JP2013193954A - Method for producing nickel coating nanocarbon by using electroless plating - Google Patents
Method for producing nickel coating nanocarbon by using electroless plating Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Abstract
Description
本発明は、無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法に係り、より詳細には、無電解めっき法の工程変数の制御を通じて形状制御された無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法に関する。 The present invention relates to a method of manufacturing nickel-coated nanocarbon using an electroless plating method, and more particularly, nickel coating using an electroless plating method whose shape is controlled through control of process variables of the electroless plating method. The present invention relates to a method for producing nanocarbon.
ナノカーボンは、高い強度と弾性係数、優れた熱および電気伝導度などの優れた機械的、物理的特性を有し、最近では、ナノカーボンを金属材料でコーティングし、ナノカーボン／金属複合体として様々な分野に応用しようとする試みがなされている。例えば、ニッケルコーティングされたナノカーボン（Ｎｉ−ｃｏａｔｅｄ Ｎａｎｏ−ｃａｒｂｏｎｓ）は、電磁波遮蔽素材、遠距離場用吸収素材として優れた性能を示すため、ナノカーボンにニッケルをコーティングしようとする試みがなされている。 Nanocarbon has excellent mechanical and physical properties such as high strength and elastic modulus, excellent heat and electrical conductivity. Recently, nanocarbon is coated with metal material as nanocarbon / metal composite Attempts have been made to apply to various fields. For example, nickel-coated nano-carbons (Ni-coated Nano-carbons) exhibit excellent performance as electromagnetic shielding materials and far-field absorption materials, and therefore, attempts have been made to coat nickel on nano-carbons. .
最近では、ナノカーボンにニッケルをコーティングする方法として無電解めっき法が多く使用されている。
例えば、特許文献１は、無電解めっき方式でカーボンナノチューブに金属をコーティングし、カーボンナノチューブ金属の複合体を作る方法を開示している。
一方、ナノカーボンの代表例である炭素ナノチューブは、黒鉛面（ｇｒａｐｈｉｔｅ ｓｈｅｅｔ）がナノスケールの直径のシリンダ形態を有し、ｓｐ２結合構造を有する。この黒鉛面が巻かれる角度および構造に応じて、ナノカーボンは導体または半導体の特性を示す。このようなナノカーボンは、壁をなしている結合数に応じて、単一壁炭素ナノチューブ（以下、ＳＷＣＮＴと略す。）、二重壁炭素ナノチューブ（以下、ＤＷＣＮＴと略す。）、多重壁炭素ナノチューブ（以下、ＭＷＣＮＴと略す。）および束状炭素ナノチューブ（ｒｏｐｅ ｃａｒｂｏｎ ｎａｎｏｔｕｂｅ）に分類できる（例えば、特許文献２を参照）。
Recently, electroless plating is often used as a method of coating nanocarbon with nickel.
For example, Patent Document 1 discloses a method of making a carbon nanotube metal composite by coating a carbon nanotube with a metal by an electroless plating method.
On the other hand, a carbon nanotube, which is a typical example of nanocarbon, has a cylinder shape with a graphite surface having a nanoscale diameter and an sp2 bond structure. Depending on the angle and structure at which this graphite surface is wound, nanocarbon exhibits the properties of a conductor or semiconductor. Such nanocarbons are single-walled carbon nanotubes (hereinafter abbreviated as SWCNT), double-walled carbon nanotubes (hereinafter abbreviated as DWCNT), multi-walled carbon nanotubes, depending on the number of bonds forming the wall. (Hereinafter abbreviated as MWCNT) and bundle carbon nanotubes (see, for example, Patent Document 2).
このうち、ＳＷＣＮＴは、金属的な特性と半導体的な特性を併せ持っており、多様な電気的、化学的、物理的および光学的特性を示す。一般的に、ＳＷＣＮＴの合成時、金属性ＳＷＣＮＴと半導体性ＳＷＣＮＴが必然的に混合される。
カーボンナノファイバー（Ｃａｒｂｏｎ ｎａｎｏ ｆｉｂｅｒ：以下、ＣＮＦと略す。）、ＭＷＣＮＴ、三重壁炭素ナノチューブ（以下、ＴＷＣＮＴと略す。）、ＤＷＣＮＴ、金属性ＳＷＣＮＴなどの金属性ナノカーボンと、半導体性ＳＷＣＮＴないしＳＷＣＮＴバンドルなどの半導体性ナノカーボンとは、その電気的性質が異なる。無電解めっき法は、被めっき体の表面上で化学反応が行われるものであるため、無電解めっき法を適用してナノカーボンに金属をコーティングするにあたり、被めっき体の電気的性質に応じた、差別化されたプロセスが要求されているが、従来技術はこれに対する解答を提供することができなかった。
Among them, SWCNT has both metallic characteristics and semiconductor characteristics, and exhibits various electrical, chemical, physical and optical characteristics. Generally, when SWCNT is synthesized, metallic SWCNT and semiconductive SWCNT are necessarily mixed.
Carbon nanofiber (hereinafter abbreviated as CNF), MWCNT, triple-walled carbon nanotube (hereinafter abbreviated as TWCNT), DWCNT, metallic SWCNT, and other metallic nanocarbon, and semiconducting SWCNT or SWCNT bundle Its electrical properties are different from those of semiconducting nanocarbon. In the electroless plating method, a chemical reaction is performed on the surface of the object to be plated. Therefore, in applying the metal to nanocarbon by applying the electroless plating method, it depends on the electrical properties of the object to be plated. Although a differentiated process is required, the prior art has not been able to provide an answer to this.
そこで、本発明は、かかる問題点を解決するためになされたものであって、その目的とするところは、無電解めっき法を用いてナノカーボンにニッケルをコーティングするにあたり、ナノカーボンの電気的性質に応じて差別化されたコーティング方法を提供することにある。
より具体的には、本発明は、無電解めっき法を用いて金属性ナノカーボン、すなわち、ＣＮＦ、ＭＷＣＮＴ、ＴＷＣＮＴ，ＤＷＣＮＴまたは金属性ＳＷＣＮＴにニッケルをコーティングする方法を提供する。
また、本発明は、無電解めっき法を用いて半導体性ナノカーボン、すなわち、半導体性ＳＷＣＮＴまたはＳＷＣＮＴバンドル（ｂｕｎｄｌｅ）にニッケルをコーティングする方法を提供する。
さらに、本発明は、無電解めっき法を用いてナノカーボンに形状制御されたニッケルコーティングを形成する方法を提供する。
Therefore, the present invention has been made to solve such problems, and the object of the present invention is to apply the electrical properties of nanocarbon when coating nanocarbon with electroless plating. It is an object of the present invention to provide a coating method differentiated according to the above.
