed dispersed in a resin can improve the rigidity and electrical properties of the resin.
ところで、図１に示す粒状物は、ＣＮＴ同士がニッケル層を介することなく直接接触する部分が存在する。このため、図１に示す粒状物は、電気伝導性及び伝熱性がニッケルよりも優れたにＣＮＴ同士が直接接触するため、ニッケル層を介してＣＮＴ同士が接触する図２に示す粒状物に比較して、その電気伝導性及び伝熱性が良好である。
更に、図１に示す粒状物は、ＣＮＴ間に隙間が形成されているため、樹脂に含浸する際に、かかる隙間に樹脂が入り込みアンカー効果を奏することも期待できる。
一方、図２に示す粒状物は、その全面がニッケル層によって覆われているため、樹脂との濡れ性が、部分的にニッケル層が形成されている図１に示す粒状物に比較して良好であり、樹脂への分散性を向上できる。
尚、図１及び図２に示す粒状物の大きさは、１０〜３０μｍである。
Incidentally, it is shown to particle Jobutsu in FIG. 1, CNT each other there is direct contact with the portion without passing through the nickel layer. Therefore, shown to particle Jobutsu in FIG. 1, the electric conductivity and heat conductivity is CNT contact each other directly to better than nickel, shown to grains in Figure 2 the CNT come into contact with each other through the nickel layer The electrical conductivity and heat transfer properties are better than those of the product.
Further, it is shown to particle Jobutsu in FIG. 1, since it is a gap is formed between the CNT, when impregnated with the resin, can be expected to exhibit the anchoring effect resin enters the take gap.
On the other hand, indicates to particle Jobutsu in FIG. 2, since the entire surface is covered by a nickel layer, the wettability of the resin is partially shown to the particle-like material in Figure 1, the nickel layer is formed Compared to this, it is good and the dispersibility in the resin can be improved.
The size of the shown to particle-like material in Figures 1 and 2 are 10 to 30 [mu] m.
かかる図１及び図２に示す粒状物は、複数本のＣＮＴが塊状に固まって形成されているものであるが、図３及び図４に示す粒状物の様に、複数本のＣＮＴによって形成された線状体を含有する粒状物であってもよい。この粒状物を形成するＣＮＴの各表面には、めっき金属層としてのニッケル層が形成されている
かかる粒状物の一例を、図３（ａ）（ｂ）に示す、図３（ｂ）は、図３（ａ）に示す線状粒状物の拡大顕微鏡写真である。図３（ａ）に示す粒状物には、図３（ｂ）に示す複数本のＣＮＴが線状に繋がって形成された線状体を含有しており、ＣＮＴの長手方向に球状のめっき金属層としてのニッケル層が間欠的に形成されていると共に、電解めっき金属間にＣＮＴの表面が露出している。
図３（ａ）（ｂ）に示す粒状物は、ＣＮＴ同士がニッケル層を介することなく直接接触する部分が存在するため、電気伝導性及び伝熱性がニッケルよりも優れたにＣＮＴ同士が直接接触し、その電気伝導性及び伝熱性が良好である。
Granules shown in such Figures 1 and 2, but in which a plurality of CNT is formed solidified in bulk, as a granulate 3 and 4, formed by CNT of several double The granular material containing the made linear body may be sufficient. Each surface of the CNT to form grain shape of this, an example of a particle-like material that embarking nickel layer as a plating metal layer is formed, shown in FIG. 3 (a) (b), FIG. 3 (B) is an enlarged photomicrograph of the linear granular material shown in FIG. The granular material shown in FIG. 3 (a) contains a linear body formed by connecting a plurality of CNTs shown in FIG. 3 (b) in a linear form, and a spherical plated metal in the longitudinal direction of the CNTs. The nickel layer as a layer is intermittently formed, and the surface of the CNT is exposed between the electroplated metals .
Shown to particle Jobutsu in FIG 3 (a) (b), since the CNT each other there is direct contact with the portion without using a nickel layer, is CNT between the electrical conductivity and heat conductivity is better than nickel Direct contact, good electrical conductivity and heat transfer.
