KR101185009B1 - Manufacturing method of metal composite carbon nano tube - Google Patents

Manufacturing method of metal composite carbon nano tube Download PDF

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KR101185009B1
KR101185009B1 KR1020040111840A KR20040111840A KR101185009B1 KR 101185009 B1 KR101185009 B1 KR 101185009B1 KR 1020040111840 A KR1020040111840 A KR 1020040111840A KR 20040111840 A KR20040111840 A KR 20040111840A KR 101185009 B1 KR101185009 B1 KR 101185009B1
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김선복
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재단법인 포항산업과학연구원
주식회사 포스코
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Abstract

본 발명은 카본나노튜브(CNT)에 금속을 코팅하여 카본나노튜브 금속의 복합체를 만드는 방법에 관한 것으로, 그 구성은 부피비로 1:1의 아세톤 / 증류수용액에서 카본나노튜브를 초음파로 세척하고, 그를 알칼리세척 후 증류수세척 및 산 세척 후 증류수세척을 순차적으로 실시하는 단계;The present invention relates to a method of making a composite of carbon nanotube metal by coating a metal on the carbon nanotube (CNT), the configuration is ultrasonic cleaning of carbon nanotubes in acetone / distilled water of 1: 1 by volume ratio, Performing alkaline washing followed by distilled water washing and acid washing followed by distilled water washing;

상기 단계를 거친 카본나노튜브를 Sn++와 PdCl2 방식으로 60～100℃의 0.1mol SnCl2 / 0.1mol HCl 용액에 침지시켜 예민화 처리하고 그를 다시 0.1mol PdCl2 / 0.2mol EDTA / 0.5mol HF 용액에서 활성화 처리하는 단계;0.1 mol SnCl 2 / of 60 ~ 100 ℃ in the carbon nanotubes having the above steps by Sn ++ and PdCl 2 method Immersion in 0.1 mol HCl solution to subject it to sensitization, followed by activation treatment in 0.1 mol PdCl 2 / 0.2 mol EDTA / 0.5 mol HF solution;

상기의 단계를 거친 카본나노튜브를 하기 조건의 도금용액에서 Carbon nanotubes subjected to the above steps in the plating solution of the following conditions

Nickel Sulfate(니켈원) NiSO4.6H2O(0.12mol/L)Nickel Sulfate NiSO 4 .6H 2 O (0.12 mol / L)

DMAB(환원제) (CH3)2HNBH3(0.5~3.0g/L)DMAB (reducing agent) (CH 3 ) 2 HNBH 3 (0.5-3.0 g / L)

Sodium Acetate(착화제) CH3COONa.3H2O(0.07mol/L)Sodium Acetate CH 3 COONa.3H 2 O (0.07 mol / L)

pH 4.3 10% H2SO4사용으로 pH조절pH 4.3 Adjust pH by using 10% H 2 SO 4

온도 90℃(±1℃)Temperature 90 degrees Celsius (± 1 degrees Celsius)

도금하는 단계를 포함하는 구성으로 이루어진다. It consists of a configuration comprising the step of plating.

카본나노튜브, 카본나노튜브 금속 복합체, 예민화, 활성화Carbon Nanotubes, Carbon Nanotubes Metal Composites, Sensitization, Activation

Description

카본나노튜브 금속 복합체 제조방법{Manufacturing method of metal composite carbon nano tube}Manufacturing method of metal composite carbon nano tube

도1은 본 발명에 의해 제조된 카본나노튜브 금속 복합체의 조직사진. 1 is a tissue photograph of the carbon nanotube metal composite prepared by the present invention.

도2는 카본나노튜브 비자화를 보여주는 그림 Figure 2 shows the carbon nanotubes non-magnetic

도3은 카본나노튜브 금속 복합체의 자화를 보여주는 그림Figure 3 shows the magnetization of the carbon nanotube metal composite

본 발명은 카본나노튜브(CNT)에 금속을 코팅하여 카본나노튜브 금속의 복합체를 만드는 방법에 관한 것으로, 강자성체의 금속을 카본나노튜브에 코팅하여 자장중 성형과 비용이 저렴하며 대량의 카본나노튜브 금속 복합체를 제조하고자 하는 것이다. The present invention relates to a method of making a composite of carbon nanotube metal by coating a metal on the carbon nanotube (CNT), the coating of the ferromagnetic metal on the carbon nanotube in the form of magnetic field and low cost and a large amount of carbon nanotube To prepare a metal complex.