More specifically, the present invention provides a method for coating nickel on metallic nanocarbon, that is, CNF, MWCNT, TWCNT, DWCNT, or metallic SWCNT using an electroless plating method.
In addition, the present invention provides a method for coating semiconducting nanocarbon, that is, semiconducting SWCNT or SWCNT bundle using an electroless plating method.
Furthermore, the present invention provides a method of forming a shape-controlled nickel coating on nanocarbon using an electroless plating method.
上記目的を達成するための、本発明の無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法は、ナノカーボンを溶媒中で洗浄したり熱酸化処理して不純物を除去する第１ステップと、洗浄または熱酸化処理されたナノカーボンをパラジウム（Ｐｄ）含有溶液に浸漬し、ナノカーボンの表面に活性化されたパラジウム（Ｐｄ）核を形成させる第２ステップと、パラジウム（Ｐｄ）核が形成されたナノカーボンを強酸処理する第３ステップと、強酸処理されたナノカーボンを無電解ニッケルめっき液に浸漬し、ナノカーボンの表面にニッケルめっき層を形成する第４ステップと、ニッケルめっき層が形成されたナノカーボンを高温熱処理して結晶化する第５ステップとを含むことを特徴とする。 In order to achieve the above object, a method for producing a nickel-coated nanocarbon using the electroless plating method of the present invention includes a first step of removing impurities by washing the nanocarbon in a solvent or thermally oxidizing it. A second step of immersing the washed or thermally oxidized nanocarbon in a palladium (Pd) -containing solution to form activated palladium (Pd) nuclei on the nanocarbon surface; and formation of palladium (Pd) nuclei A third step of treating the nanocarbon with a strong acid, a fourth step of immersing the strong acid-treated nanocarbon in an electroless nickel plating solution to form a nickel plating layer on the surface of the nanocarbon, and forming a nickel plating layer And a fifth step of crystallizing the nanocarbon by heat treatment at a high temperature.
本発明によれば、無電解めっき法を用いてナノカーボンの電気的性質を反映し、簡単かつ便利に大量で多様な形態の金属コーティングが形成されたナノカーボンを製造することができる。 ADVANTAGE OF THE INVENTION According to this invention, the nanocarbon by which the electrical property of nanocarbon was reflected using the electroless-plating method and the metal coating of various forms was formed in large quantities easily and conveniently can be manufactured.
以下、本発明の構成および作用をより詳細に説明する。
本発明は、ナノカーボンを溶媒中で洗浄したり熱酸化処理して不純物を除去する第１ステップと、洗浄または熱酸化処理されたナノカーボンをＰｄ含有溶液に浸漬し、ナノカーボンの表面に活性化されたＰｄ核を形成させる第２ステップと、Ｐｄ核が形成されたナノカーボンを強酸処理する第３ステップと、強酸処理されたナノカーボンを無電解ニッケルめっき液に浸漬し、ナノカーボンの表面にニッケルめっき層を形成する第４ステップと、ニッケルめっき層が形成されたナノカーボンを高温熱処理して結晶化する第５ステップとを含む、無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法を提供する。
本発明において、ナノカーボンは、ＣＮＦ、ＭＷＣＮＴ、ＴＷＣＮＴ、ＤＷＣＮＴおよび金属性ＳＷＣＮＴなどの金属性ナノカーボンと、半導体性ＳＷＣＮＴおよびＳＷＣＮＴバンドル（ｂｕｎｄｌｅ）などの半導体性ナノカーボンとに分類する。
本発明において、ニッケルコーティングは、無電解めっき時に使用される還元剤の種類に応じて、Ｎｉ−ＰまたはＮｉ−Ｂコーティングを含む意味として使われる。すなわち、Ｎｉ−Ｐコーティングは、リン（Ｐ）系の還元剤を用いてニッケルを無電解めっきする場合に形成され、Ｎｉ−Ｂコーティングは、ホウ素（Ｂ）系の還元剤を用いる場合に形成される。
Hereinafter, the configuration and operation of the present invention will be described in more detail.
In the present invention, the first step of removing impurities by washing the nanocarbon in a solvent or thermally oxidizing it, and immersing the washed or thermally oxidized nanocarbon in a Pd-containing solution to activate the surface of the nanocarbon. A second step of forming the oxidized Pd nucleus, a third step of treating the nanocarbon with the Pd nucleus formed with a strong acid, and immersing the strong acid-treated nanocarbon in an electroless nickel plating solution to form a surface of the nanocarbon. Manufacturing a nickel-coated nanocarbon using an electroless plating method, which includes a fourth step of forming a nickel plating layer on the substrate and a fifth step of crystallizing the nanocarbon having the nickel plating layer formed thereon by high-temperature heat treatment. Provide a method.
In the present invention, nanocarbons are classified into metallic nanocarbons such as CNF, MWCNT, TWCNT, DWCNT and metallic SWCNT, and semiconducting nanocarbons such as semiconducting SWCNT and SWCNT bundles.
In the present invention, nickel coating is used to include Ni-P or Ni-B coating, depending on the type of reducing agent used during electroless plating. That is, the Ni-P coating is formed when nickel is electrolessly plated using a phosphorus (P) -based reducing agent, and the Ni-B coating is formed when a boron (B) -based reducing agent is used. The
本発明の無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法において、第１ステップは、純度の向上を目的として、ナノカーボンを有機溶媒または酸水溶液中で超音波でナノカーボンを洗浄するステップである。例えば、ナノカーボンをアルコールなどの有機溶媒または酸水溶液などに浸漬させ、超音波処理を行うことにより、非晶質炭素などの不純物を除去することができる。
あるいは、第１ステップは、４００〜６００℃で３０分〜５時間空気中の熱酸化処理を行うステップである。
図２は、熱処理前後のＣＮＦの熱量分析（ＴＧＡ）の結果である。図２に示したとおり、４００〜６００℃で３時間空気中の熱酸化処理を行った結果、ＣＮＦの純度が８７重量％から９９重量％に増加した。したがって、アルコールなどの溶媒を用いてＣＮＦを洗浄する工程を熱酸化処理に代替することができる。熱酸化処理工程は、洗浄工程に比べると、溶媒などの使用が減少し、経済的および環境的な面で有利である。
In the method for producing nickel-coated nanocarbon using the electroless plating method of the present invention, the first step is to clean the nanocarbon with ultrasonic waves in an organic solvent or an acid aqueous solution for the purpose of improving purity. It is a step. For example, it is possible to remove impurities such as amorphous carbon by immersing nanocarbon in an organic solvent such as alcohol or an aqueous acid solution and performing ultrasonic treatment.