また、ＣＮＴを含有する粒状体の他の例を図４及び図５に示す。図５は、図４の粒状物の拡大断面図である。かかる図４に示す粒状物は、ＣＮＴ１０の全面がめっき金属層としてのニッケル層１２によって覆われている。このニッケル層１２のうち、ＣＮＴ１０の側面を覆う部分は、多数の凹凸が形成されて凹凸状表面に形成されている。
他方、ＣＮＴ１０の端部を覆う部分は、図５（ａ）に示す様に、単一のＣＮＴ１０の端部の一方が、ＣＮＴ１０の側面を覆うニッケル層１２よりも厚く形成されているものと、図５（ｂ）に示す様に、単一のＣＮＴ１０の両端部が、共にＣＮＴ１０の側面を覆うニッケル層１２よりも厚く形成されているものとが存在する。
この様に、ＣＮＴ１０の実質的全面がニッケル層１２によって覆われている図４及び図５（ａ）（ｂ）に示す粒状物は、樹脂との濡れ性が、部分的にニッケル層が形成されている図３（ａ）（ｂ）に示す粒状物に比較して良好であり、樹脂への分散性を向上できる。
更に、ＣＮＴ１０を覆うニッケル層１２は、その表面が凹凸状面に形成されているため、ニッケル層１２の凹凸状表面による樹脂とのアンカー効果も期待できる。
尚、ＣＮＴの表面にめっき金属層が形成された図１〜図５に示す粒状物を樹脂に配合することによって、樹脂に優れた電磁波の遮断性を付与できる。
Moreover, the other example of the granular material containing CNT is shown in FIG.4 and FIG.5 . Figure 5 is an enlarged sectional view of a particle-like material in FIG. Shown to particle Jobutsu in such Figure 4, the entire surface of the C NT10 is covered by a nickel layer 12 as a plated metal layer. A portion of the nickel layer 12 that covers the side surface of the CNT 10 is formed on a concavo-convex surface with a large number of concavo-convex portions.
On the other hand, as shown in FIG. 5A, the part covering the end of the CNT 10 is such that one end of the single CNT 10 is formed thicker than the nickel layer 12 covering the side surface of the CNT 10. As shown in FIG. 5B, there is a case where both ends of a single CNT 10 are formed thicker than the nickel layer 12 that covers the side surfaces of the CNT 10.
Thus, FIGS. 4 and shown to particle Jobutsu in FIG 5 (a) (b) substantially the entire surface of the CNT10 is covered by a nickel layer 12, wettability with resins, partially nickel layer 3 which is formed (a) (b) as compared to the shown to particle-like material is good, it is possible to improve the dispersibility in the resin.
Furthermore, since the surface of the nickel layer 12 covering the CNT 10 is formed in a concavo-convex surface, an anchor effect with the resin due to the concavo-convex surface of the nickel layer 12 can also be expected.
In addition, the resin can be provided with excellent electromagnetic wave shielding properties by blending the resin shown in FIGS.
図１〜図５に示す粒状物は、図６に示す電解装置によって得ることができる。図６に示す電解装置は、電解めっき槽１４に貯留されて攪拌機２４によって攪拌されている電解めっき液１６に、直流電源１８に接続された陽極２０と陰極２２とが浸漬されている。陽極２０は、ＣＮＴ１０の表面に析出させたい金属から成る金属部材を用いる。
かかる電解めっき液１６にＣＮＴ１０が分散されており、めっき金属が析出したＣＮＴ１０から成る粒状物は、陰極２２の表面に析出すると共に、電解めっき液１６中に浮遊し、電解めっき槽１４の底面にも沈殿する。
The granular material shown in FIGS. 1 to 5 can be obtained by the electrolysis apparatus shown in FIG. In the electrolysis apparatus shown in FIG. 6, an anode 20 and a cathode 22 connected to a DC power source 18 are immersed in an electroplating solution 16 stored in an electroplating tank 14 and stirred by a stirrer 24. For the anode 20, a metal member made of a metal to be deposited on the surface of the CNT 10 is used.
The CNT 10 is dispersed in the electrolytic plating solution 16, and the particulate matter composed of the CNT 10 on which the plating metal is deposited is deposited on the surface of the cathode 22, floats in the electrolytic plating solution 16, and is deposited on the bottom surface of the electrolytic plating tank 14. Also precipitate.
かかる電解めっき液１６には、ＣＮＴ１０を電解めっき液１６に充分に分散することが肝要である。このためには、分散剤として、アルキンジオール分子中にオキシエチレン側鎖を有するアルキンジオール化合物であって、このアルキンジオール化合物の分子量の少なくとも２０重量％をオキシエチレン側鎖が占める分散剤を用いることによって、ＣＮＴを電解めっき液１６に充分に分散できる。
或いは、分散として、カチオン活性剤から成る分散剤、特に炭化水素系のカチオン活性剤とフッ素化水素系のカチオン活性剤とから成る分散剤も用いることができる。
この様な分散剤を用いることのできる電解めっき液であれば、ＣＮＴの表面に所望の金属を析出し得る公知の電解めっき液を用いることができ、例えばニッケルをＣＮＴの表面に析出し得る電解めっき液としては、ワット浴を用いることができる。
尚、界面活性剤としても、公知の界面活性剤を用いることができる。
It is important that the CNT 10 is sufficiently dispersed in the electrolytic plating solution 16 in the electrolytic plating solution 16. For this purpose, an alkyne diol compound having an oxyethylene side chain in the alkyne diol molecule is used as the dispersant, and the dispersant occupies at least 20% by weight of the molecular weight of the alkyne diol compound. Thus, CNT can be sufficiently dispersed in the electrolytic plating solution 16.