카본나노튜브는 나노 크기에 내부가 비어있는 탄소 튜브형태로서 그 제조비용이 저렴하고 여러 가지 특성을 보유하고 있어 산업에 활용할 수 있는 가능성이 큰 물질이다. 그 중에서 전자재료로서 그 발광효과는 디스플레이 제품에 응용이 가능한 것으로 알려져 있다. Carbon nanotubes are nano-sized, hollow carbon tubes, which are cheap to manufacture and possess various characteristics, making them highly applicable to the industry. Among them, the light emitting effect of the electronic material is known to be applicable to display products.

이러한 발광소자로서의 카본나노튜브는 그 배열방위에 따라서 발광효과(밝 기)가 달라지는데 카본나노튜브의 길이방향에 따라 정렬이 가능하고 금속산화물인 NiO, MgO, ZnO와 같은 이차전자 방출 능력이 우수한 물질이 코팅되어 있을 경우 그 효과는 크게 향상될 수 있다.Carbon nanotubes as light emitting devices have different light emitting effects (brightness) depending on their arrangement directions. The carbon nanotubes can be aligned in the longitudinal direction of carbon nanotubes and have excellent secondary electron emission ability such as metal oxides such as NiO, MgO, and ZnO. If it is coated, the effect can be greatly improved.

또한, 나노 크기의 카본나노튜브는 그 입자 크기가 극 미세한 만큼 일정한 정렬에 의한 성형체로 제작이 된다면 그 표면적의 극대화로 인한 촉매제로서의 상업화도 가능하다.In addition, nano-sized carbon nanotubes can be commercialized as catalysts due to the maximization of their surface area if the particles are manufactured in a molded body with a constant alignment as the particle size is extremely fine.

종래의 코팅방법으로는 CVD 방법과 플라즈마를 이용한 방법 등이 있으나 이는 생산 단가가 높으며 카본나노튜브 선단부분 만을 코팅하기 때문에 그 효과가 미약하다.Conventional coating methods include a CVD method and a plasma method, but the production cost is high and the effect is weak because only the carbon nanotube tip portion is coated.

본 발명은 수용액 중에서 금속을 환원제로 환원시켜 카본나노튜브 전표면에 코팅시키는 무전해도금 방식을 이용한 것으로, 강자성체의 금속을 카본나노튜브에 코팅하여 자장중 성형과 비용이 저렴하며 대량의 카본나노튜브 금속 복합체를 제조하는 방법을 제공함에 그 목적이 있다. The present invention uses an electroless plating method of coating a metal nanotube on the entire surface of a carbon nanotube by reducing the metal with a reducing agent in an aqueous solution. Its purpose is to provide a method for producing a metal composite.

상기 목적을 달성하기 위한 본 발명의 카본나노튜브 금속 복합체 제조방법의 특징적인 기술적 구성은, 부피비로 1:1의 아세톤 / 증류수용액에서 카본나노튜브를 초음파로 세척하고, 그를 알칼리세척 후 증류수세척 및 산 세척 후 증류수세척을 순차적으로 실시하는 단계;Characteristic technical configuration of the carbon nanotube metal composite production method of the present invention for achieving the above object is, by ultrasonic cleaning of carbon nanotubes in acetone / distilled aqueous solution in a volume ratio of 1: 1, washed with distilled water after alkaline washing and Carrying out distilled water washing sequentially after acid washing;

상기 단계를 거친 카본나노튜브를 Sn++와 PdCl2 방식으로 60～100℃의 0.1mol SnCl2 / 0.1mol HCl 용액에 침지시켜 예민화 처리하고 그를 다시 0.1mol PdCl2 / 0.2mol EDTA / 0.5mol HF 용액에서 활성화 처리하는 단계;0.1 mol SnCl 2 / of 60 ~ 100 ℃ in the carbon nanotubes having the above steps by Sn ++ and PdCl 2 method Immersion in 0.1 mol HCl solution to subject it to sensitization, followed by activation treatment in 0.1 mol PdCl 2 / 0.2 mol EDTA / 0.5 mol HF solution;