Or a 1st step is a step which performs the thermal oxidation process in the air for 30 minutes-5 hours at 400-600 degreeC.
FIG. 2 shows the results of calorimetric analysis (TGA) of CNF before and after heat treatment. As shown in FIG. 2, as a result of performing thermal oxidation treatment in air at 400 to 600 ° C. for 3 hours, the purity of CNF increased from 87 wt% to 99 wt%. Therefore, the process of cleaning CNF using a solvent such as alcohol can be replaced with thermal oxidation treatment. The thermal oxidation treatment process is advantageous in terms of economy and environment because the use of a solvent or the like is reduced compared to the cleaning process.
第２ステップは、洗浄または熱酸化処理されたナノカーボンをＰｄ含有溶液に浸漬し、ナノカーボンの表面でＰｄイオンの還元を生じさせ、ナノカーボンの表面に活性化されたＰｄ核を生成させるステップである。
無電解めっきはナノカーボンの活性化された表面でのみ進行し、ナノカーボンの表面の活性化程度は無電解めっき層の密着力に影響を与える。
したがって、本ステップでは、洗浄または熱酸化処理されたナノカーボンをＰｄを含有した溶液に浸漬し、ナノカーボンの表面でＰｄイオンを還元して、ナノカーボンの表面に活性化されたＰｄ核を生成させることにより、ナノカーボンの表面を活性化する。
The second step includes immersing the cleaned or thermally oxidized nanocarbon in a Pd-containing solution, causing reduction of Pd ions on the surface of the nanocarbon, and generating activated Pd nuclei on the surface of the nanocarbon. It is.
Electroless plating proceeds only on the activated surface of nanocarbon, and the degree of activation of the nanocarbon surface affects the adhesion of the electroless plating layer.
Therefore, in this step, the cleaned or thermally oxidized nanocarbon is immersed in a solution containing Pd, and Pd ions are reduced on the surface of the nanocarbon to generate activated Pd nuclei on the surface of the nanocarbon. By activating, the surface of the nanocarbon is activated.
ナノカーボンが半導体性ＳＷＣＮＴおよびＳＷＣＮＴバンドル（ｂｕｎｄｌｅ）の場合、Ｓｎ含有溶液に半導体性ナノカーボンを浸漬し、Ｓｎ２＋イオンを半導体性ナノカーボンの表面に吸着させて水洗するステップ、すなわち、鋭敏化処理ステップを追加的に含む。
ナノカーボンがＣＮＦ、ＭＷＣＮＴ、ＴＷＣＮＴ、ＤＷＣＮＴおよび金属性ＳＷＣＮＴの場合は、鋭敏化処理ステップを必要としないが、半導体性ＳＷＣＮＴおよびＳＷＣＮＴバンドル（ｂｕｎｄｌｅ）の場合、活性化処理前に鋭敏化処理を行う。
When the nanocarbon is a semiconducting SWCNT or SWCNT bundle, the step of immersing the semiconducting nanocarbon in an Sn-containing solution and adsorbing Sn 2+ ions to the surface of the semiconducting nanocarbon, that is, washing with water, that is, sensitization treatment Includes additional steps.
When the nanocarbon is CNF, MWCNT, TWCNT, DWCNT, and metallic SWCNT, the sensitizing treatment step is not required. However, in the case of the semiconducting SWCNT and SWCNT bundle (bundle), the sensitizing treatment is performed before the activation treatment. .
第３ステップは、加速化処理ステップであって、金属性ナノカーボン（ＣＮＦ、ＭＷＣＮＴ、ＴＷＣＮＴ、ＤＷＣＮＴおよび金属性ＳＷＣＮＴ）の場合、精製されたＰｄを析出するために、Ｐｄ核が形成されたナノカーボンを強酸で処理するステップである。
また、第３ステップは、ナノカーボンが半導体性（半導体性ＳＷＣＮＴおよびＳＷＣＮＴバンドル）の場合、鋭敏化処理および活性化処理後に表面に残っているＳｎ成分を除去し、精製されたＰｄを析出するステップである。すなわち、半導体性ナノカーボンは、鋭敏化処理および活性化処理によってＳｎ２＋＋Ｐｄ２＋＝Ｓｎ４＋＋Ｐｄ０反応が進行して表面にＰｄ核が形成される。ナノカーボン表面にはＳｎ４＋が残るが、これを強酸で処理することによって除去する。
The third step is an acceleration treatment step. In the case of metallic nanocarbons (CNF, MWCNT, TWCNT, DWCNT, and metallic SWCNT), the nanocrystals in which Pd nuclei are formed to precipitate purified Pd. This is a step of treating carbon with a strong acid.
In the third step, when the nanocarbon is semiconducting (semiconductor SWCNT and SWCNT bundle), the Sn component remaining on the surface after the sensitization treatment and activation treatment is removed, and purified Pd is deposited. It is. That is, the semiconducting nanocarbon undergoes Sn 2+ + Pd 2+ = Sn 4+ + Pd 0 reaction through sensitization and activation treatment, and Pd nuclei are formed on the surface. Sn 4+ remains on the nanocarbon surface, but is removed by treatment with a strong acid.
第４ステップは、強酸処理されたナノカーボンを無電解ニッケルめっき液に浸漬し、ナノカーボンの表面にニッケルめっき層を形成するステップである。
ナノカーボンの表面にＰｄ触媒が活性化されていても、自己触媒めっき反応（Ａｕｔｏ ｃａｔａｌｙｔｉｃ Ｐｌａｔｉｎｇ）が引き続き進行するためには、一定温度以上を維持しなければならず、ひいては、温度が増加するほどめっき反応の速度は増加する。ニッケルめっき液は、常温タイプのニッケルめっき液（４０℃以下で反応）と、高温タイプのニッケルめっき液（１００℃以下で反応）とに分けられる。
また、めっき速度はｐＨ調整によって調整可能である。すなわち、ｐＨは、４．８を基準として、これより高いほどめっき速度は増加する。
めっき厚さはめっき時間に比例して増加するため、ターゲットの厚さに応じて、めっき速度は調整される。
The fourth step is a step of immersing nanoacid-treated nanocarbon in an electroless nickel plating solution to form a nickel plating layer on the nanocarbon surface.
Even if the Pd catalyst is activated on the surface of the nanocarbon, in order for the autocatalytic plating reaction to continue, the temperature must be maintained above a certain temperature, and as the temperature increases. The rate of plating reaction increases. The nickel plating solution is classified into a normal temperature type nickel plating solution (reaction at 40 ° C. or less) and a high temperature type nickel plating solution (reaction at 100 ° C. or less).