Alternatively, as a dispersion, a dispersant composed of a cationic activator, particularly a dispersant composed of a hydrocarbon-based cationic activator and a hydrogen fluoride-based cationic activator can also be used.
As long as the electrolytic plating solution can use such a dispersant, a known electrolytic plating solution capable of depositing a desired metal on the surface of the CNT can be used. For example, electrolysis capable of depositing nickel on the surface of the CNT. A watt bath can be used as the plating solution.
A known surfactant can also be used as the surfactant.
かかる電解めっき液１６を用いた電解めっきの際に、電解めっきの電流密度を、３Ａ／ｄｍ2以上とすることが好ましく、図２及び図４に示す様に、ＣＮＴの全面にめっき金属を形成する場合には、電流密度を１０Ａ／ｄｍ2以上とすることが好ましい。
この電解めっきによって生成した粒状物は、陰極２２の表面に析出すると共に、電解めっき液１６中に浮遊し、電解めっき槽１４の底面にも沈殿するため、電解めっき液１６を電解めっき槽１４の底面に沈殿した粒状物と共にスポイト等によって吸引し、粒状物を沈殿させることによって得ることができる。粒状物は、ＣＮＴの表面にめっき金属が形成されており、その比重は電解めっき液１６よりも大きく容易に沈殿するからである。
この様に、粒状物の比重が電解めっき液１６よりも大きいため、電解めっきを所定時間継続して終了した後、攪拌機２４による攪拌を停止することによって、電解めっき液１６に浮遊している粒状物は電解めっき槽１４の底面に容易に沈殿し、生成した粒状物を容易に回収できる。
また、陰極２２に析出する粒状物は、陰極２２の表面をフッ素樹脂製のヘラ等によって削ぎ落として回収できる。かかる削ぎ落としを、電解めっき中に定期的に行なうことによって、陰極表面に付着した粒状物が形成されることを防止できる。
尚、めっき金属として、ニッケル等の磁性を有する金属を用いた場合には、電解めっき槽１４の底面に沈殿した粒状物を磁石によって容易に回収できる。
In the electrolytic plating using the electrolytic plating solution 16, it is preferable that the current density of the electrolytic plating is 3 A / dm 2 or more. As shown in FIGS. 2 and 4, a plated metal is formed on the entire surface of the CNT. In this case, the current density is preferably 10 A / dm 2 or more.
The particulate matter generated by the electrolytic plating is deposited on the surface of the cathode 22, floats in the electrolytic plating solution 16, and also settles on the bottom surface of the electrolytic plating bath 14. It can be obtained by sucking with a dropper together with the particulate matter precipitated on the bottom surface to precipitate the particulate matter. This is because the granular material has a plated metal formed on the surface of the CNT, and its specific gravity is larger than that of the electrolytic plating solution 16 and easily precipitates.
As described above, since the specific gravity of the granular material is larger than that of the electrolytic plating solution 16, the electrolytic plating is continued for a predetermined time, and then the stirring by the stirrer 24 is stopped, whereby the particulate floating in the electrolytic plating solution 16. The product easily settles on the bottom surface of the electrolytic plating tank 14, and the generated granular material can be easily recovered.
The particulate matter deposited on the cathode 22 can be recovered by scraping off the surface of the cathode 22 with a spatula made of fluororesin. By periodically carrying out such scraping during the electroplating, it is possible to prevent the formation of granular materials attached to the cathode surface.
In addition, when a metal having magnetism such as nickel is used as the plating metal, the particulate matter precipitated on the bottom surface of the electrolytic plating tank 14 can be easily recovered with a magnet.
この様に、電解めっきによってＣＮＴにめっき金属層を形成できるメカニズムは、図７に示すように考えることができる。
すなわち、陽極２０と陰極２２との間に存在するＣＮＴ１０が分極化され、分極化されたＣＮＴ１０の一端部が、図７（ａ）に示す様に、陰極２２の陰極面に引き寄せられて付着する。陰極２２に一端部が付着したＣＮＴ１０は、その他端部の電流密度が他の部分よりも高くなるため、めっき金属が集中的に析出し、図７（ｂ）に示す様に、ＣＮＴ１０の先端部に厚いめっき金属層１２が形成される。
形成されためっき金属層１２の先端部には、図７（ｃ）に示す様に、分極化されたＣＮＴ１０が付着する。この様に、新たなＣＮＴ１０が付着すると、新たに付着したＣＮＴ１０の先端部が最も電流密度が高くなるため、図７（ｄ）に示す様に、新たに付着したＣＮＴ１０にめっき金属が集中的に析出する。
Thus, the mechanism by which the plated metal layer can be formed on the CNTs by electrolytic plating can be considered as shown in FIG.