상기의 단계를 거친 카본나노튜브를 하기 조건의 도금용액에서 Carbon nanotubes subjected to the above steps in the plating solution of the following conditions

Nickel Sulfate(니켈원): NiSO4.6H2O(0.12mol/L)Nickel Sulfate: NiSO 4 .6H 2 O (0.12 mol / L)

DMAB(환원제) (CH3)2HNBH3(0.5~3.0g/L)DMAB (reducing agent) (CH 3 ) 2 HNBH 3 (0.5-3.0 g / L)

Sodium Acetate(착화제) CH3COONa.3H2O(0.07mol/L)Sodium Acetate CH 3 COONa.3H 2 O (0.07 mol / L)

pH 4.3 10% H2SO4사용으로 pH조절pH 4.3 Adjust pH by using 10% H 2 SO 4

온도 90℃(±1℃)Temperature 90 degrees Celsius (± 1 degrees Celsius)

도금하는 단계를 포함하는 구성으로 이루어진다.It consists of a configuration comprising the step of plating.

그리고, 상기 알칼리세척은 부피비로 1:5의 NH4OH/H2O 용액에서 60～100℃로 하고, 상기 산 세척은 부피비로 1:6 HCl / H2O의 용액에서 60～100℃로 한다.In addition, the alkaline washing is 60 ~ 100 ℃ in a 1: 5 NH 4 OH / H 2 O solution by volume ratio, the acid wash is 60 ~ 100 ℃ in a 1: 6 HCl / H 2 O solution by volume ratio. do.

상기와 같은 특징을 갖는 본 발명의 카본나노튜브 금속 복합체 제조방법을 실시예를 들어 설명하면 다음과 같다. Referring to the carbon nanotube metal composite manufacturing method of the present invention having the characteristics as described above with reference to Examples.

(실시예)(Example)

본 발명에서 응용한 복합체의 금속은 Ni 및 Ni-B로서 일반적인 Ni-B 무전해도금은 수소화붕소화합물, 디메칠아민모란(DMAB), 디에칠아민보란(DEAB), 트리메칠 아민보란(TMAB) 등이 있으며 DMAB를 사용하는 산성도금욕에서의 반응은 다음과 같다. The metals of the composite applied in the present invention are Ni and Ni-B. In general, Ni-B electroless plating is a borohydride compound, dimethylamine peony (DMAB), diethylamine borane (DEAB), trimethyl amine borane (TMAB). The reaction in acidic plating bath using DMAB is as follows.

3Ni2++(CH3)2HNBH3+3H2O →3Ni+H3BO 3+(CH3)2H2N++5H+ 3Ni 2+ + (CH 3 ) 2 HNBH 3 + 3H 2 O → 3Ni + H 3 BO 3 + (CH 3 ) 2 H 2 N + + 5H +

4Ni2++2(CH3)2HNBH3+3H2O →2Ni+Ni2B+H 3BO3+2(CH3)2HN++6H+ 4Ni 2+ +2 (CH 3 ) 2 HNBH 3 + 3H 2 O → 2Ni + Ni 2 B + H 3 BO 3 +2 (CH 3 ) 2 HN + + 6H +

HCl+(CH3)2HNBH3+3H2O →H3BO3+(CH3 )2HNHCl+3H2↑ HCl + (CH 3 ) 2 HNBH 3 + 3H 2 O → H 3 BO 3 + (CH 3 ) 2 HNHCl + 3H 2 ↑

등이다. And so on.

따라서 석출물은 Ni2B와 Ni를 내포한 Ni금속나노복합체 합금으로서 자성의 특성을 가지므로 자장 중 성형에 의한 일정한 배열을 가지는 성형체가 가능하고 코팅 후 후처리로서 산화에 의한 금속산화물이 코팅된 카본나노튜브 복합체 역시 가능하다.Therefore, the precipitate is Ni 2 B and Ni containing Ni metal nanocomposite alloy having magnetic properties, so it is possible to have a molded body having a certain arrangement by molding in the magnetic field, and carbon coated with metal oxide by oxidation as a post-treatment after coating. Nanotube composites are also possible.