The plating rate can be adjusted by adjusting the pH. That is, on the basis of 4.8, the higher the pH, the higher the plating rate.
Since the plating thickness increases in proportion to the plating time, the plating rate is adjusted according to the thickness of the target.
本発明において、第４ステップが、常温タイプのニッケルめっき液の場合、２０〜４０℃の範囲で５〜２０分、高温タイプのニッケルめっき液の場合、７０〜１００℃で１〜１０分間進行することが好ましい。
また、第４ステップにおいて、ｐＨは４〜６に維持されることが好ましい。ｐＨが４〜６の範囲内に維持される場合、無電解ニッケルめっき液がより安定的に維持でき、めっき速度が速く、めっき効率に優れる。
本発明にかかる無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法は、めっき液の濃度、蒸着時間、反応温度、めっき液のｐＨなどを制御し、金属の積載量、形状、分布密度、パーティクルサイズを制御することができる。
めっき液は、リン（Ｐ）の含有量に応じて、高濃度めっき液（１０〜１３％）、中濃度めっき液（７〜９％）、低濃度めっき液（１〜５％）に分類される。リンの含有量が増加するほど、めっき速度は減少し、耐食性は増加し、耐熱性は減少する。
In the present invention, the fourth step proceeds in the range of 20 to 40 ° C. for 5 to 20 minutes in the case of a normal temperature type nickel plating solution, and in the case of a high temperature type nickel plating solution in 1 to 10 minutes at 70 to 100 ° C. It is preferable.
In the fourth step, the pH is preferably maintained at 4-6. When the pH is maintained within the range of 4 to 6, the electroless nickel plating solution can be maintained more stably, the plating rate is high, and the plating efficiency is excellent.
The method for producing nickel-coated nanocarbon using the electroless plating method according to the present invention controls the concentration of the plating solution, the deposition time, the reaction temperature, the pH of the plating solution, etc., and the metal loading, shape, and distribution density. , Particle size can be controlled.
The plating solution is classified into a high concentration plating solution (10 to 13%), a medium concentration plating solution (7 to 9%), and a low concentration plating solution (1 to 5%) according to the phosphorus (P) content. The As the phosphorus content increases, the plating rate decreases, the corrosion resistance increases, and the heat resistance decreases.
本発明によれば、無電解めっき溶液の濃度、蒸着時間、反応温度、ｐＨなどの工程変数の制御を通じてＮｉ−Ｐ、Ｎｉ−ＢまたはＮｉの積載量、Ｎｉ−Ｐ、Ｎｉ−ＢまたはＮｉの形状、分布密度またはパーティクルサイズを制御することができる。
特に、工程変数の制御を通じてナノカーボンの表面に繊維状（ｆｉｂｒｏｕｓ）のＮｉ−ＰまたはＮｉ−Ｂコーティング、鱗状（ｓｃａｌｅｌｉｋｅ ｓｔｒｕｃｔｕｒｅ）のＮｉ−ＰまたはＮｉ−Ｂコーティング、球状（ｓｐｈｅｒｉｃａｌ）のＮｉ−ＰまたはＮｉ−Ｂコーティングなど、様々な形態のＮｉ−ＰまたはＮｉ−Ｂコーティングを行うことができる。
According to the present invention, the load of Ni—P, Ni—B or Ni, Ni—P, Ni—B or Ni can be controlled through control of process variables such as the concentration of electroless plating solution, deposition time, reaction temperature, and pH. Shape, distribution density or particle size can be controlled.
In particular, a fibrous Ni-P or Ni-B coating, a scalelike Ni-P or Ni-B coating, a spherical Ni-P on the nanocarbon surface through control of process variables. Alternatively, various forms of Ni-P or Ni-B coating can be performed, such as Ni-B coating.
図１は、本発明のパラジウム（Ｐｄ）およびニッケル（Ｎｉ）がコーティングされたナノカーボンの概念図である。図１に示したとおり、繊維状のコーティングは、多量のＰｄイオン、低い温度、低いｐＨ（基準４．８）の条件で反応速度が遅い場合に実現できる。
また、鱗状のコーティングは、多量のＰｄイオン、高い温度、高いｐＨ（基準４．８）の条件で反応が急激に起こる場合に実現できる。
さらに、球状のコーティングは、少量のＰｄイオン、高い温度、高いｐＨ（基準４．８）の条件で実現できるが、ニッケルイオンが積層できるようにシードの役割を果たすＰｄの濃度が低く、かつ、温度とｐＨが高ければ、反応が急激に起こりながらＰｄの周辺にのみニッケルイオンが積層され、球状のコーティングがなされる。
FIG. 1 is a conceptual diagram of nanocarbon coated with palladium (Pd) and nickel (Ni) according to the present invention. As shown in FIG. 1, a fibrous coating can be realized when the reaction rate is low under the conditions of a large amount of Pd ions, a low temperature, and a low pH (standard 4.8).
Also, scaly coating can be realized when the reaction occurs rapidly under the conditions of a large amount of Pd ions, high temperature, and high pH (standard 4.8).
Furthermore, the spherical coating can be realized under the conditions of a small amount of Pd ions, high temperature, and high pH (standard 4.8), but the concentration of Pd that plays a role of seeding so that nickel ions can be laminated, and If the temperature and pH are high, nickel ions are deposited only around Pd while the reaction occurs rapidly, and a spherical coating is formed.
具体的には、第４ステップは、Ｐｄの濃度０．４〜１ｇ／Ｌ、Ｎｉめっき液の濃度５〜１０ｇ／Ｌ、蒸着時間１０〜１５分、反応温度７０〜８０℃、ｐＨ４〜５で進行することにより、繊維状のニッケルめっき層を形成することができる。
また、第４ステップは、Ｐｄの濃度０．４〜１ｇ／Ｌ、Ｎｉめっき液の濃度５〜１０ｇ／Ｌ、蒸着時間５〜１０分、反応温度８０〜１００℃、ｐＨ５〜６で進行することにより、鱗状のニッケルめっき層を形成することができる。
さらに、第４ステップは、Ｐｄの濃度０．１２５〜０．２ｇ／Ｌ、Ｎｉめっき液の濃度５〜１０ｇ／Ｌ、蒸着時間５〜１０分、反応温度８０〜１００℃、ｐＨ５〜６で進行することにより、球状のニッケルめっき層を形成することができる。
繊維状のコーティングがなされたナノカーボンは、強度が高いという利点があり、鱗状のコーティングがなされたナノカーボンは、表面積が広く、電磁波遮蔽、水素の吸着に有利であり、球状のコーティングがなされたナノカーボンは、燃料電池の触媒支持体としての使用に有利である。
Specifically, in the fourth step, the concentration of Pd is 0.4 to 1 g / L, the concentration of the Ni plating solution is 5 to 10 g / L, the deposition time is 10 to 15 minutes, the reaction temperature is 70 to 80 ° C., and the pH is 4 to 5. By proceeding, a fibrous nickel plating layer can be formed.
The fourth step proceeds at a Pd concentration of 0.4-1 g / L, a Ni plating solution concentration of 5-10 g / L, a deposition time of 5-10 minutes, a reaction temperature of 80-100 ° C., and a pH of 5-6. Thus, a scale-like nickel plating layer can be formed.
Further, the fourth step proceeds at a Pd concentration of 0.125 to 0.2 g / L, a Ni plating solution concentration of 5 to 10 g / L, a deposition time of 5 to 10 minutes, a reaction temperature of 80 to 100 ° C., and a pH of 5 to 6. By doing so, a spherical nickel plating layer can be formed.
Nanocarbon with a fibrous coating has the advantage of high strength, and the nanocarbon with a scaly coating has a large surface area, which is advantageous for electromagnetic shielding and hydrogen adsorption, and has a spherical coating. Nanocarbons are advantageous for use as fuel cell catalyst supports.
無電解ニッケルめっき液の成分は、主成分と、補助成分とに分けられる。
主成分は、ニッケル塩およびニッケルイオンに電子を供与してニッケルに還元させる還元剤からなる。ニッケル塩としては、塩化ニッケル、硫酸ニッケル、スルファミン酸ニッケルなどのニッケル塩水和物が使用可能であり、還元剤としては、次亜リン酸塩、水素化ホウ素塩、ジメチルアミンボラン、ヒドラジンなどが使用可能である。
補助成分としては、錯化剤、緩衝剤、ｐＨ調整剤、促進剤、安定剤、改良剤などがあり、めっき液の寿命延長および還元剤の効率性の向上などのために添加される。
The components of the electroless nickel plating solution are divided into a main component and an auxiliary component.
The main component consists of a reducing agent that donates electrons to nickel salts and nickel ions to reduce them to nickel. Nickel salt hydrates such as nickel chloride, nickel sulfate, and nickel sulfamate can be used as the nickel salt, and hypophosphite, borohydride, dimethylamine borane, hydrazine, etc. are used as the reducing agent. Is possible.
Auxiliary components include complexing agents, buffering agents, pH adjusting agents, accelerators, stabilizers, improving agents and the like, which are added to extend the life of the plating solution and improve the efficiency of the reducing agent.
錯化剤は、金属錯イオンを形成して還元反応に参加する金属イオンの総量を調整したり、金属イオンが金属塩として沈澱するのを遅延させることにより、金属イオンの安定化を助ける役割を果たす。その種類は特に限定しないが、酢酸ナトリウム、エチレングリコールなどの有機酸や、それらの塩を使用することができる。
緩衝剤は、無電解めっき時にｐＨの変化幅を減少させるために使用し、その種類は特に限定されない。
ｐＨ調整剤は、無電解めっきの速度、効率、めっき皮膜の状態に影響を与えるｐＨの変化を防止するために使用され、その種類は特に限定しないが、水酸化アンモニウム、無機酸、有機酸、苛性ソーダなどを使用することができる。
促進剤は、めっき速度を促進して金属析出効率を向上させる役割を果たし、その種類は特に限定せず、硫化物、フッ化物などを使用することができる。
安定剤は、めっきしようとする表面以外に還元反応が起こるのを抑制し、めっき浴の自然分解を抑制する役割を果たし、その種類は特に限定しないが、鉛の塩化物、硫化物、硝酸物などを使用することができる。
改良剤は、めっき皮膜の光沢を向上させる役割を果たし、通常、界面活性剤を微量添加する。
The complexing agent plays a role in stabilizing metal ions by adjusting the total amount of metal ions participating in the reduction reaction by forming metal complex ions or by delaying the precipitation of metal ions as metal salts. Fulfill. Although the kind is not specifically limited, Organic acids, such as sodium acetate and ethylene glycol, and those salts can be used.
The buffering agent is used for reducing the change width of the pH during electroless plating, and the kind thereof is not particularly limited.
The pH adjuster is used to prevent a change in pH that affects the speed, efficiency, and plating film state of electroless plating, and the type thereof is not particularly limited, but ammonium hydroxide, inorganic acid, organic acid, Caustic soda can be used.
The promoter plays the role of promoting the plating rate and improving the metal deposition efficiency, and the type thereof is not particularly limited, and sulfides, fluorides and the like can be used.
Stabilizers suppress the occurrence of reduction reactions on the surface other than the surface to be plated and play a role in suppressing the spontaneous decomposition of the plating bath. The type is not particularly limited, but lead chloride, sulfide, nitrate Etc. can be used.
The improving agent plays a role of improving the gloss of the plating film, and usually a trace amount of a surfactant is added.
第５ステップは、ニッケルめっき層が形成されたナノカーボンを高温熱処理して結晶化するステップであって、不活性気体（Ａｒ、Ｎ２、Ｈｅなど）雰囲気または真空雰囲気（１０〜３ｔｏｒｒ）またはエアー雰囲気で、３００〜７００℃に３時間高温熱処理するステップである。
第４ステップの結果、ナノカーボンに形成されたニッケルめっき層は、非晶質ニッケルめっき層であり得る。このような非晶質ニッケルめっき層は、熱酸化処理されることにより、結晶質ニッケルめっき層に転換可能である。例えば、Ｎｉ−ＰまたはＮｉ−Ｂをナノカーボンに無電解めっきする場合、ナノカーボンを無電解ニッケルめっき液に浸漬して形成された非晶質のＮｉ−ＰまたはＮｉ−Ｂコーティングは、熱処理を経て結晶質のＮｉ−ＰまたはＮｉ−Ｂコーティングに転換可能である。
The fifth step is a step of crystallizing the nanocarbon on which the nickel plating layer is formed by high-temperature heat treatment, and is an inert gas (Ar, N 2 , He, etc.) atmosphere, a vacuum atmosphere (10-3 torr) or air This is a step of high-temperature heat treatment at 300 to 700 ° C. for 3 hours in an atmosphere.
As a result of the fourth step, the nickel plating layer formed on the nanocarbon may be an amorphous nickel plating layer. Such an amorphous nickel plating layer can be converted into a crystalline nickel plating layer by thermal oxidation treatment. For example, when Ni-P or Ni-B is electrolessly plated on nanocarbon, an amorphous Ni-P or Ni-B coating formed by immersing nanocarbon in an electroless nickel plating solution is subjected to heat treatment. It can then be converted to a crystalline Ni-P or Ni-B coating.
結論的に、本発明の無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法は、ナノカーボンがＣＮＦ、ＭＷＣＮＴ、ＴＷＣＮＴ、ＤＷＣＮＴおよび金属性ＳＷＣＮＴの場合、前処理、活性化処理および加速化処理を行った後、めっき処理することを特徴とし、ナノカーボンが半導体性ＳＷＣＮＴおよびＳＷＣＮＴバンドルの場合、前処理、鋭敏化処理、活性化処理および加速化処理を行った後、めっき処理することを特徴とする。
本発明は、ナノカーボンの電気的性質を考慮して差別化されたプロセスに従って無電解めっきを進行するため、めっき工程の成果および信頼性を改善する効果がある。
In conclusion, the method for producing nickel-coated nanocarbons using the electroless plating method of the present invention includes pretreatment, activation treatment and acceleration when the nanocarbon is CNF, MWCNT, TWCNT, DWCNT and metallic SWCNT. It is characterized by plating after the treatment, and when the nanocarbon is semiconducting SWCNT and SWCNT bundle, the pretreatment, sensitization treatment, activation treatment and acceleration treatment are performed, and then the plating treatment is performed. Features.
The present invention proceeds with electroless plating according to a differentiated process in consideration of the electrical properties of nanocarbon, and thus has the effect of improving the results and reliability of the plating process.
以下、実施例を通じて本発明をより詳細に説明する。しかし、下記の実施例は、本発明をより具体的に説明するためのものであって、本発明の範囲が下記の実施例によって限定されるものではない。下記の実施例は、本発明の範囲内において当業者によって適切に修正、変更可能である。
実施例１ないし３：ＣＮＦのニッケルコーティング
エタノール溶液にＣＮＦ（ＶＧＣＦ○Ｒ−Ｈ、昭和電工社製）を浸漬させ、３０分間超音波処理した後、下記の表１の条件に応じて、［ＰｄＣｌ２＋ＨＣｌ＋Ｈ２Ｏ］溶液にＣＮＦを浸漬させ、１０分間超音波処理した。その後、ＣＮＦを濃硫酸溶液に浸漬して、３分間超音波処理した後、ＳＸ−Ａ、ＳＸ−ＭおよびＨ２Ｏを含むニッケルめっき液に浸漬させ、２００ｒｐｍ、９０℃の条件で１０分間撹拌し、Ｎｉ−ＰコーティングされたＣＮＦを得た。
ＳＸ−Ａは、硫酸ニッケル２．１３８Ｍを含有するニッケルめっき液であり、ＳＸ−Ｍは、次亜リン酸ナトリウム２．３６Ｍを含有する還元液である。
ニッケルコーティングされたＣＮＦを、エアー雰囲気中、３００〜７００℃に３時間熱処理した。
Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
Examples 1 to 3: CNF (VGCF ○ R-H, manufactured by Showa Denko KK) was immersed in a nickel-coated ethanol solution of CNF, subjected to ultrasonic treatment for 30 minutes, and then [PdCl CNF was immersed in a solution of ( 2 + HCl + H 2 O) and sonicated for 10 minutes. Thereafter, CNF is immersed in a concentrated sulfuric acid solution, subjected to ultrasonic treatment for 3 minutes, then immersed in a nickel plating solution containing SX-A, SX-M and H 2 O, and stirred for 10 minutes at 200 rpm and 90 ° C. Thus, CNF coated with Ni-P was obtained.
SX-A is a nickel plating solution containing 2.138M nickel sulfate, and SX-M is a reducing solution containing 2.36M sodium hypophosphite.
Nickel-coated CNF was heat-treated at 300 to 700 ° C. for 3 hours in an air atmosphere.
実施例１ないし３で得たＮｉ−ＰコーティングされたＣＮＦを、４００℃、エアー雰囲気で、３時間高温熱処理し、結晶質のＮｉ−ＰコーティングされたＣＮＦを製造した。
実施例４：ＳＷＣＮＴバンドルのニッケルコーティング
エタノール溶液に半導体性ＳＷＣＮＴバンドルを浸漬させ、３０分間超音波処理を行った後（洗浄ステップ）、［ＰｄＣｌ２＋ＨＣｌ＋Ｈ２Ｏ］溶液にＳＷＣＮＴバンドルを浸漬させ、１０分間超音波処理した。その後、ＳＷＣＮＴバンドルを０．１ｍｏｌのＳｎＣｌ２／０．１ｍｏｌのＨＣｌ溶液に数秒間浸漬させて鋭敏化処理し、濃硫酸溶液に浸漬させ、３分間超音波処理した後、ＳＸ−Ａ、ＳＸ−ＭおよびＨ２Ｏを含むニッケルめっき液に浸漬させた後、２００ｒｐｍ、９０℃の条件で１０分間撹拌し、ニッケルコーティングされたＳＷＣＮＴバンドルを製造した。
試験例：ニッケルコーティングＣＮＦの特性の評価
実施例１ないし３で得た非晶質および結晶質のＮｉ−ＰコーティングされたＣＮＦに対してＳＥＭ分析およびＴＥＭ分析を行った。
図３は、実施例１ないし３の非晶質および結晶質の繊維状、鱗状および球状のニッケルめっきの形状による走査型電子顕微鏡（ＳＥＭ）画像であり、図４は、実施例１ないし３の非晶質および結晶質の繊維状、鱗状および球状のニッケルめっきの形状による透過型電子顕微鏡（ＴＥＭ）画像である。
図３の上段に示したとおり、ナノカーボンの表面にめっきされている非晶質の繊維状、鱗状、球状のニッケルめっき層を確認することができる。また、図３の下段に示したとおり、結晶質の繊維状、鱗状、球状のニッケルめっき層を確認することができる。ＳＥＭ画像を通じて、非晶質めっき層は、高温熱処理を通じて表面の形態が変化することを確認することができた。
Example 4: A semiconducting SWCNT bundle was immersed in a nickel-coated ethanol solution of a SWCNT bundle, subjected to ultrasonic treatment for 30 minutes (cleaning step), and then the SWCNT bundle was immersed in a [PdCl 2 + HCl + H 2 O] solution. Sonicate for minutes. Thereafter, the SWCNT bundle is immersed in a 0.1 mol SnCl 2 /0.1 mol HCl solution for several seconds to be sensitized, immersed in a concentrated sulfuric acid solution, subjected to ultrasonic treatment for 3 minutes, and then SX-A, SX- After dipping in a nickel plating solution containing M and H 2 O, the mixture was stirred for 10 minutes at 200 rpm and 90 ° C. to produce a nickel-coated SWCNT bundle.
Test Example: Evaluation of Characteristics of Nickel-Coated CNF SEM analysis and TEM analysis were performed on the amorphous and crystalline Ni-P coated CNF obtained in Examples 1 to 3.
FIG. 3 is a scanning electron microscope (SEM) image of the amorphous and crystalline fibrous, scale-like, and spherical nickel plating shapes of Examples 1 to 3, and FIG. It is a transmission electron microscope (TEM) image by the shape of amorphous and crystalline fibrous, scale-like, and spherical nickel plating.
As shown in the upper part of FIG. 3, amorphous fibrous, scale-like, and spherical nickel plating layers plated on the nanocarbon surface can be confirmed. Moreover, as shown in the lower part of FIG. 3, crystalline fibrous, scale-like, and spherical nickel plating layers can be confirmed. Through the SEM image, it was confirmed that the surface morphology of the amorphous plating layer changed through high-temperature heat treatment.
また、図４に示したとおり、ＴＥＭ分析の結果、ナノカーボンに積層されているＮｉ−Ｐめっき層の厚さおよび積層された形態を断面積で確認することができた。
さらに、実施例１ないし３の非晶質および結晶質の繊維状、鱗状、球状のＮｉ−ＰコーティングされたＣＮＦに対してＴＧＡ分析を行った。図５は、実施例１ないし３の非晶質の繊維状、鱗状および球状のニッケルめっきの形状に応じた熱的特性を分析した熱量分析（ＴＧＡ）の結果である。
図５に示したとおり、めっき層の形態に応じて熱的特性が異なり、ナノカーボンの表面にめっき層の分布が多いほど熱的に安定していることを確認することができた。
図６は、実施例１ないし３の４００℃、エアー雰囲気で、３時間高温熱処理を通じて生成された結晶質の繊維状、鱗状および球状のニッケルめっきの形状に応じた熱的特性を分析した熱量分析（ＴＧＡ）の結果である。
図６に示したとおり、めっき層が結晶質化されることにより、熱的に安定した状態になることを確認することができた。
Moreover, as shown in FIG. 4, as a result of TEM analysis, the thickness and the laminated form of the Ni—P plating layer laminated on the nanocarbon could be confirmed by the cross-sectional area.
Further, TGA analysis was performed on the amorphous and crystalline fibrous, scaly, and spherical Ni-P coated CNFs of Examples 1 to 3. FIG. 5 shows the results of calorimetric analysis (TGA) in which the thermal characteristics according to the shapes of the amorphous fibrous, scale-like and spherical nickel platings of Examples 1 to 3 were analyzed.
As shown in FIG. 5, the thermal characteristics differed depending on the form of the plating layer, and it was confirmed that the more the plating layer was distributed on the nanocarbon surface, the more thermally stable.
FIG. 6 is a calorimetric analysis of the thermal characteristics according to the shape of the crystalline fibrous, scale-like and spherical nickel plating produced in Examples 1 to 3 through high-temperature heat treatment for 3 hours at 400 ° C. in an air atmosphere. It is a result of (TGA).
As shown in FIG. 6, it was confirmed that the plated layer was crystallized to be in a thermally stable state.
Claims (12)
前記洗浄または熱酸化処理されたナノカーボンをパラジウム（Ｐｄ）含有溶液に浸漬し、ナノカーボンの表面に活性化されたパラジウム（Ｐｄ）核を形成させる第２ステップと、
前記パラジウム（Ｐｄ）核が形成されたナノカーボンを強酸処理する第３ステップと、
前記強酸処理されたナノカーボンを無電解ニッケルめっき液に浸漬し、ナノカーボンの表面にニッケルめっき層を形成する第４ステップと、
前記ニッケルめっき層が形成されたナノカーボンを高温熱処理して結晶化する第５ステップとを含むことを特徴とする無電解めっき法を用いてニッケルコーティングナノカーボンを製造する方法。 A first step of removing impurities by washing the nanocarbon in a solvent or performing a thermal oxidation treatment;
A second step of immersing the washed or thermally oxidized nanocarbon in a palladium (Pd) -containing solution to form activated palladium (Pd) nuclei on the surface of the nanocarbon;
A third step of treating the nanocarbon with the palladium (Pd) nucleus formed thereon with a strong acid;
A fourth step of immersing the nanocarbon treated with the strong acid in an electroless nickel plating solution to form a nickel plating layer on the surface of the nanocarbon;
And a fifth step of crystallizing the nanocarbon on which the nickel plating layer has been formed by high-temperature heat treatment. A method for producing nickel-coated nanocarbon using an electroless plating method.
The fifth step is a step of performing a high temperature heat treatment at 300 to 700 ° C. for 3 hours in an inert gas atmosphere, a vacuum atmosphere or an air atmosphere, on the nanocarbon on which the nickel plating layer is formed. The method of manufacturing nickel coating nanocarbon using the electroless-plating method of description.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016074578A (en) * | 2014-10-07 | 2016-05-12 | ドンイー ホールディングス カンパニー リミテッド | Metal and oxide hybrid-coated nanocarbon production process |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2655073T3 (en) * | 2009-06-09 | 2018-02-16 | Ramesh Sivarajan | Coatings based on solutions of nanostructured carbon materials (NCM) on bipolar plates in fuel cells |
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| US11512390B2 (en) | 2018-07-16 | 2022-11-29 | Rochester Institute Of Technology | Method of site-specific deposition onto a free-standing carbon article |
| WO2020089690A2 (en) * | 2018-10-30 | 2020-05-07 | The American University In Cairo | Method for aluminum electroless deposition |
| JP7032348B2 (en) * | 2019-03-26 | 2022-03-08 | 矢崎総業株式会社 | Metal-plated carbon material and its manufacturing method |
| WO2022056059A1 (en) * | 2020-09-09 | 2022-03-17 | Macmoy Richard Ian | Thermal-diffused metal on electroless metal or metal alloy having a phosphorous component |
| CN113151868B (en) * | 2021-04-28 | 2022-08-12 | 西北工业大学 | Porous nickel-tungsten alloy material and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201484A (en) * | 1987-10-06 | 1989-08-14 | Hitachi Ltd | Chemical nickel plating liquid and method of using said liquid |
| JPH05101972A (en) * | 1991-09-25 | 1993-04-23 | Matsushita Electric Ind Co Ltd | Method for forming electrode on ceramic |
| JPH08124577A (en) * | 1994-08-31 | 1996-05-17 | Sumitomo Electric Ind Ltd | Manufacture of metallic porous material |
| JP2003246613A (en) * | 2002-02-26 | 2003-09-02 | Denso Corp | Metal-added carbon material manufacturing method, and electrode material for fuel cell, catalyst carrier for chemical reaction and gas storage material obtained by using the metal-added carbon material manufactured thereby |