That is, the CNT 10 existing between the anode 20 and the cathode 22 is polarized, and one end of the polarized CNT 10 is attracted to and attached to the cathode surface of the cathode 22 as shown in FIG. . In the CNT 10 having one end attached to the cathode 22, the current density at the other end is higher than that at the other part, so that the plating metal is concentrated, and as shown in FIG. A thick plated metal layer 12 is formed.
As shown in FIG. 7C, polarized CNTs 10 adhere to the tip of the formed plated metal layer 12. Thus, when new CNT 10 adheres, the tip of the newly attached CNT 10 has the highest current density. Therefore, as shown in FIG. 7D, the plating metal is concentrated on the newly attached CNT 10. Precipitate.
ここで、陰極２２の陰極面にＣＮＴ１０が高密度に付着する場合には、めっき金属１２が付着する際に、隣接するＣＮＴ１０のめっき金属１２と接合され易くなり、塊状の粒状物が形成され易い。
他方、陰極２２の陰極面に付着するＣＮＴ１０の密度が比較的低い場合には、隣接するＣＮＴ１０のめっき金属１２と接合され難くなり、線状体を含む粒状物が形成され易い。
また、電流密度が高く、陰極面に付着したＣＮＴ１０にめっき金属１２が析出し易い場合には、陰極面に付着したＣＮＴ１０の全面がめっき金属層１２によって覆われた後、新たなＣＮＴ１０が付着するため、全面がめっき金属層１２で覆われたＣＮＴ１０から成る粒状物が形成され易くなる。
他方、電流密度が低い場合には、陰極面に付着したＣＮＴ１０の全面がめっき金属層１２によって覆われる前に、ＣＮＴ１０の先端部を覆うめっき金属層１２に新たなＣＮＴ１０が付着し、新たなＣＮＴ１０の先端部にめっき金属が析出する。このため、ＣＮＴ１０に間欠的にめっき金属層１２が形成された粒状物が形成され易くなる。
Here, when the CNT10 the cathode surface of the cathode 22 is adhered at a high density, when the plating metal 12 is attached, becomes easier to be bonded to the plating metal 12 adjacent CNT10, particle-like material in bulk is formed easy.
On the other hand, when the density of the CNTs 10 adhering to the cathode surface of the cathode 22 is relatively low, it becomes difficult to be joined to the plating metal 12 of the adjacent CNTs 10 and a granular material including a linear body is easily formed.
In addition, when the current density is high and the plating metal 12 is likely to be deposited on the CNT 10 attached to the cathode surface, new CNT 10 is attached after the entire surface of the CNT 10 attached to the cathode surface is covered with the plating metal layer 12. Therefore, a granular material made of CNT 10 whose entire surface is covered with the plated metal layer 12 is easily formed.
On the other hand, when the current density is low, before the entire surface of the CNT 10 attached to the cathode surface is covered with the plated metal layer 12, new CNT 10 is attached to the plated metal layer 12 covering the tip of the CNT 10, and the new CNT 10 The plated metal is deposited on the tip of the plate. For this reason, it becomes easy to form a granular material in which the plated metal layer 12 is intermittently formed on the CNT 10.
ところで、図７では、陰極２２の陰極面に付着するＣＮＴ１０の一端部が付着した場合について説明したが、この場合、全面がめっき金属層１２によって覆われたＣＮＴ１０は、図５（ａ）に示す様に、その端部の一方が側面を覆うニッケル層１２よりも厚く形成され易くなる。
他方、図８に示す様に、陰極２２の陰極面に湾曲したＣＮＴ１０の側面が付着した場合、全面がめっき金属層１２によって覆われたＣＮＴ１０は、図５（ｂ）に示す様に、その両端部が側面を覆うニッケル層１２よりも厚く形成され易くなる。
By the way, although FIG. 7 demonstrated the case where the one end part of CNT10 adhering to the cathode surface of the cathode 22 adhered, in this case, CNT10 with which the whole surface was covered with the plating metal layer 12 is shown to Fig.5 (a). Similarly, one of the end portions is easily formed thicker than the nickel layer 12 covering the side surface.