본 발명에서 비금속(카본나노튜브)에 금속을 도금하기 위해서는 가장 중요한 공정이 전처리 공정인 바, 먼저 비금속인 카본나노튜브 표면에 이물질을 제거하기 위하여 1:1의 아세톤/증류수(부피비) 용액에서 초음파로 5분간 세척하였다.In the present invention, in order to plate the metal on the non-metal (carbon nanotube), the most important process is a pretreatment process. First, in order to remove the foreign matter on the surface of the non-metal carbon nanotube, ultrasonic waves in a 1: 1 acetone / distilled water (volume ratio) solution Washed for 5 minutes.

그리고, 알카리 세척으로 1:5 비율의 NH4OH/H2O(부피비)용액에서 80℃ 5분간 및 산세로 1:6 HCl//H2O(부피비)용액에서 80℃ 5분간 더욱 완벽한 세정작업을 실시하였다. 이때 각각의 공정 후에는 반드시 증류수를 이용하여 세척작업을 실시하였다.Alkaline washing is more complete at 80 ° C for 5 minutes in a 1: 5 ratio of NH 4 OH / H 2 O (volume ratio) and at 80 ° C for 5 minutes in a 1: 6 HCl // H 2 O (volume ratio) solution. Work was carried out. At this time, after each process, the washing operation was always performed using distilled water.

상기와 같이 하여 카본나노튜브의 전처리가 끝나면 그를 예민화 및 활성화처 리 해야하는데, 그 방법은 Sn++와 PdCl2 방식으로 70℃의 0.1mol SnCl2 / 0.1mol HCl 용액에 수초간 침지시켜 예민화 처리하고, 그를 다시 0.1mol PdCl2 / 0.2mol EDTA / 0.5mol HF 용액에서 수초간 활성화 처리한다.To be the end of the sensitization and activation processing him pretreatment of the carbon nanotube Li as described above, the method is sensitive to a few seconds, immersed in 0.1mol SnCl 2 / 0.1mol HCl solution of 70 ℃ with Sn ++ and PdCl 2 way And then activated again for several seconds in a 0.1 mol PdCl 2 / 0.2 mol EDTA / 0.5 mol HF solution.

이때, 사용하는 EDTA는 미세한 나노입자에 금속의 환원 물질이 미세하게 환원될 수 있도록 핵 생성을 촉진시키는 역할을 한다.At this time, the EDTA used serves to promote nucleation so that the reducing material of the metal is finely reduced to the fine nanoparticles.

상기와 같이 예민화 및 활성화처리 공정을 마친 카본나노튜브는 초음파 발진기로 분산을 시킨 후 도금조로 옮겨 하기와 같은 도금용액에서 도금을 실시하여 카본나노튜브 금속 복합체를 제조하였다. Carbon nanotubes that have been subjected to the sensitization and activation treatment as described above were dispersed in an ultrasonic oscillator and transferred to a plating bath to prepare a carbon nanotube metal composite by plating in a plating solution as described below.

Nickel Sulfate(니켈원): NiSO4.6H2O(0.12mol/L)Nickel Sulfate: NiSO 4 .6H 2 O (0.12 mol / L)

DMAB(환원제) (CH3)2HNBH3(0.5~3.0g/L)DMAB (reducing agent) (CH 3 ) 2 HNBH 3 (0.5-3.0 g / L)

Sodium Acetate(착화제) CH3COONa.3H2O(0.07mol/L)Sodium Acetate CH 3 COONa.3H 2 O (0.07 mol / L)

pH 4.3 10% H2SO4사용으로 pH조절pH 4.3 Adjust pH by using 10% H 2 SO 4

온도 90℃(±1℃)Temperature 90 degrees Celsius (± 1 degrees Celsius)

상기와 같이하여 카본나노튜브 금속 복합체를 제조하고 제조된 카본나노튜브 금속 복합체를 투과전자현미경으로 관찰한 조직사진을 도1에 나타내었고, 도2 및 도3은 본 발명에 의해 제조된 카본나노튜브 금속 복합체의 자장중 성형이 가능한 것을 비교하여 보여주고 있다.The carbon nanotube metal composite was prepared as described above, and the structure of the carbon nanotube metal composite prepared according to the transmission electron microscope is shown in FIG. 1, and FIGS. 2 and 3 illustrate the carbon nanotubes prepared according to the present invention. It is shown that the molding of the metal composite in the magnetic field is possible.

상술한 바와 같은 방법으로 제조된 본 발명의 카본나노튜브 금속 복합체는 디스플레이 제품에 응용이 가능하고, 또, 표면적의 극대화로 인한 촉매제로서의 상업화도 가능한 효과가 있다. Carbon nanotube metal composite of the present invention prepared by the method as described above can be applied to display products, and there is an effect that can be commercialized as a catalyst by maximizing the surface area.

Claims (3)

카본나노튜브에 Ni를 무전해도금 하여 카본나노튜브 금속 복합체를 제조하는 방법으로서,As a method of producing a carbon nanotube metal composite by electroless plating Ni on a carbon nanotube, 부피비로 1:1의 아세톤 / 증류수용액에서 카본나노튜브를 초음파로 세척하고, 그를 알칼리세척 후 증류수세척한 다음, 산 세척 후 증류수세척하는 과정을 순차적으로 실시하는 단계;Performing a step of sequentially washing carbon nanotubes in an acetone / distilled aqueous solution at a volume ratio of 1 by ultrasonic, washing the distilled water after alkali washing, and then washing the distilled water after acid washing; 상기 단계를 거친 카본나노튜브를 Sn++와 PdCl2 방식으로 60～100℃의 0.1mol SnCl2 / 0.1mol HCl 용액에 침지시켜 예민화 처리하고 그를 다시 0.1mol PdCl2 / 0.2mol EDTA / 0.5mol HF 용액에서 활성화 처리하는 단계;0.1 mol SnCl 2 / of 60 ~ 100 ℃ in the carbon nanotubes having the above steps by Sn ++ and PdCl 2 method Immersion in 0.1 mol HCl solution to subject it to sensitization, followed by activation treatment in 0.1 mol PdCl 2 / 0.2 mol EDTA / 0.5 mol HF solution; 상기의 단계를 거친 카본나노튜브를 하기 조건의 도금용액에서 Carbon nanotubes subjected to the above steps in the plating solution of the following conditions Nickel Sulfate(니켈원): NiSO4.6H2O(0.12mol/L)Nickel Sulfate: NiSO 4 .6H 2 O (0.12 mol / L) DMAB(환원제) (CH3)2HNBH3(0.5~3.0g/L)DMAB (reducing agent) (CH 3 ) 2 HNBH 3 (0.5-3.0 g / L) Sodium Acetate(착화제) CH3COONa.3H2O(0.07mol/L)Sodium Acetate CH 3 COONa.3H 2 O (0.07 mol / L) pH 4.3 10% H2SO4사용으로 pH조절pH 4.3 Adjust pH by using 10% H 2 SO 4 온도 90℃(±1℃)Temperature 90 degrees Celsius (± 1 degrees Celsius) 도금하는 단계를 포함하는 구성을 특징으로 하는 카본나노튜브 금속 복합체 제조방법.Carbon nanotube metal composite manufacturing method characterized in that the composition comprising the step of plating. 제1항에 있어서, 상기 알칼리세척은 부피비로 1:5의 NH4OH/H2O 용액에서 60～100℃로 하는 것을 특징으로 하는 카본나노튜브 금속 복합체 제조방법.The method of claim 1, wherein the alkaline cleaning is a carbon nanotube metal composite manufacturing method, characterized in that 60 to 100 ℃ in a volume ratio of 1: 5 NH 4 OH / H 2 O solution. 제1항에 있어서, 상기 산 세척은 부피비로 1:6 HCl / H2O의 용액에서 60～100℃로 하는 것을 특징으로 하는 카본나노튜브 금속 복합체 제조방법. The method of claim 1, wherein the acid wash is a carbon nanotube metal composite manufacturing method, characterized in that 60 to 100 ℃ in a solution of 1: 6 HCl / H 2 O by volume ratio.
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