| JP2004018973A (en) * | 2002-06-18 | 2004-01-22 | Nippon Oil Corp | Method for manufacturing hydrogen-absorbing carbon material, and hydrogen-absorbing method |
| JP2004122031A (en) * | 2002-10-03 | 2004-04-22 | Toshiba Corp | Catalyst for synthesizing carbon fiber, method of producing carbon fiber, catalyst material for fuel cell, and method of producing catalyst material for fuel cell |
| JP2004238240A (en) * | 2003-02-05 | 2004-08-26 | Nissan Motor Co Ltd | Gas storage material, method of manufacturing the same and gas storage tank |
| JP2005330151A (en) * | 2004-05-20 | 2005-12-02 | Nikon Corp | Carbon material having cavity layer and its producing method |
| JP2007152492A (en) * | 2005-12-05 | 2007-06-21 | Bridgestone Corp | Metallic nanotube and method of producing the same |
| JP2009185378A (en) * | 2008-02-05 | 2009-08-20 | Korea Inst Of Machinery & Materials | Hollow metal fiber for absorbing electromagnetic wave and its manufacturing method |
| JP2010037623A (en) * | 2008-08-07 | 2010-02-18 | Surface Giken Kk | Plating method for carbon material and method for producing carbon material |
| JP2012006819A (en) * | 2010-06-23 | 2012-01-12 | Korea Inst Of Science & Technology | Method for fabricating composite material comprising nano carbon and metal or ceramic |
| JP2012211364A (en) * | 2011-03-31 | 2012-11-01 | Erc:Kk | Method for plating carbon material, and method for plating substrate containing carbon material and resin |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6406750B1 (en) * | 1999-05-28 | 2002-06-18 | Osaka Municipal Government | Process of forming catalyst nuclei on substrate, process of electroless-plating substrate, and modified zinc oxide film |
| CN1089121C (en) * | 1999-06-09 | 2002-08-14 | 冶金工业部钢铁研究总院 | Chemical nickel-plating method for surface of metal material |
| DE60239443D1 (en) * | 2001-10-24 | 2011-04-28 | Rohm & Haas Elect Mat | Stabilizers for electroless plating solutions and method of use |
| KR20060127584A (en) * | 2005-06-08 | 2006-12-13 | 삼성전자주식회사 | Method for separating of semiconductor and metal carbon nano tube |
| KR100721921B1 (en) * | 2005-10-13 | 2007-05-28 | 주식회사 포스코 | Method for manufacturing carbon nano tubes coated by transition metal elements in nanoscale for field emission based lighting source |
| US20080173864A1 (en) * | 2007-01-20 | 2008-07-24 | Toshiba America Research, Inc. | Carbon nanotube transistor having low fringe capacitance and low channel resistance |
| CN100564595C (en) * | 2007-05-23 | 2009-12-02 | 湖北工业大学 | The method of multiple-wall carbon nanotube chemical nickel plating on surface zinc |
| TW201041009A (en) * | 2009-05-08 | 2010-11-16 | Univ Nat Taiwan Science Tech | Fabrication method of carbon nanotube field emission cathode |
| KR101261184B1 (en) * | 2009-07-01 | 2013-05-09 | 히타치가세이가부시끼가이샤 | Coated conductive particles and method for producing same |
| DE102010011269B4 (en) * | 2009-11-10 | 2014-02-13 | Ami Doduco Gmbh | A method of depositing a palladium layer suitable for wire bonding onto circuit traces of a circuit board and using a palladium bath in the method |
| CN101818337A (en) * | 2009-11-16 | 2010-09-01 | 兰州理工大学 | Coating method of high-density Ni layer of carbon nano tube |
-
2012
- 2012-03-15 KR KR1020120026650A patent/KR101365457B1/en not_active IP Right Cessation
-
2013
- 2013-01-21 US US13/745,959 patent/US20130243974A1/en not_active Abandoned
- 2013-01-24 JP JP2013010975A patent/JP5602260B2/en not_active Expired - Fee Related
- 2013-02-05 CN CN201310045558.7A patent/CN103303897B/en not_active Expired - Fee Related
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201484A (en) * | 1987-10-06 | 1989-08-14 | Hitachi Ltd | Chemical nickel plating liquid and method of using said liquid |
| JPH05101972A (en) * | 1991-09-25 | 1993-04-23 | Matsushita Electric Ind Co Ltd | Method for forming electrode on ceramic |
| JPH08124577A (en) * | 1994-08-31 | 1996-05-17 | Sumitomo Electric Ind Ltd | Manufacture of metallic porous material |
| JP2003246613A (en) * | 2002-02-26 | 2003-09-02 | Denso Corp | Metal-added carbon material manufacturing method, and electrode material for fuel cell, catalyst carrier for chemical reaction and gas storage material obtained by using the metal-added carbon material manufactured thereby |
| JP2004018973A (en) * | 2002-06-18 | 2004-01-22 | Nippon Oil Corp | Method for manufacturing hydrogen-absorbing carbon material, and hydrogen-absorbing method |
| JP2004122031A (en) * | 2002-10-03 | 2004-04-22 | Toshiba Corp | Catalyst for synthesizing carbon fiber, method of producing carbon fiber, catalyst material for fuel cell, and method of producing catalyst material for fuel cell |
| JP2004238240A (en) * | 2003-02-05 | 2004-08-26 | Nissan Motor Co Ltd | Gas storage material, method of manufacturing the same and gas storage tank |
| JP2005330151A (en) * | 2004-05-20 | 2005-12-02 | Nikon Corp | Carbon material having cavity layer and its producing method |
| JP2007152492A (en) * | 2005-12-05 | 2007-06-21 | Bridgestone Corp | Metallic nanotube and method of producing the same |
| JP2009185378A (en) * | 2008-02-05 | 2009-08-20 | Korea Inst Of Machinery & Materials | Hollow metal fiber for absorbing electromagnetic wave and its manufacturing method |
| JP2010037623A (en) * | 2008-08-07 | 2010-02-18 | Surface Giken Kk | Plating method for carbon material and method for producing carbon material |
| JP2012006819A (en) * | 2010-06-23 | 2012-01-12 | Korea Inst Of Science & Technology | Method for fabricating composite material comprising nano carbon and metal or ceramic |
| JP2012211364A (en) * | 2011-03-31 | 2012-11-01 | Erc:Kk | Method for plating carbon material, and method for plating substrate containing carbon material and resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016074578A (en) * | 2014-10-07 | 2016-05-12 | ドンイー ホールディングス カンパニー リミテッド | Metal and oxide hybrid-coated nanocarbon production process |
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