On the other hand, as shown in FIG. 8, when the side surface of the curved CNT 10 adheres to the cathode surface of the cathode 22, the entire surface of the CNT 10 covered with the plated metal layer 12 has both ends as shown in FIG. The portion is more easily formed thicker than the nickel layer 12 covering the side surface.
攪拌機が設けられ、下記表１の組成の電解めっき液が貯留されている電解めっき槽に、陽極としてのニッケル板と陰極としての銅板とを挿入し、この電解めっき液にＣＮＴとしてマルチウォールカーボンナノチューブ（ＭＷＣＮＴ）１ｇ／リットルを添加した。
次いで、電解めっき液を攪拌機で攪拌しつつ、電解めっきを施した。この際の電流密度は５Ａ／ｄｍ2であった。
回収した粒状物を電子顕微鏡で観察したところ、図１に示す様に、塊状の粒状物であって、ニッケル層で覆われていないＭＷＣＮＴの端部が粒状物の外方にウニ状に突出することなく形成されており、ＭＷＣＮＴの各表面に間欠的に形成された球状のニッケル層によってＣＮＴ同士が相互に固着されていると共に、ＭＷＣＮＴ間には隙間が形成されているものであった。
A nickel plate as an anode and a copper plate as a cathode are inserted into an electrolytic plating tank in which an agitator is provided and an electrolytic plating solution having the composition shown in Table 1 below is stored. (MWCNT) 1 g / liter was added.
Next, electrolytic plating was performed while stirring the electrolytic plating solution with a stirrer. The current density at this time was 5 A / dm 2 .
The collected granules were observed by an electron microscope, as shown in FIG. 1, a particle shape of lump, protruding sea urchin-like outward end of MWCNT not covered with a layer of nickel granules The CNTs are formed on each surface of the MWCNTs, and the CNTs are fixed to each other by a spherical nickel layer intermittently formed on each surface of the MWCNTs, and a gap is formed between the MWCNTs.
実施例１において、分散剤として、分子量の８０wt％をオキシエチレン側鎖が占めるアルキンジオール化合物を用い、その添加量を２ｇ／リットルに変更し、且つ電流密度が１０Ａ／ｄｍ2の電解めっきを１５分間実施した他は、実施例１と同様にしてＭＷＣＮＴに電解めっきを施し、電解めっき槽の底面に沈殿した粒状物を回収した。
回収した粒状物を電子顕微鏡で観察したところ、図２に示す様に、塊状の粒状物であって、ニッケル層で覆われていないＭＷＣＮＴの端部が粒状物の外方にウニ状に突出することなく形成されおり、塊状の粒状物の外周面は、ニッケル層によって覆われている。
更に、外周面近傍のＭＷＣＮＴは、その全面が凹凸状表面のニッケル層によって覆われており、このＣＮＴの端部を覆うニッケル層がＭＷＣＮＴの他の部分を覆うニッケル層よりも厚く形成されている。
In Example 1, an alkynediol compound in which 80% by weight of the molecular weight is occupied by the oxyethylene side chain is used as the dispersant, the amount added is changed to 2 g / liter, and electroplating with a current density of 10 A / dm 2 is applied to 15 The MWCNT was subjected to electrolytic plating in the same manner as in Example 1 except that it was carried out for a minute, and the particulate matter precipitated on the bottom of the electrolytic plating tank was recovered.
The collected granules were observed by an electron microscope, as shown in FIG. 2, a particle shape of lump, protruding sea urchin-like outward end of MWCNT not covered with a layer of nickel granules and it is formed without the outer circumferential surface of the particle-like material in bulk is covered by a nickel layer.
Further, the entire surface of the MWCNT near the outer peripheral surface is covered with a nickel layer having a concavo-convex surface, and the nickel layer covering the end of the CNT is formed thicker than the nickel layer covering the other part of the MWCNT. .
実施例１において、電流密度を３Ａ／ｄｍ2の電解めっきを３０分間実施した他は、実施例１と同様にしてＭＷＣＮＴに電解めっきを施し、電解めっき槽の底面に沈殿した粒状物を回収した。
回収した粒状物を電子顕微鏡で観察したところ、図３（ａ）に示す粒状物には、図３（ｂ）に示す複数本のＭＷＣＮＴが線状に繋がって形成された線状体が含まれており、ＭＷＣＮＴの長手方向に球状のニッケル層が間欠的に形成されていた。
In Example 1, except that electroplating at a current density of 3 A / dm 2 was performed for 30 minutes, MWCNT was electroplated in the same manner as in Example 1, and the particulate matter precipitated on the bottom surface of the electroplating tank was collected. .
When the collected particulate matter was observed with an electron microscope, the particulate matter shown in FIG. 3A includes a linear body formed by connecting a plurality of MWCNTs shown in FIG. The spherical nickel layer was intermittently formed in the longitudinal direction of MWCNT.
実施例１において、電解めっき液を下記表２に示す組成の電解めっき液に、ＭＷＣＮＴを０．１ｇ／リットル添加した後、電流密度を１０Ａ／ｄｍ2の電解めっきを５分間実施した他は、実施例１と同様にしてＭＷＣＮＴに電解めっきを施し、電解めっき槽の底面に沈殿した粒状物を回収した。
また、ＭＷＣＮＴ１０の端部の一方を覆うニッケル層１２の部分が、ＭＷＣＮＴ１０の側面を覆うニッケル層１２よりも厚く形成されているものと、ＭＷＣＮＴ１０の両端部を覆うニッケル層１２の部分が、ＭＷＣＮＴ１０の側面を覆うニッケル層１２よりも厚く形成されているものとが混在されていた。
In Example 1, except that 0.1 g / liter of MWCNT was added to the electrolytic plating solution having the composition shown in Table 2 below, and then electroplating at a current density of 10 A / dm 2 was performed for 5 minutes. In the same manner as in Example 1, the MWCNT was subjected to electrolytic plating, and the particulate matter precipitated on the bottom surface of the electrolytic plating tank was collected.
Moreover, the part of the nickel layer 12 covering one end of the MWCNT 10 is formed thicker than the nickel layer 12 covering the side surface of the MWCNT 10, and the part of the nickel layer 12 covering both ends of the MWCNT 10 What was formed thicker than the nickel layer 12 which covers a side surface was mixed.
実施例１において、陰極２２の陰極面を５分ごとにフッ素樹脂製のヘラで擦り、陰極面に形成された粒状物を削ぎ落とした他は、実施例１と同様にしてＭＷＣＮＴに電解めっきを施し、電解めっき槽の底面に沈殿した粒状物を回収した。回収した粒状物は、図１に示す塊状の粒状物であった。 In Example 1, electrolytic plating was applied to MWCNT in the same manner as in Example 1 except that the cathode surface of the cathode 22 was rubbed with a fluorine resin spatula every 5 minutes and the granular material formed on the cathode surface was scraped off. The granular material which settled on the bottom face of the electroplating tank was collected. The recovered granules was grain shape of massive shown in FIG.
実施例１において、電解めっき終了後に、電解めっき槽１４の底面に沈殿する粒状物を、磁石によって回収した他は、実施例１と同様にしてＭＷＣＮＴに電解めっきを施した。回収した粒状物は、図１に示す塊状の粒状物であった。 In Example 1, after the completion of the electrolytic plating, the MWCNT was subjected to electrolytic plating in the same manner as in Example 1 except that the particulate matter precipitated on the bottom surface of the electrolytic plating tank 14 was collected by a magnet. The recovered granules was grain shape of massive shown in FIG.
実施例２において、電流密度を３Ａ／ｄｍ2の電解めっきを４５分間実施した他は、実施例２と同様にしてＭＷＣＮＴに電解めっきを施した。
しかし、電解めっきを終了しても、粒状物は形成されず、陰極２２の陰極面にＭＷＣＮＴとニッケル層との複合めっき皮膜層が形成されていた。
In Example 2, MWCNT was subjected to electrolytic plating in the same manner as in Example 2 except that electrolytic plating at a current density of 3 A / dm 2 was performed for 45 minutes.
However, even when the electrolytic plating is finished, no particulate matter is formed, and a composite plating film layer of MWCNT and a nickel layer is formed on the cathode surface of the cathode 22.
本発明に係る粒状物は、そのＣＮＴの表面にめっき金属層が形成されているため、ＣＮＴの樹脂との濡れ性を改善できる。このため、本発明に係る粒状物を樹脂に添加して攪拌や混練によって、容易に樹脂中に分散することができる。
したがって、剛性、電磁波の遮断性及び伝熱性に劣る樹脂に対し、優れた剛性、電磁波の遮断性及び伝熱性を付与でき、従来の樹脂では用いることができなかった用途、例えば電子機器用の筐体に適用できる。
Since the plated metal layer is formed on the surface of the CNT, the granular material according to the present invention can improve the wettability of the CNT with the resin. For this reason, the granular material which concerns on this invention can be easily disperse | distributed in resin by stirring and kneading | mixing to resin.
Therefore, it is possible to impart excellent rigidity, electromagnetic wave shielding properties and heat transfer properties to resins having poor rigidity, electromagnetic wave shielding properties and heat transfer properties, and for applications that cannot be used with conventional resins, such as housings for electronic devices. Applicable to the body.
１０ カーボンナノチューブ（ＣＮＴ）
１２ ニッケル層（めっき金属層）
１４ 電解めっき槽
１６ 電解めっき液
１８ 直流電源
２０ 陽極
２２ 陰極
２４ 攪拌機
10 Carbon nanotubes (CNT)
12 Nickel layer (plated metal layer)
14 Electrolytic plating tank 16 Electrolytic plating solution 18 DC power source 20 Anode 22 Cathode 24 Agitator
Claims (16)
該塊状粒状物を形成するカーボンナノチューブの各々は、その端部が前記塊状粒状物の外方に露出状態で突出することなく、前記めっき金属層によって相互に固着されていることを特徴とする塊状粒状物。 A massive granular material formed by a large number of carbon nanotubes having a plated metal layer formed on at least a part of the surface,
Each of the carbon nanotubes forming the massive granular material has a massive shape characterized in that the end portions thereof are fixed to each other by the plated metal layer without protruding in an exposed state to the outside of the massive granular material. Granules.
該カーボンナノチューブを分散する分散剤として、アルキンジオール分子中にオキシエチレン側鎖を有するアルキンジオール化合物であって、前記アルキンジオール化合物の分子量の少なくとも２０重量％をオキシエチレン側鎖が占める分散剤を用いることを特徴とする粒状物の製造方法。 When producing a granular material composed of the carbon nanotube and the plating metal by electrolytic plating using an electrolytic plating solution in which carbon nanotubes are dispersed,
As the dispersant for dispersing the carbon nanotubes, an alkynediol compound having an oxyethylene side chain in the alkynediol molecule, wherein the oxyethylene side chain accounts for at least 20% by weight of the molecular weight of the alkynediol compound is used. The manufacturing method of the granular material characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009222004A JP5342976B2 (en) | 2004-05-07 | 2009-09-28 | Granules and method for producing the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004139131A JP4993157B2 (en) | 2004-05-07 | 2004-05-07 | Granular material and method for producing granular material |
| JP2009222004A JP5342976B2 (en) | 2004-05-07 | 2009-09-28 | Granules and method for producing the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004139131A Division JP4993157B2 (en) | 2004-05-07 | 2004-05-07 | Granular material and method for producing granular material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010001569A true JP2010001569A (en) | 2010-01-07 |
| JP5342976B2 JP5342976B2 (en) | 2013-11-13 |
Family
ID=35468054
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004139131A Expired - Fee Related JP4993157B2 (en) | 2004-05-07 | 2004-05-07 | Granular material and method for producing granular material |
| JP2009222004A Expired - Fee Related JP5342976B2 (en) | 2004-05-07 | 2009-09-28 | Granules and method for producing the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004139131A Expired - Fee Related JP4993157B2 (en) | 2004-05-07 | 2004-05-07 | Granular material and method for producing granular material |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP4993157B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100748228B1 (en) | 2006-02-28 | 2007-08-09 | 한국과학기술원 | Method of making metal/carbon nanotube composite materials by electroplating |
| KR101413366B1 (en) * | 2007-02-20 | 2014-06-27 | 도레이 카부시키가이샤 | Carbon nanotube assembly and electrically conductive film |
| KR101022857B1 (en) * | 2008-01-16 | 2011-03-17 | 인하대학교 산학협력단 | Preparation method of carbon nano fiber composites electroplated transition metal for hydrogen storage |
| JP5736270B2 (en) | 2010-09-14 | 2015-06-17 | 新光電気工業株式会社 | Heat dissipation component and manufacturing method thereof |
| EP2660361A1 (en) * | 2010-12-28 | 2013-11-06 | National Institute of Advanced Industrial Science And Technology | Carbon nanotube metal composite material and production method for same |
| JP6112639B2 (en) | 2013-07-22 | 2017-04-12 | 国立研究開発法人産業技術総合研究所 | CNT metal composite and manufacturing method thereof |
| JP7185695B2 (en) | 2018-10-19 | 2022-12-07 | ラシフィ インコーポレイテッド | Artificial eyelash extension applicator and method of use and manufacture thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5989788A (en) * | 1982-11-11 | 1984-05-24 | C Uyemura & Co Ltd | Method for electroplating staple fiber having electric conductivity |
| JPH0615744B2 (en) * | 1987-06-29 | 1994-03-02 | 三菱石油株式会社 | Electroplating method for carbon fiber |
| JPH03257194A (en) * | 1990-03-06 | 1991-11-15 | Fuji Kobunshi Kk | Method for electroplating fine metal powder |
| JP2953996B2 (en) * | 1995-05-31 | 1999-09-27 | 日本電気株式会社 | Metal-coated carbon nanotube and method for producing the same |
| JP3730476B2 (en) * | 2000-03-31 | 2006-01-05 | 株式会社東芝 | Field emission cold cathode and manufacturing method thereof |
| US6975063B2 (en) * | 2002-04-12 | 2005-12-13 | Si Diamond Technology, Inc. | Metallization of carbon nanotubes for field emission applications |
| JP4324434B2 (en) * | 2003-09-18 | 2009-09-02 | 新光電気工業株式会社 | Heat dissipation member and manufacturing method thereof |
| JP4001291B2 (en) * | 2004-03-31 | 2007-10-31 | 日精樹脂工業株式会社 | Processing method of carbon nanofiber |
| JP3973039B2 (en) * | 2004-03-31 | 2007-09-05 | 日精樹脂工業株式会社 | Composite plated product and method for producing the same |
-
2004
- 2004-05-07 JP JP2004139131A patent/JP4993157B2/en not_active Expired - Fee Related
-
2009
- 2009-09-28 JP JP2009222004A patent/JP5342976B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| JPN6010058446; Ｓｕｓｕｍｕ Ａｒａｉ他: 'Ｃａｒｂｏｎ ｎａｎｏｆｉｂｅｒ-ｃｏｐｐｅｒ ｃｏｍｐｏｓｉｔｅ ｐｏｗｄｅｒ ｐｒｅｐａｒｅｄ ｂｙ ｅｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ' Ｅｌｅｃｔｒｏｃｈｅｍｉｓｔｒｙ Ｃｏｍｍｕｎｉｃａｔｉｏｎｓ ５（９）, 2003, ７９７-７９９, Ｅｌｓｅｖｉｅｒ * |
| JPN6010058447; Ｓｕｓｕｍｕ Ａｒａｉ他: 'Ｎｉ-ｄｅｐｏｓｉｔｅｄ ｍｕｌｔｉ-ｗａｌｌｅｄ ｃａｒｂｏｎ ｎａｎｏｔｕｂｅｓ ｂｙ ｅｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ' Ｃａｒｂｏｎ ４２（３）, 2004, ６４１-６４４, Ｅｌｓｅｖｉｅｒ * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5342976B2 (en) | 2013-11-13 |
| JP2005320579A (en) | 2005-11-17 |
| JP4993157B2 (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5342976B2 (en) | Granules and method for producing the same | |
| Arai et al. | Ni-deposited multi-walled carbon nanotubes by electrodeposition | |
| KR101066751B1 (en) | Metal plating structure and method for production thereof | |
| TWI570196B (en) | Silver-clad copper powder | |
| JP2007070689A (en) | Nanocarbon/aluminum composite material, method for producing the same, and plating liquid used therefor | |
| JP2008231530A (en) | Surface coating material | |
| Panek et al. | Production and electrochemical characterization of Ni-based composite coatings containing titanium, vanadium or molybdenum powders | |
| Wang et al. | Preparation of nickel–carbon nanofiber composites by a pulse-reverse electrodeposition process | |
| Arai et al. | Fabrication of nickel–multiwalled carbon nanotube composite films with excellent thermal conductivity by an electrodeposition technique | |
| JP4351120B2 (en) | Method for producing metal particles | |
| JP4421556B2 (en) | Metal particle and method for producing the same | |
| JP2012082510A (en) | Heat radiating component and method of producing the same | |
| JP2007211305A (en) | Composite foil of electrolytic copper, and production method therefor | |
| Arai et al. | Carbon nanofiber-copper composites fabricated by electroplating | |
| JP2008169402A (en) | Electrochemical reaction process | |
| JP5544527B2 (en) | Composite plating film, method for forming the same, and electrolytic plating solution | |
| WO2017061443A1 (en) | Sn-COATED COPPER POWDER, CONDUCTIVE PASTE USING SAME, AND PRODUCING METHOD FOR Sn-COATED COPPER POWDER | |
| JP6804574B2 (en) | Composite plating material and its manufacturing method | |
| JP4617327B2 (en) | Preparation method of molybdenum disulfide composite plating solution, molybdenum disulfide composite plating method and nickel-molybdenum disulfide composite plating film | |
| JP3973039B2 (en) | Composite plated product and method for producing the same | |
| CN110268103A (en) | The forming method of coating | |
| JP2005290474A (en) | Treatment method for carbon nanofiber and composite plated article | |
| JP6978568B2 (en) | Composite plating material and its manufacturing method | |
| Daneshvar | Carbon nanotube/metal corrosion issues for nanotube coatings and inclusions in a matrix | |
| JP2004162096A (en) | Paste for electroless plating, and method for producing metallic structure and fine metallic component obtained by using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091027 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091027 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120828 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121022 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130806 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130812 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5342976 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |