KR20090089012A - Highly conductive carbon nanofibers and polymer / carbon nanofiber nanocomposites using the same - Google Patents
Highly conductive carbon nanofibers and polymer / carbon nanofiber nanocomposites using the same Download PDFInfo
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- KR20090089012A KR20090089012A KR1020080014314A KR20080014314A KR20090089012A KR 20090089012 A KR20090089012 A KR 20090089012A KR 1020080014314 A KR1020080014314 A KR 1020080014314A KR 20080014314 A KR20080014314 A KR 20080014314A KR 20090089012 A KR20090089012 A KR 20090089012A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
본 발명은 고전도성 탄소나노섬유를 이용한 탄소나노섬유/고분자 나노복합재에 관한 것으로서, 보다 상세하게는 탄소나노섬유의 합성공정을 정밀하게 제어하여 전기전도도 특성 발현이 되는 특정한 헤링본 구조의 탄소나노섬유 및 이의 겉보기 밀도를 최적화하는 공정을 제공하는 것이다. 또한 본 발명은 ⅰ) 흑연 망상면이 섬유축 방향에 대하여 10∼20도 기울기를 갖고 겉보기 밀도가 0.01∼0.06g/cm3인 헤링본 구조를 갖는 탄소나노섬유를 제조하는 단계; ⅱ) 건식분쇄방식을 이용하여 탄소나노섬유의 번들을 풀어 겉보기 밀도를 줄이는 단계; 및 ⅲ) 탄소나노섬유와 고분자 수지를 용융 혼합하여 복합화하는 단계를 포함하여 제조된 탄소나노섬유/고분자 나노복합재를 제공한다.The present invention relates to carbon nanofibers / polymer nanocomposites using high-conductivity carbon nanofibers, and more particularly, to carbon nanofibers having a specific herringbone structure which exhibits electrical conductivity characteristics by precisely controlling the synthesis process of carbon nanofibers. It is to provide a process to optimize its apparent density. In another aspect, the present invention provides a method for preparing carbon nanofibers having a herringbone structure in which the graphite network surface has an inclination of 10 to 20 degrees with respect to the fiber axis direction and an apparent density of 0.01 to 0.06 g / cm 3 ; Ii) reducing the apparent density by releasing bundles of carbon nanofibers using a dry grinding method; And iii) melting and mixing carbon nanofibers and polymer resin to provide a composite carbon nanofibers / polymer nanocomposite.
Description
본 발명은 고전도성을 나타내는 탄소나노섬유(carbon nanofiber) 및 이를 이용한 탄소나노섬유/고분자 나노복합재에 관한 것이다. 더욱 상세하게는, 탄소나노섬유의 합성공정을 정밀하게 제어하여 전기전도도 특성 발현이 되는 특정한 헤링본 구조의 탄소나노섬유를 제조하고 이의 겉보기 밀도를 최적화시켜 고 전도성을 나타내는 탄소나노섬유 및 이를 이용한 나노복합재에 관한 것이다.The present invention relates to carbon nanofibers having high conductivity and carbon nanofibers / polymer nanocomposites using the same. More specifically, carbon nanofibers having a specific herringbone structure exhibiting electrical conductivity characteristics by precisely controlling the synthesis process of carbon nanofibers, and optimizing their apparent density, exhibiting high conductivity and nanocomposites using the same It is about.
따라서 본 발명은 전기전도성이 기존의 탄소나노섬유보다 월등히 향상되어, 탄소나노튜브와는 유사한 수준의 값을 나타내는 새로운 고전도성 탄소나노섬유/고분자 나노복합재 제조에 관한 것이다. 따라서 전도성 고분자 복합재의 충전재로서 고가의 탄소나노튜브 대신 제조비용이 저렴한 탄소나노섬유를 이용함으로서 이를 이용한 응용제품의 가격 경쟁력을 높일 수 있는 경제적 이점을 제공할 수 있다. Therefore, the present invention relates to the production of a new highly conductive carbon nanofibers / polymer nanocomposites exhibiting significantly improved electrical conductivity compared to conventional carbon nanofibers, showing a level similar to that of carbon nanotubes. Therefore, by using carbon nanofibers, which are inexpensive to manufacture, instead of expensive carbon nanotubes as fillers for conductive polymer composites, they can provide an economic advantage that can increase the price competitiveness of applications using them.
1991년도 탄소나노튜브(carbon nanotube)의 발견으로 인하여 더욱 더 나노탄소물질에 대한 관심이 집중되고 세계적인 연구개발이 진행되면서 나노탄소소재가 갖고 있는 다양하고 유익한 물리적, 화학적 특성들은 최근 구조 제어 기술의 발달로 인하여 고분자 보강재 분야, 의약품분야, 에너지 저장분야, 고분자합성 촉매담지 분야 등에서 새로운 소재 가치를 추구하는 중이다.As the discovery of carbon nanotubes in 1991 attracted more and more attention to nanocarbon materials and global research and development, the various and beneficial physical and chemical properties of nanocarbon materials have been recently developed. As a result, the company is pursuing new material values in the field of polymer reinforcement, pharmaceuticals, energy storage, and polymer catalyst support.
나노탄소소재 중에서 탄소나노섬유(carbon nanofiber)는 제조되는 촉매조성에 따라 600℃이하의 온도에서도 섬경을 50nm 이하로 제공하면서 높은 흑연 결정화도를 나타낼 수 있어 제조 에너지 비용 측면에서 탄소나노튜브보다 유리하며 제조되는 탄소나노섬유의 촉매 수율은 탄소나노튜브에 비해 수배에서 수십 배 이상 높아 연속식 양산공정 적용 시 제조 원가를 탄소나노튜브에 비해 2배 이상 낮출 수 있게 된다.Among nano carbon materials, carbon nanofibers are more advantageous than carbon nanotubes in terms of manufacturing energy cost because they can provide high crystallinity of crystallinity while providing island diameters of 50 nm or less even at temperatures below 600 ° C, depending on the catalyst composition. The catalyst yield of the carbon nanofibers is several times to several tens of times higher than that of the carbon nanotubes, and thus, the manufacturing cost can be lowered more than two times compared to the carbon nanotubes when the continuous mass production process is applied.
그러므로 기존의 카본 복합재 시장을 주도하고 있는 탄소섬유(Carbon Fiber) 가격대비 성능과 비교할 때 탄소나노튜브보다 탄소나노섬유가 복합재의 충전재로서의 가격 경쟁력이 클 것으로 기대되고 있다. 특히 탄소나노섬유는 합성조건에 따라 헤링본(herringbone) 구조, 플레이트 구조(platelet), 튜블라(tubelar) 구조가 만들어 질 수 있으며 특히 흑연 망상면(graphite basal plane)이 섬유 성장 방향에 경사지거나 수직된 구조는 리튬이온전지용 음극재의 인터칼레이션 물질로서 혹은 커패시터의 전하 저장매체 소재로서 응용가능성이 높은 것으로 보고되고 있다.Therefore, carbon nanofibers are expected to be more competitive as fillers for composite materials than carbon nanotubes compared to carbon fiber cost-performance, which leads the existing carbon composites market. Particularly, carbon nanofibers can be made of herringbone structure, platelet, and tubelar structure according to the synthetic conditions. In particular, the graphite basal plane is inclined or perpendicular to the fiber growth direction. The structure is reported to have high applicability as an intercalation material of a negative electrode material for a lithium ion battery or as a charge storage medium material of a capacitor.
그러나 섬유상 카본소재의 수요는 응용분야에 따라 고전기전도성, 고열전도성, 고강도등 다양한 소재 물성을 요구하지만 현실적으로 이와 같은 여러 가지 물성을 동시에 만족하는 소재는 아직까지 보고된 바가 없다. 예를 들면, 엔지니어링 플라스틱과 복합재의 경우 탄소나노튜브는 전기전도성이 우수한 반면 강도 특성이 부족하고, 탄소나노섬유는 강도특성이 우수하나 전기전도도 특성이 낮은 단점이 있다. 특히 탄소나노섬유는 섬경이나 구조에 따라서 발현 물성에 현격히 차이가 나는 것으로 알려져 있다. 탄소나노튜브보다 표면 개질이 용이한 구조를 갖는 탄소나노섬유는 다양한 고분자, 세라믹, 금속 복합매질 내에서의 우수한 분산성, 계면특성을 나타내지만 이들과 복합화하는 가혹한 가공조건에서 소재의 특성을 상실하는 경우가 많아 산업적 이용이 제한되고 있다.However, the demand for fibrous carbon materials requires a variety of material properties such as high conductivity, high thermal conductivity, and high strength, depending on the field of application, but in reality, there are no materials that satisfy these properties at the same time. For example, in the case of engineering plastics and composites, carbon nanotubes have excellent electrical conductivity while lacking strength characteristics, and carbon nanofibers have excellent strength characteristics but low electrical conductivity characteristics. In particular, carbon nanofibers are known to have a marked difference in their physical properties depending on their size and structure. Carbon nanofibers, which have a structure that is more easily modified than carbon nanotubes, exhibit excellent dispersibility and interfacial properties in various polymers, ceramics, and metal composite media, but lose their material properties under the harsh processing conditions combined with them. In many cases, industrial use is limited.
대한민국 특허 등록 제10-0691837호 '탄소 나노 섬유 및 폴리이미드 복합물 및 그 제조 방법'에서는 탄소나노섬유를 이용한 인시츄 고분자 합성법(in-situ polymerization)을 예시하고 있으나 복합화 공정 도입 시 제조비용이 많이 들고 적용 고분자 선정에 한계가 있다.Republic of Korea Patent Registration No. 10-0691837 'Carbon nanofibers and polyimide composites and manufacturing method thereof exemplifies in-situ polymerization using carbon nanofibers, but the manufacturing cost is high when the compounding process is introduced. There is a limit to the selection of polymers.
한편 탄소나노섬유의 결정 구조 해석에 대한 연구는 미국의 Baker 및 N.M. Rodriguez 연구그룹에 의해 상세히 진행된 바 있다(J. Mater. Res. Vol8 : 3233~3250,1993). 대한민국 특허 등록 제10-0726368호 '섬유상 나노탄소', 대한민국 특허 등록 제10-0713609호 '섬유쌍 탄소', 대한민국 특허 등록 제10-0497775호 '탄소 나노 섬유 합성용 촉매 및 그 제조 방법과, 이를 이용한 탄소 나노 섬유 및 그 제조 방법', 대한민국 특허 등록 제10-0475254호 '신규 구조의 섬유상 탄소', 대한민국 특허 등록 제10-0542095호 '극세 섬유상 나노탄소 제조법' 등에서는 촉매 금속 조성물 제조에 전이 금속 외에 제2의 금속 혹은 제3의 금속을 도입하거나 촉매 담지체 도입 등을 통해 탄소나노섬유의 구조를 칼럼 구조(columnar structure), 직선형, 꼬인형, 가지형, 혹은 섬유쌍 구조, 단위소 개념이 있는 구조 등과 같이 세분화된 형태를 언급하고 있으며 탄소나노섬유의 섬경 또한 50nm 이하로 제조하는 방법을 기술하고 있다.Meanwhile, studies on the crystal structure analysis of carbon nanofibers have been conducted in Baker and N.M. This was done in detail by the Rodriguez research group (J. Mater. Res. Vol 8: 3233-3250, 1993). Republic of Korea Patent Registration No. 10-0726368 'Fiber-like nano carbon', Republic of Korea Patent Registration No. 10-0713609 'Fiber Pair Carbon', Republic of Korea Patent Registration No. 10-0497775 'Catalyst for synthesizing carbon nanofibers Used carbon nanofibers and a method of manufacturing the same, Korean Patent Registration No. 10-0475254 'New Fiber Fibrous Carbon', Korean Patent Registration No. 10-0542095 'Microfiber Nanocarbon Manufacturing Method', etc. In addition, the structure of the carbon nanofibers may be changed into a column structure, a straight line, a twisted shape, a branched shape, a fiber pair structure, or a unit element by introducing a second metal or a third metal or introducing a catalyst carrier. It refers to the subdivided form, such as the present structure, and describes the method of producing carbon nanofibers in less than 50 nm.
그러나 이러한 방법으로 제조한 탄소나노섬유의 경우 용융 혼합법등과 같은 고분자 수지와 복합화 하는 가혹한 가공조건에서 소재의 특성을 상실하여 전기전도도 발현이 안 되어 산업적 이용이 제한되고 있다. 이러한 물성 저하 원인을 찾고자 본 발명자는 탄소나노섬유의 제조공정을 정밀하게 제어하는 실험을 반복한 결과 헤링본 타입의 탄소나노섬유가 섬유 성장축에 대하여 흑연 망상면(graphite basal plane)의 배향각이 일정한 각도 범위와 특정한 겉보기 밀도(bulk density) 값을 보유할 때 전기전도도 물성 발현이 된다는 사실을 발견하고 본 발명을 완성하게 되었다. However, in the case of carbon nanofibers manufactured in this way, the characteristics of the material are lost under severe processing conditions complexed with polymer resins, such as melt mixing, and the like, and electrical conductivity is not expressed. In order to find the cause of such deterioration of properties, the inventors repeated the experiments to precisely control the manufacturing process of carbon nanofibers, and as a result, the herringbone-type carbon nanofibers have a constant angle of graphite basal plane with respect to the fiber growth axis. The present invention has been completed by discovering that electrical conductivity is also manifested in physical properties when possessing a range and specific bulk density values.
본 발명이 해결하고자 하는 과제는 상기와 같은 문제점, 즉 고분자 수지와 탄소나노섬유를 복합화 하는 가혹한 가공조건에서 탄소나노섬유가 소재의 특성을 상실하여 전기전도도 발현이 안 되는 문제점을 해결하기 위해, 나노촉매 제조기술 도입 및 탄소나노섬유의 제조공정을 정밀하게 제어함에 의해 제조된 탄소나노섬유의 미세구조와 겉보기 밀도가 전기전도성과 긴밀한 관계가 있음을 발견하여 전기전도성이 기존의 탄소나노섬유보다 월등히 뛰어나고, 더 나아가 탄소나노튜브와 비교하여 유사한 고전도성 발현이 가능한 탄소나노섬유/고분자 나노복합재를 개발코자 한 것이다. 즉 기존의 탄소나노섬유가 갖고 있는 열약한 전기전도성 물성을 극복한 신규한 방법으로서 정전기방지기능, 전자기차폐 기능이 요구되는 반도체 트레이, 전자기부품소재 등과 같은 응용 분야에 가격 경쟁력이 있는 고전도성 탄소나노섬유/고분자 복합재를 개발코자 한 것이다.The problem to be solved by the present invention is to solve the above problems, that is, the carbon nanofibers in the harsh processing conditions of complexing the polymer resin and carbon nanofibers in order to solve the problem that the electrical conductivity is not expressed by the loss of the material properties, nano By introducing a catalyst manufacturing technology and precisely controlling the manufacturing process of carbon nanofibers, we found that the microstructure and apparent density of carbon nanofibers produced were closely related to their electrical conductivity. Furthermore, it aims to develop carbon nanofibers / polymer nanocomposites with similar high conductivity expression compared to carbon nanotubes. In other words, it is a new method that overcomes the weak electrical conductivity properties of existing carbon nanofibers, and is a highly competitive carbon nanocomposite that is competitive in applications such as semiconductor trays and electromagnetic component materials requiring antistatic and electromagnetic shielding functions. To develop fiber / polymer composites.
본 발명의 목적은 ⅰ) 흑연 망상면이 섬유축 방향에 대하여 10∼20도 기울기를 갖고 겉보기 밀도가 0.01∼0.06g/cm3인 헤링본 구조를 갖는 탄소나노섬유를 제조 하는 단계; ⅱ) 건식분쇄방식을 이용하여 탄소나노섬유의 번들(carbon nanofiber bundles)을 풀어 겉보기 밀도를 줄이는 단계; 및 ⅲ) 탄소나노섬유와 고분자 수지를 용융 혼합하여 복합화하는 단계를 포함하여 제조된 탄소나노섬유/고분자 나노복합재를 제공하는 것이다.An object of the present invention is to prepare a carbon nanofiber having a herringbone structure in which the graphite network surface has an inclination of 10 to 20 degrees with respect to the fiber axis direction and an apparent density of 0.01 to 0.06 g / cm 3 ; Ii) reducing the apparent density by releasing bundles of carbon nanofibers using dry grinding; And iii) to provide a carbon nanofibers / polymer nanocomposites prepared by melting and mixing the carbon nanofibers and polymer resin composite.
또한 상기 헤링본 구조를 갖는 탄소나노섬유를 제조하는 단계는 ⅰ) Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb 및 In의 촉매군에서 선택된 1종 이상의 전이금속 촉매 또는 상기 금속의 알콕사이드, 옥사이드, 클로라이드, 나이트레이트, 카보네이트 형태의 촉매 혼합물을 400∼ 800℃에서 열산화 한 후 반응기 내에 분말 도포시키는 단계; 및 ⅱ) 촉매 혼합물을 수소와 질소 가스 혼합물로 400∼600℃ 반응 온도까지 승온시킨 후, 에틸렌, 아세틸렌, 메탄, 일산화탄소에서 선택된 1종 이상의 탄소 공급원을 수소 가스와 함께 반응 온도에서 0.1∼4시간 탄소화 증착 반응시키는 화학적 기상 증착단계로 구성됨을 특징으로 한다. In addition, the step of producing a carbon nanofiber having the herringbone structure is iii) Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In selected from the catalyst group Thermally oxidizing the above transition metal catalyst or catalyst mixture in the form of an alkoxide, oxide, chloride, nitrate, or carbonate of the metal at 400 to 800 ° C., followed by powder coating in a reactor; And ii) the catalyst mixture is heated to a reaction temperature of 400-600 ° C. with a mixture of hydrogen and nitrogen, and at least one carbon source selected from ethylene, acetylene, methane, and carbon monoxide is reacted with hydrogen gas at 0.1 to 4 hours carbon. It is characterized by consisting of a chemical vapor deposition step of the vapor deposition reaction.
또한 상기 촉매 혼합물은 합성 주촉매인 Fe, Co, Ni 외에 조촉매 역할을 하는 망간(Mn), 크롬(Cr), 텅스텐(W) 등을 사용하고, 금속 담지효과를 향상시키기 위해 알루미늄(Al), 마그네슘(Mg), 실리콘(Si) 등을 이용한 산화물 담지체를 사용함을 특징으로 한다.In addition, the catalyst mixture uses manganese (Mn), chromium (Cr), tungsten (W), etc., which acts as a promoter in addition to the synthetic main catalysts Fe, Co, Ni, and aluminum (Al) to improve the metal carrying effect. , An oxide carrier using magnesium (Mg), silicon (Si), or the like.
또한 상기 화학적 기상 증착 단계는 ⅰ) 촉매 혼합물을 수소가스 : 질소가스 (부피비, 1 : 1∼4) 혼합가스로 8∼12℃/분의 속도로 500∼600℃의 반응 온도까지 0.5∼2시간 승온 시키는 단계(R1); ⅱ) 촉매 혼합물을 수소가스 : 질소가스(부피비, 1 : 1∼4) 혼합가스로 500∼600℃ 반응 온도에서 0.1∼2시간 유지시키는 단계(R2); ⅲ) 가온된 촉매 혼합물에 수소가스 : 에틸렌 가스(부피비, 1 : 1∼4) 혼합가스를 0.1∼2시간 반응시키는 탄소화 반응 단계(R3); 및 ⅳ) 불활성 가스를 사용하여 상온까지 0.5∼2시간 냉각시키는 냉각단계(R4)로 구성됨을 특징으로 한다.In the chemical vapor deposition step, i) the catalyst mixture is a mixture of hydrogen gas: nitrogen gas (volume ratio, 1: 1-4) at a rate of 8-12 ° C./min to a reaction temperature of 500-600 ° C. for 0.5-2 hours. Raising the temperature (R1); Ii) maintaining the catalyst mixture in a hydrogen gas: nitrogen gas (volume ratio, 1: 1 to 4) mixed gas at a reaction temperature of 500 to 600 ° C. for 0.1 to 2 hours (R2); V) a carbonization reaction step (R3) for reacting a hydrogen gas: ethylene gas (volume ratio, 1: 1-4) mixed gas for 0.1 to 2 hours to a heated catalyst mixture; And iii) a cooling step (R4) for cooling 0.5-2 hours to room temperature using an inert gas.
또한 촉매 혼합물 내의 철, 코발트, 니켈 등의 전이금속 촉매금속과 Mn, Cr, Mo, W, Zr, Ti 등에서 선택된 불활성 금속 입자간의 중량비율이 90∼20 : 10∼80인 것을 특징으로 한다.In addition, the weight ratio between the transition metal catalyst metal, such as iron, cobalt, nickel, and the like, and the inert metal particles selected from Mn, Cr, Mo, W, Zr, Ti, etc. in the catalyst mixture is characterized in that 90 to 20: 10 to 80.
한편 상기 고분자 수지는 엔지니어링플라스틱(Engineering Plastics)인 것을 특징으로 한다.The polymer resin is characterized in that the engineering plastics (Engineering Plastics).
또한 상기 고분자 수지는 아크릴로니트릴부타디엔스티렌(ABS), 폴리카보네이트(PC), 아크릴로니트릴부타디엔스티렌/폴리카보네이트 복합수지(ABS/PC), 폴리부틸렌테레프탈레이트(PBT), 폴리에틸렌테레프탈레이트(PET), 폴리아마이드(PA), 폴리페닐렌설파이드(PPS), 폴리에테르에테르케톤(PEEK)에서 선택된 1종 이상의 수지 특징으로 한다. In addition, the polymer resin is acrylonitrile butadiene styrene (ABS), polycarbonate (PC), acrylonitrile butadiene styrene / polycarbonate composite resin (ABS / PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET) ), Polyamide (PA), polyphenylene sulfide (PPS), and polyether ether ketone (PEEK).
본 발명의 효과는 반도체 트레이용 전도성 고분자복합재 조성물로 고전도성 탄소나노섬유/고분자 나노복합재를 적용함으로써, 기존의 탄소나노섬유를 이용한 고분자 복합재 조성물과 비교하여 뛰어난 고전기전도성 고분자 복합재를 제조하는 방법을 제공함으로서, 고가의 탄소나노튜브를 사용하는 대신 제조비용이 저렴한 탄소나노섬유를 이용하여 이를 이용한 응용제품의 가격 경쟁력을 높일 수 있는 경제적 이점을 제공할 수 있다.The effect of the present invention is to provide a method for producing a highly conductive polymer composite excellent in comparison with a conventional polymer composite composition using carbon nanofibers by applying a high conductive carbon nanofibers / polymer nanocomposites as a conductive polymer composite composition for a semiconductor tray. By using the carbon nanofibers, which are inexpensive to manufacture, instead of using expensive carbon nanotubes, it is possible to provide an economic advantage to increase the price competitiveness of applications using the same.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
상기의 목적을 달성하기 위한 본 발명은 엔지니어링 플라스틱 고분자 수지 조성물에 탄소나노섬유를 나노복합화한 탄소나노섬유/고분자 나노복합재를 포함한다.The present invention for achieving the above object comprises a carbon nanofibers / polymer nanocomposites nanocomposite carbon nanofibers in the engineering plastic polymer resin composition.
본 발명에서 사용되는 엔지니어링 플라스틱 고분자 수지는 그 종류에 특정한 한정은 없으나 용융혼합법으로 사용이 가능한 것으로서 용용온도가 80∼350℃인 것이 바람직하다.The engineering plastic polymer resin used in the present invention is not particularly limited in its kind, but may be used by melt mixing, and the melting temperature thereof is preferably 80 to 350 ° C.
본 발명에서 사용되는 탄소나노섬유/고분자 나노복합재 제조방법은 다음과 같은 단계로 구성되어진다.The carbon nanofibers / polymer nanocomposite manufacturing method used in the present invention is composed of the following steps.
1단계 : 고전도성 탄소나노섬유 제조 단계Step 1: manufacturing high conductivity carbon nanofibers
2단계 : 탄소나노섬유의 겉보기 밀도를 낮추는 건식분쇄 단계Step 2: Dry grinding step to lower the apparent density of carbon nanofibers
3단계 : 탄소나노섬유/고분자 복합재를 용융 혼합하는 단계Step 3: melt mixing carbon nanofibers / polymer composite
탄소나노섬유 제조용 촉매는 이미 공지되어 있으며, 대표적인 촉매로는 전이금속 촉매인 Fe, Co, Ni 등이다 (CATAL.REV.-SCI.ENG., 42(4) 481-510(2000)).Catalysts for producing carbon nanofibers are already known, and representative catalysts are Fe, Co, Ni, and the like, which are transition metal catalysts (CATAL. REV.-SCI.ENG., 42 (4) 481-510 (2000)).
본 발명에서는 Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb 및 In로 이루어진 전이금속 촉매군에서 선택된 적어도 1종 이상의 금속원소를 포함하는 촉매를 사용한다. 본 발명에 사용되는 촉매는 상기 촉매 금속의 화합물 형태인 알콕사이드(alkoxide), 옥사이드(oxide), 클로라이드(chloride), 나이트레이트(nitrate), 카보네이트(carbonate)의 형태로 사용할 수 있다.In the present invention, a catalyst containing at least one metal element selected from the group of transition metal catalysts consisting of Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In is used. do. The catalyst used in the present invention may be used in the form of alkoxide, oxide, chloride, nitrate, carbonate, which are compounds of the catalyst metal.
탄소나노섬유의 균일성 및 섬경을 제어하기 위하여 합성 주촉매인 Fe, Co, Ni 외에 조촉매 역할을 하는 망간(Mn), 크롬(Cr), 텅스텐(W) 등을 사용할 수 있으며 금속 담지효과를 높이기 위하여 알루미늄(Al), 마그네슘(Mg), 실리콘(Si) 등을 이용한 산화물 담지법이 적용될 수 있다.To control the uniformity and fineness of carbon nanofibers, manganese (Mn), chromium (Cr), tungsten (W), etc., which act as cocatalysts, can be used in addition to the synthetic main catalysts Fe, Co, and Ni. In order to increase, an oxide supporting method using aluminum (Al), magnesium (Mg), silicon (Si), or the like may be applied.
또한 균일한 금속 나노촉매입자들을 담지하기 위해서 졸-겔공정, 침전법, 수열반응법, 메카노케미칼반응(mechanochemical reaction), 볼밀, 분무 열분해법, 분무건조법 등이 사용될 수 있다. 탄소나노섬유의 합성에 사용되는 금속촉매들은 1000℃ 이내 범위에서 바람직하게는 400∼800℃ 범위의 산화 분위기에서 열처리를 통해 촉매입자의 담지체 고정화 공정을 행하는 것이 바람직하다.In addition, a sol-gel process, precipitation method, hydrothermal reaction method, mechanochemical reaction, ball mill, spray pyrolysis method, and spray drying method may be used to support uniform metal nanocatalyst particles. Metal catalysts used for the synthesis of carbon nanofibers are preferably carried out in the carrier-immobilized process of the catalyst particles through heat treatment in an oxidizing atmosphere in the range of 1000 ° C to 400 ° C.
활성 촉매 담지량은 담지체 기준으로 볼 때 10∼80 중량% 범위에서 바람직하게는 30∼80 중량% 범위에서 제조하는 것이 촉매 수율을 극대화 할 수 있다.The amount of the active catalyst supported in the range of 10 to 80% by weight, preferably 30 to 80% by weight, can be maximized in terms of catalyst yield.
반응 온도는 400∼800℃ 범위에서 바람직하게는 450∼550℃ 범위이다. 반응 가스는 에틸렌, 아세틸렌, 메탄, 일산화탄소 등 다양하게 사용할 수 있으며 고전도도성 탄소나노섬유 제조에 있어서 에틸렌 가스를 사용하는 것이 바람직하다. 반응가스 비율은 반응 온도까지의 승온 단계(R1), 반응 온도에서 유지단계(R2), 반응단계(R3), 냉각단계(R4)로 구분하여 조절할 수 있다.The reaction temperature is preferably in the range of 450 to 550 ° C in the range of 400 to 800 ° C. The reaction gas may be used in various ways such as ethylene, acetylene, methane, carbon monoxide, etc. It is preferable to use ethylene gas in the production of highly conductive carbon nanofibers. The reaction gas ratio may be adjusted by dividing into a temperature rising step R1 to the reaction temperature, a holding step R2 at the reaction temperature, a reaction step R3, and a cooling step R4.
이하 본 발명에서 사용된 반응가스 조성 비율에 따른 총 반응시간을 수식화하여 표현하면 다음과 같다. 이는 제조된 탄소나노섬유의 겉보기 밀도를 제어하는 수단으로 사용한다.Hereinafter, the total reaction time according to the reaction gas composition ratio used in the present invention is expressed as follows. This is used as a means of controlling the apparent density of the produced carbon nanofibers.
반응 온도까지의 승온 단계(R1), 반응 온도에서 유지단계(R2), 반응단계(R3)의 총 반응시간은 최소 1시간 이상 최대 4시간 이하이며, 냉각단계(R4)의 반응시간은 2시간 이하이다.The total reaction time of the temperature rising step R1 to the reaction temperature, the holding step R2 at the reaction temperature, and the reaction step R3 is at least 1 hour and at most 4 hours, and the reaction time of the cooling step R4 is 2 hours. It is as follows.
한편 반응 온도까지의 승온 단계(R1)의 바람직한 반응시간은 0.5∼2시간이며, 이 때 사용되는 수소가스 : 질소가스 부피비는 1 : 1∼4(리터/분)이다. 또한 반응 온도에서 유지단계(R2)의 바람직한 반응시간은 0.1∼2시간이며, 이 때 사용되는 수소가스 : 질소가스 부피비는 1 : 1∼4(리터/분)이다. 또한 반응단계(R3)의 바람직한 반응시간은 0.1∼2시간이며, 이 때 사용되는 수소가스 : 에틸렌 가스 부피비는 1 : 1∼4(리터/분)이다. On the other hand, the preferable reaction time of the temperature rising step R1 to the reaction temperature is 0.5 to 2 hours, and the volume ratio of hydrogen gas to nitrogen gas used at this time is 1: 1 to 4 (liters / minute). In addition, the preferable reaction time of the holding step (R2) at the reaction temperature is 0.1 to 2 hours, and the hydrogen gas: nitrogen gas volume ratio is 1: 1 to 4 (liters / minute). In addition, the preferable reaction time of reaction stage (R3) is 0.1 to 2 hours, and the volume ratio of hydrogen gas: ethylene gas used at this time is 1: 1-4 (liters / minute).
또한 냉각단계(R4)의 바람직한 반응시간은 0.5∼2시간이며, 이 때 불활성 가스를 사용하여 상온까지 냉각시킨다.In addition, a preferable reaction time of the cooling step (R4) is 0.5 to 2 hours, at which time it is cooled to room temperature using an inert gas.
승온 속도는 1∼20℃/분 범위에서, 바람직하게는 5∼10℃/분 범위에서 유지하는 것이 금속 촉매의 균일한 열처리에 효과적이다. 금속 촉매는 열산화 공정을 통해 제조되기 때문에 산화물 형태로 존재하게 되는데 이러한 산화물 형태는 환원분위기 조건에 따라 다양한 촉매 금속입자로 성장하는 것으로 알려져 있다.It is effective for uniform heat treatment of a metal catalyst to maintain a temperature increase rate in the range of 1-20 degreeC / min, Preferably it is 5-10 degreeC / min. Since the metal catalyst is prepared through a thermal oxidation process, it is present in the form of an oxide, which is known to grow into various catalyst metal particles according to the reducing atmosphere conditions.
헤링본 구조를 결정하는 촉매의 결정 모양은 마름모꼴 모양의 촉매 구조로부터 해석될 수 있다. 도 3에 나타낸 그림은 전형적인 헤링본 타입의 탄소나노섬유의 촉매의 모습을 투과현미경으로 관찰한 사진이다.The crystal shape of the catalyst that determines the herringbone structure can be interpreted from the rhombic catalyst structure. 3 is a photograph of a typical herringbone type carbon nanofiber catalyst catalyst observed with a transmission microscope.
나노크기의 촉매 금속입자는 고온의 열 반응에 노출되는 시간, 온도 조건에 따라 용융 및 소결이 동시에 일어나 촉매 금속 입자의 크기 및 모양이 변하여 이 금속 촉매 입자로부터 성장하는 탄소나노섬유의 섬경과 섬유 성장 축에 대한 흑연 망상면(graphite basal plane)의 배향각이 변한다는 사실을 발견하였다.The nano-sized catalyst metal particles are melted and sintered at the same time as they are exposed to high temperature thermal reactions and temperature conditions, and thus the size and shape of the catalyst metal particles change, so that the carbon nanofibers grow and grow on the carbon nanoparticles. It was found that the orientation angle of the graphite basal plane with respect to the axis changes.
또한 반응 가스에 대해 촉매 활성을 보이는 철, 코발트, 니켈 등의 전이금속 입자를 고온에서 반응시간 동안 입자간의 응집을 최대한 억제하기 위해서는 Mn, Cr, Mo, W, Zr, Ti 등 비활성 금속입자를 촉매 구성 성분 중량대비 5∼80 중량비, 바람직하게는 5∼50 중량비로 합금화 혹은 복합화 하는 것이 바람직하다. 특히 Mn 금속의 경우 560℃ 이하의 반응온도에서 반응가스 조성비율에 따른 탄소나노섬유의 구조제어가 더욱 용이함을 발견하였다.In addition, in order to suppress aggregation between particles during the reaction time at a high temperature for transition metal particles such as iron, cobalt, and nickel, which exhibit catalytic activity to the reaction gas, inert metal particles such as Mn, Cr, Mo, W, Zr, and Ti are catalyzed. It is preferable to alloy or compound in a 5 to 80 weight ratio, preferably 5 to 50 weight ratio relative to the weight of the component. In particular, the Mn metal was found to be easier to control the structure of the carbon nanofibers according to the reaction gas composition ratio at the reaction temperature of less than 560 ℃.
환원분위기에 노출되는 시간은 승온단계를 포함하여 반응온도에서의 유지시간으로 합산할 수 있으며 환원노출 시간이 반응시간보다 2배 이상 크거나 반응시간보다 적게 되면 제조되는 탄소나노섬유의 다발(carbon nanofiber bundles)에 의한 엉킴 현상이 증가하여 겉보기 밀도가 0.08g/ml이상 증가하게 되었다.The exposure time to the reducing atmosphere can be summed up as the holding time at the reaction temperature, including the step of raising the temperature, and a bundle of carbon nanofibers produced when the reduction exposure time is more than two times or less than the reaction time (carbon nanofiber). The increase in entanglement caused by bundles) increased the apparent density by more than 0.08 g / ml.
헤링본 구조를 갖는 탄소나노섬유의 반응온도는 제조되는 촉매 조성에 따라 달라질 수 있으나 400∼600℃ 범위에서 바람직하게는 450∼580℃ 범위에서 제조할 경우 섬경이 5∼20nm 범위에 있으면서 섬유 성장축에 대하여 흑연 망상면(graphite basal plane)의 배향각이 10∼30도 기울기를 유지할 수 있었다.The reaction temperature of the carbon nanofibers having a herringbone structure may vary depending on the catalyst composition to be prepared. However, when manufactured in the range of 400 to 600 ° C., preferably in the range of 450 to 580 ° C., the fiber diameter is about 5 to 20 nm and the fiber growth axis is The orientation angle of the graphite basal plane could maintain a slope of 10 to 30 degrees.
반응온도가 580℃ 이상이 되면 탄소나노튜브 구조형태인 튜블라(tubelar) 구조로 전환되어 헤링본 구조를 벗어나게 되었다. 일반적으로 열화학증착법(Thermal Chemical Vapor Deposition)에 의해 제조되는 탄소나노섬유는 대체로 섬경이 80nm이하로 작아지게 되면 섬유끼리 서로 엉킴 현상이 증가하게 되어 섬유의 겉보기 밀도가 증가하게 된다.When the reaction temperature was higher than 580 ℃, the carbon nanotube structure was converted into a tubular (tubelar) structure is out of the herringbone structure. In general, carbon nanofibers manufactured by Thermal Chemical Vapor Deposition generally have an island diameter of 80 nm or less, whereby the fibers are entangled with each other to increase the apparent density of the fibers.
이러한 번들(Bundle) 형태의 탄소나노섬유들은 복합재 제조 시 균일한 분산이 어려워 섬유의 네트워크 분산이 요구되는 전도성 충진제로서의 역할을 충분히 수행하지 못하게 된다. 이러한 엉킴 현상은 겉보기 밀도라는 물리학적 분체평가 방법으로 예측 가능하다. 탄소나노튜브 혹은 탄소나노섬유의 고 분산을 위해 탄소나노섬유의 표면에 관능기를 부여할 수 있는 산 혹은 염기용액에 의한 화학적 처리 방법 등이 사용될 수 있지만 화학적 처리시간이 짧지 않고 부수적인 폐액이 발생하여 사용자 입장에서 볼 때 부대 공정비용 부담이 더 늘어나는 단점이 있다.Such bundle-type carbon nanofibers are difficult to uniformly disperse when manufacturing a composite material, and thus cannot fully serve as conductive fillers requiring network dispersion of the fiber. This entanglement can be predicted by the physical powder evaluation method of apparent density. For high dispersion of carbon nanotubes or carbon nanofibers, a chemical treatment method using an acid or a base solution that can impart functional groups to the surface of the carbon nanofibers may be used, but the chemical treatment time is short and ancillary wastes are generated. From the user's point of view, there is a drawback that the burden of additional process costs increases.
이러한 단점을 피하기 위한 일련의 실험 결과, 밀폐된 상태에서 용기가 회전하면서 동시에 용기 내부에 임펠러가 설치되어 고속으로 회전할 수 있는 구조를 갖는 건식분쇄기(한국, 대화테크제품, LS-2K 모델)를 사용할 경우 폐수 오염문제가 전혀 없으면서 임펠러(impeller) 회전 속도와 시간을 적절히 조절함에 의해 탄소나노섬유에 손상을 주지 않으면서 엉켜있는 탄소나노섬유 분체 덩어리를 수 마이크로 이하로 미립자화 할 수 있음을 발견하였다.As a result of a series of experiments to avoid these drawbacks, a dry grinding machine (Korea, Daehwa Tech, LS-2K model) has a structure that can rotate at high speed by rotating the container in a closed state and at the same time installing an impeller inside the container. When used, it has been found that by properly adjusting the impeller rotation speed and time without any waste water contamination, tangled carbon nanofiber powder particles can be micronized to several micrometers or less without damaging the carbon nanofibers. .
건식 분쇄는 회전속도가 10∼10000 rpm 범위에서, 시간은 수초∼1시간 범위에서 사용 가능하나 바람직하게는 회전속도가 100∼8000 rpm 범위에서, 시간은 10∼300초 범위가 탄소나노섬유의 구조에 손상을 주지 않고 겉보기 밀도를 조절할 수 있는 방법임을 알 수 있었다. 평균적으로 건식분쇄기를 이용하면 탄소나노섬유의 초기 겉보기 밀도를 10∼50% 까지 낮출 수 있었다.Dry grinding can be used in the range of rotational speed of 10 to 10000 rpm, time of several seconds to 1 hour, but preferably of rotational speed of 100 to 8000 rpm, time of 10 to 300 seconds of structure of carbon nanofibers. It can be seen that it is a method that can control the apparent density without damaging. On average, using a dry mill could lower the initial apparent density of carbon nanofibers by 10-50%.
고전도성 고분자 나노복합재를 제조하기 위해서 탄소나노섬유를 이용한 많은 실험을 진행한 결과 섬유 성장축에 대하여 흑연 망상면(graphite basal plane)의 배향각이 10∼20도 범위에 있는 헤링본 구조를 보유하면서 겉보기 밀도가 0.06g/cm3 이하인 탄소나노섬유를 제조하여 적용함으로서 탄소나노섬유 고분자 복합재의 전기전도도 물성 발현이 가능함을 알 수 있었다.Many experiments using carbon nanofibers have been carried out to produce high-conductivity polymer nanocomposites and have a herringbone structure in which the orientation angle of the graphite basal plane is 10-20 degrees with respect to the fiber growth axis. It can be seen that the electrical conductivity of the carbon nanofiber polymer composite can be expressed by applying carbon nanofibers having a thickness of 0.06 g / cm 3 or less.
고전도성 탄소나노섬유 고분자 복합재 제조공정도를 도 4에 나타내었다. 비록 겉보기 밀도는 0.06g/cm3 이하이지만 흑연 망상면(graphite basal plane)의 배향각이 40도 이상인 경우에는 전기전도도 뿐만 아니라 기계적 물성이 열악하였다.4 shows a manufacturing process chart of the highly conductive carbon nanofiber polymer composite. Although the apparent density was less than 0.06 g / cm 3 , when the orientation angle of the graphite basal plane was more than 40 degrees, the electrical properties as well as the mechanical properties were poor.
이하 실시예를 통하여 본 발명을 더욱 상세하게 설명하나 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
(제조실시예 1) 본 발명의 탄소나노섬유/고분자 복합재의 제조Preparation Example 1 Preparation of Carbon Nanofibers / Polymer Composites of the Present Invention
아이런나이트레이트(Fe(NO3)2 9H2O) 11.80g, 망간나이트레이트(Mn((NO3)2 6H2O) 6.82g, 코발트나이트레이트(Co(NO3)3 9H2O) 25.53g, 마그네슘나이트레이트(Mg((NO3)2 6H2O) 21.52g을 증류수 300ml에 넣고 1시간 동안 마그네틱 바를 사용하여 혼합 용해시켰다. 금속염이 용해된 상기 수용액의 PH가 7.4에 도달할 때까지 암모늄바이카보네이트(NH4HCO3)를 투입하고 1시간 동안 마그네틱 교반을 유지하면서 현탁액을 만들었다. 상기 현탁액으로부터 일반적인 펀넬 필터를 사용하여 수분을 1차 제거한 다음 얻어진 고형물을 진공오븐을 사용 100℃에서 24시간 건조하였다. 건조된 고형물 15g을 알루미나 보트에 넣고 800℃에서 열 산화를 시켰다.Iron nitrate (Fe (NO 3 ) 2 9H 2 O) 11.80 g, Manganese nitrate (Mn ((NO 3 ) 2 6H 2 O) 6.82 g, Cobalt nitrate (Co (NO 3 ) 3 9H 2 O) 25.53 g and 21.52 g of magnesium nitrate (Mg ((NO 3 ) 2 6H 2 O)) were added to 300 ml of distilled water and dissolved by using a magnetic bar for 1 hour until the pH of the aqueous solution in which the metal salt was dissolved reached 7.4. The suspension was prepared by adding ammonium bicarbonate (NH 4 HCO 3 ) and maintaining magnetic stirring for 1 hour from the suspension using a general funnel filter to remove moisture first, and then obtaining the solid obtained at 24 ° C. using a vacuum oven. 15 g of dried solid was placed in an alumina boat and thermally oxidized at 800 ° C.
열산화 시킨 촉매 분말 1g을 석영으로 된 반응기에 균일하게 분말 도포시킨 후 수직형반응기를 사용하여 10℃/분의 가열속도로 상온에서 550℃까지 질소:수소 가스 비율을 1.5 리터/(분):1.5 리터/(분) 흘려주면서 이 온도에서 1시간 유지하였다. 탄소화 반응은 에틸렌가스 : 수소의 가스 비율을 1.5 리터/(분):1.5 리터/(분) 유속으로 흘려 보내주면서 1시간 가스화 반응을 행하였다. 합성된 탄소나노섬유 양은 30g이었으며 FE-SEM 관찰을 통해 평균 섬유경은 15nm임을 알 수 있었다. 탄소나노섬유의 구조는 헤링본 구조로서(TEM 관찰) 섬유 성장축 방향에 대해 흑연 망상면(graphite basal plane)의 배향각이 15.5도 임을 확인할 수 있었다. 제조된 탄소나노섬유의 겉보기 밀도는 ASTM D 1895 규격에 따라 측정한 결과 0.06g/cm3 값을 나타내었다. 건식분쇄기를 사용하여 7000rpm 속도로 1분간 분쇄 처리할 경우 겉보기 밀도는 0.04g/cm3으로 관찰되었다. 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다.1 g of thermally oxidized catalyst powder was uniformly powder-coated in a quartz reactor, and then a nitrogen-hydrogen gas ratio of 1.5 liter / (min) from room temperature to 550 ° C. at a heating rate of 10 ° C./min using a vertical reactor: It was kept at this temperature for 1 hour while flowing 1.5 liters / (minute). The carbonization reaction performed gasification reaction for 1 hour, flowing the gas ratio of ethylene gas: hydrogen at a flow rate of 1.5 liter / (min): 1.5 liter / (min). The amount of synthesized carbon nanofibers was 30 g and the average fiber diameter was 15 nm through FE-SEM observation. The structure of the carbon nanofibers was a herringbone structure (TEM observation), and the orientation angle of the graphite basal plane with respect to the fiber growth axis direction was 15.5 degrees. The apparent density of the prepared carbon nanofibers was 0.06g / cm 3 as measured according to ASTM D 1895 standard. The apparent density of 0.04 g / cm 3 was observed when the dry mill was pulverized for 1 minute at 7000 rpm. In order to measure the electrical conductivity, the mixture was melt-mixed so that the added amount was 3 phr using MPPO, which is a polymer resin, and then a test specimen was prepared.
(제조실시예 2) 본 발명의 탄소나노섬유/고분자 복합재의 제조Preparation Example 2 Preparation of Carbon Nanofibers / Polymer Composites of the Present Invention
제조실시예 1에 기재된 방법에 의해 촉매금속을 제조 한 다음, 반응 가스 비율을 변화하여 탄소나노섬유를 제조하였다. 이를 상세히 살펴보면 다음과 같다.After preparing the catalyst metal by the method described in Preparation Example 1, carbon nanofibers were prepared by changing the reaction gas ratio. Looking at this in detail as follows.
열산화시킨 촉매 분말 1g을 석영으로 된 반응기에 균일하게 분말 도포시킨 후 수직형반응기를 사용하여 10℃/분의 가열속도로 상온에서 550℃까지 질소:수소 가스 비율을 2.4 리터/(분):0.6 리터/(분) 흘려주면서 이 온도에서 1시간 유지하였다. 탄소화 반응은 에틸렌가스 : 수소의 가스 비율을 2.4 리터/(분) : 0.6 리터/(분) 유속으로 흘려 보내주면서 1시간 가스화 반응을 행하였다. 합성된 탄소나노섬유 양은 29g이었으며 FE-SEM 관찰을 통해 평균 섬유경은 17nm임을 알 수 있었다. 탄소나노섬유의 구조는 헤링본 구조로서(TEM 관찰) 섬유 성장축 방향에 대해 흑연 망상면(graphite basal plane)의 배향각이 18.1도 임을 확인할 수 있었다. 제조된 탄소나노섬유의 겉보기 밀도는 ASTM D 1895 규격에 따라 측정한 결과 0.05g/cm3 값을 나타내었다. 건식분쇄기를 사용하여 7000rpm 속도로 1분간 분쇄 처리할 경우 겉보기 밀도는 0.03g/cm3으로 관찰되었다. 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다.1 g of thermally oxidized catalyst powder was uniformly powder-coated in a quartz reactor, and then a nitrogen-hydrogen gas ratio of 2.4 liter / (min) from room temperature to 550 ° C. at a heating rate of 10 ° C./min using a vertical reactor: 0.6 liter / (min) was maintained for 1 hour at this temperature. The carbonization reaction performed gasification reaction for 1 hour, flowing the gas ratio of ethylene gas: hydrogen at 2.4 liter / (min): 0.6 liter / (min) flow rate. The amount of synthesized carbon nanofibers was 29g and the average fiber diameter was 17nm through FE-SEM observation. The structure of the carbon nanofibers was a herringbone structure (TEM observation), and the orientation angle of the graphite basal plane with respect to the fiber growth axis direction was 18.1 degrees. The apparent density of the prepared carbon nanofibers was 0.05g / cm 3 as measured according to ASTM D 1895 standard. The apparent density of 0.03 g / cm 3 was observed when the dry mill was pulverized for 1 minute at 7000 rpm. In order to measure the electrical conductivity, the mixture was melt-mixed so that the added amount was 3 phr using MPPO, which is a polymer resin, and then a test specimen was prepared.
(제조비교예 1) 나노섬유 제조시 반응가스 비율을 변화시켜 제조된 탄소나노섬유/고분자 복합재의 제조Preparation Example 1 Preparation of Carbon Nanofibers / Polymer Composites Prepared by Changing Reaction Gas Ratios in Manufacturing Nanofibers
제조실시예 1에 기재된 방법에 의해 촉매금속을 제조 한 다음, 반응 가스 비율을 변화하여 탄소나노섬유를 제조하였다. 이를 상세히 설명하면 다음과 같다.After preparing the catalyst metal by the method described in Preparation Example 1, carbon nanofibers were prepared by changing the reaction gas ratio. This will be described in detail as follows.
열산화 시킨 촉매 분말 1g을 석영으로 된 반응기에 균일하게 분말 도포시킨 후 수직형반응기를 사용하여 10℃/분의 가열속도로 상온에서 550℃까지 질소 가스를 (부피비율, 3 리터/(분)) 흘려주고 이 온도에서 30분간 유지하였다. 탄소화 반응은 에틸렌가스 : 수소의 가스 부피비율을 1.5 리터/(분):1.5 리터/(분) 유속으로 흘려 보내주면서 1시간 가스화 반응을 행하였다. 합성된 탄소나노섬유 양은 32g이었으며 FE-SEM 관찰을 통해 평균 섬유경은 23nm임을 알 수 있었다. 탄소나노섬유의 구조는 헤링본 구조로서(TEM 관찰) 섬유 성장축 방향에 대해 흑연 망상면(graphite basal plane)의 배향각이 28.2도 임을 확인할 수 있었다. 제조된 탄소나노섬유의 겉보기 밀도는 ASTM D 1895 규격에 따라 측정한 결과 0.08g/cm3 값을 나타내었다. 건식분쇄기를 사용하여 7000rpm 속도로 1분간 분쇄 처리할 경우 겉보기 밀도는 0.05g/cm3으로 관찰되었다. 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다. 1 g of thermally oxidized catalyst powder was uniformly powder-coated in a quartz reactor, and then nitrogen gas was added at a heating rate of 10 ° C./min from room temperature to 550 ° C. using a vertical reactor (volume ratio, 3 liters / (min)). ) And held at this temperature for 30 minutes. The carbonization reaction was carried out for 1 hour while flowing the gas volume ratio of ethylene gas: hydrogen at a flow rate of 1.5 liter / (min): 1.5 liter / (min). The amount of synthesized carbon nanofibers was 32g and the average fiber diameter was 23nm through FE-SEM observation. The structure of the carbon nanofibers was a herringbone structure (TEM observation), and the orientation angle of the graphite basal plane with respect to the fiber growth axis direction was 28.2 degrees. The apparent density of the prepared carbon nanofibers was 0.08 g / cm 3 as measured according to ASTM D 1895 standard. The apparent density of 0.05 g / cm 3 was observed when the dry mill was pulverized at 7000 rpm for 1 minute. In order to measure the electrical conductivity, the mixture was melt-mixed so that the added amount was 3 phr using MPPO, which is a polymer resin, and then a test specimen was prepared.
(제조비교예 2) 상용화된 탄소나노섬유로 제조된 탄소나노섬유/고분자 복합재의 제조Preparation Example 2 Preparation of Carbon Nanofibers / Polymer Composites Made of Commercially Available Carbon Nanofibers
상업적으로 판매되고 있는 꼬인형 타입의 탄소나노섬유(한국 나노미래, spiral type, 섬경 100~120nm, 홈페이지주소: http://www.nanomirae.co.kr)를 사용하여 제조실시예 1과 동일한 방법으로 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다. 제조된 탄소나노섬유의 겉보기 밀도는 ASTM D 1895 규격에 따라 측정한 결과 0.08g/cm3 값을 나타내었다. 건식분쇄기를 사용하여 7000rpm 속도로 1분간 분쇄 처리할 경우 겉보기 밀도는 0.06g/cm3으로 관찰되었다. 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다. The same method as in Preparation Example 1 using commercially sold twisted type carbon nanofibers (Korea Nano Future, spiral type, island size 100 ~ 120nm, homepage: http://www.nanomirae.co.kr) In order to measure the electrical conductivity by using a polymer resin MPPO was added and melted so that the addition amount to 3phr, the test specimen was prepared. The apparent density of the prepared carbon nanofibers was 0.08 g / cm 3 as measured according to ASTM D 1895 standard. The apparent density was found to be 0.06 g / cm 3 when the dry mill was pulverized at 7000 rpm for 1 minute. In order to measure the electrical conductivity, the mixture was melt-mixed so that the added amount was 3 phr using MPPO, which is a polymer resin, and then a test specimen was prepared.
(제조비교예 3) 공지된 탄소나노섬유로 제조된 탄소나노섬유/고분자 복합재의 제조Preparation Example 3 Preparation of Carbon Nanofibers / Polymer Composites Made of Known Carbon Nanofibers
대한민국 특허등록 제350,535호 내의 실시예 1에 기재된 방법에 의해 탄소나노섬유를 제조한 후 본 발명 제조실시예 1과 동일한 방법으로 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다. 그 결과는 표 2에 나타내었다. 이를 상세히 살펴보면 다음과 같다.After manufacturing carbon nanofibers by the method described in Example 1 in Korean Patent Registration No. 350,535 and melting them so that the addition amount is 3phr using MPPO, a polymer resin, to measure the electrical conductivity in the same manner as in Production Example 1 of the present invention. After mixing, a test specimen was prepared. The results are shown in Table 2. Looking at this in detail as follows.
철과 니켈(철/니켈 중량비 4/1)의 합금촉매를 이용하여 섬유상 나노탄소 제 조용 촉매를 제조하기 위해 일본 와코사제 질산철 29.0g과 질산니켈 5.0g 을 3차 증류수 200ml에 첨가하여 용해시킨 후, 미쯔비시 화학사제 카본블랙(MS No. 3050) 80g을 첨가 후 30분간 교반하여 혼련하였다. 상기의 방법으로 제조한 카본블랙과 질산철 및 질산니켈의 혼합슬러리를 회전식 진공건조기(Rotary Evaporator)를 사용하여 80℃에서 40토르 (Torr)의 조건으로 수분을 건조하여 질산철과 질산니켈이 분산되어진 카본블랙을 제조하였다. 제조한 질산철과 질산니켈이 분산된 카본블랙을 석영제의 보트 (길이ｘ폭x깊이 = 10x2.5x1.5 /mm(외부값) )에 장착한 후 4.5cm의 내경을 지닌 석영관으로 이루어진 수평로의 중간에 두고 공기를 100sccm 흘리면서 400℃에서 5시간 산화처리하여 카본블랙을 연소하였다. 연소하여 카본블랙이 없어진 철-니켈 산화물을 로내에 그대로 둔 채 30 분간 헬륨 분위기를 유지한 후 수소와 헬륨가스의 혼합가스 100sccm을 사용하여 (수소분압 :20%) 480℃에서 1시간 환원처리를 행하여 철과 니켈의 합금으로 된 촉매를 제조하였다. 제조한 촉매를 상온에서 보관하기 위하여 헬륨분위기에서 상온으로 냉각시킨 후 2 %의 산소를 혼합한 헬륨혼합가스 100sccm을 흘리면서 30분간 부동화(표면산화) 처리하였다.To prepare a catalyst for the preparation of fibrous nanocarbon using an alloy catalyst of iron and nickel (iron / nickel weight ratio 4/1), 29.0 g of iron nitrate and 5.0 g of nickel nitrate manufactured by Wako, Japan were added and dissolved in 200 ml of tertiary distilled water. Thereafter, 80 g of carbon black (MS No. 3050) manufactured by Mitsubishi Chemical Corporation was added and stirred for 30 minutes to knead. The mixed slurry of carbon black, iron nitrate and nickel nitrate prepared by the above method was dried using a rotary evaporator at a temperature of 40 Torr at 80 ° C. to disperse iron nitrate and nickel nitrate. Prepared carbon black. The carbon black, in which iron nitrate and nickel nitrate were dispersed, was mounted on a quartz boat (length x width x depth = 10x2.5x1.5 / mm) and consisted of a quartz tube with an inner diameter of 4.5 cm. The carbon black was combusted by oxidation at 400 ° C. for 5 hours while flowing air at 100 sccm in the middle of the horizontal path. After burning, the iron-nickel oxide, which had lost carbon black, was kept in the furnace for 30 minutes, followed by reduction treatment at 480 ° C for 1 hour using 100 sccm of a mixed gas of hydrogen and helium gas (20% hydrogen). To prepare a catalyst of an alloy of iron and nickel. In order to store the prepared catalyst at room temperature, the resultant was cooled to room temperature in a helium atmosphere, followed by passivation (surface oxidation) for 30 minutes while flowing 100 sccm of a helium mixed gas containing 2% oxygen.
상기 제조한 촉매 30mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조 시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 495℃에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에틸렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 480℃에서 2시간 반응를 행하여 소정량(5224 mg)의 섬유상 나노탄소를 제조하였다. 합성 된 탄소나노섬유의 평균 섬경은 23nm로 관찰되었다. 탄소나노섬유의 구조는 헤링본 구조로서(TEM 관찰) 섬유 성장축 방향에 대해 흑연 망상면(graphite basal plane)의 배향각이 42도 임을 확인할 수 있었다. 제조된 탄소나노섬유의 겉보기 밀도는 ASTM D 1895 규격에 따라 측정한 결과 0.09g/cm3 값을 나타내었다. 건식분쇄기를 사용하여 7000rpm 속도로 1분간 분쇄 처리할 경우 겉보기 밀도는 0.07g/cm3으로 관찰되었다. 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다. 30 mg of the prepared catalyst was mounted in the middle of a quartz tube having an inner diameter of 4.5 cm, and then flowed at 100 sccm (20 vol% of hydrogen partial pressure) of a mixture of hydrogen and helium at 495 ° C. using a horizontal furnace used for preparing the catalyst. Reduction treatment was performed for 2 hours. The reaction was carried out at 480 DEG C for 2 hours while flowing 200 sccm (25 vol% of hydrogen partial pressure) of a mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount (5224 mg) of fibrous nanocarbon. The average diameter of the synthesized carbon nanofibers was observed to be 23nm. The structure of the carbon nanofibers was a herringbone structure (TEM observation), and it was confirmed that the orientation angle of the graphite basal plane was 42 degrees with respect to the fiber growth axis direction. The apparent density of the prepared carbon nanofibers was 0.09 g / cm 3 as measured according to ASTM D 1895 standard. The apparent density of 0.07 g / cm 3 was observed when the dry mill was pulverized for 1 minute at 7000 rpm. In order to measure the electrical conductivity, the mixture was melt-mixed so that the added amount was 3 phr using MPPO, which is a polymer resin, and then a test specimen was prepared.
(제조비교예 4) 상용화된 탄소나노튜브로 제조된 탄소나노튜브/고분자 복합재의 제조Preparation Example 4 Preparation of Carbon Nanotube / Polymer Composites Made of Commercially Available Carbon Nanotubes
상업적으로 판매되고 있는 나노실사 제품(Nanocylㄾ 7000,평균 섬경 9.5nm, 홈페이지주소:http://www.nanocyl.com)를 사용하여 제조실시예 1과 동일한 방법으로 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다.Using a commercially-available nano-real product (Nanocyl, 7000, average island diameter 9.5nm, homepage address: http://www.nanocyl.com) in the same manner as in Preparation Example 1 to measure the electrical conductivity of the polymer resin MPPO was used to melt the mixture so that the added amount was 3 phr, and then a test specimen was prepared.
사용된 탄소나노튜브의 겉보기 밀도는 ASTM D 1895 규격에 따라 측정한 결과 0.05g/cm3 값을 나타내었다. 건식분쇄기를 사용하여 7000rpm 속도로 1분간 분쇄 처리할 경우 겉보기 밀도는 0.04g/cm3으로 관찰되었다. 전기전도도 측정을 위하여 고분자 수지인 MPPO를 사용하여 첨가량이 3phr이 되도록 용융 혼합한 다음, 측정용 시편을 제조하였다. The apparent density of the carbon nanotubes used was 0.05g / cm 3 as measured according to ASTM D 1895. The apparent density of 0.04 g / cm 3 was observed when the dry mill was pulverized for 1 minute at 7000 rpm. In order to measure the electrical conductivity, the mixture was melt-mixed so that the added amount was 3 phr using MPPO, which is a polymer resin, and then a test specimen was prepared.
(실시예) 탄소나노섬유/고분자 복합재의 물성 측정EXAMPLES Measurement of Physical Properties of Carbon Nanofibers / Polymer Composites
(전도도 물성 측정 시편 제조)(Manufacture of test piece for measuring conductivity property)
제조된 탄소나노섬유 1.5g, 엔지니어링플라스틱 MPPO 50g을 함께 비닐용기에 넣은 다음 1분간 건식 혼합시킨 다음, 하케믹서(Hakke mixer)를 사용하여 용융 혼합을 진행시켰다. 이때 가공온도는 270℃, 스크루 회전속도는 50rpm, 가공시간은 10분이었다.1.5 g of the prepared carbon nanofibers and 50 g of engineering plastic MPPO were put together in a vinyl container, followed by dry mixing for 1 minute, followed by melt mixing using a Hakke mixer. At this time, the processing temperature was 270 ℃, screw rotation speed was 50rpm, processing time was 10 minutes.
용융된 탄소나노섬유/MPPO 고분자 복합재를 10cm x 10cm x 5mm 크기로 프레스 가공하였다. 이때 가공온도는 270℃, 압력 3500kgf/cm2로 10분간 성형 가공하였다.The molten carbon nanofibers / MPPO polymer composite was pressed into a size of 10 cm x 10 cm x 5 mm. At this time, the processing temperature was molded for 10 minutes at 270 ℃, pressure 3500kgf / cm 2 .
제조된 시편은 표면저항 측정장치인 Ohmmeter(미국, Static Solutions, Inc., 모델 :OHM-STAT RT-1000)를 사용하여 2전극방식에 의한 표면 저항값을 측정하였다.The prepared specimens were measured using Ohmmeter (USA, Static Solutions, Inc., Model: OHM-STAT RT-1000), which is a surface resistance measurement device, to measure surface resistance by two-electrode method.
표 1은 상기 제조실시예 1∼2 및 제조비교예 1∼4에서 제조된 탄소나노섬유/고분자 복합재 시편의 구조와 겉보기 밀도의 측정 결과를 나타낸 도표이다.Table 1 is a table showing the measurement results of the structure and the apparent density of the carbon nanofibers / polymer composite specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 4.
표 2는 상기 제조실시예 1∼2 및 제조비교예 1∼4에서 제조된 탄소나노섬유/고분자 복합재 시편의 전기 전도도의 측정 결과를 나타낸 도표이다.Table 2 is a chart showing the measurement results of the electrical conductivity of the carbon nanofibers / polymer composite specimens prepared in Preparation Examples 1-2 and Comparative Examples 1-4.
도 1은 본 발명의 고전도성 탄소나노섬유의 FE-SEM 관찰사진이다.1 is a FE-SEM observation picture of the highly conductive carbon nanofibers of the present invention.
도 2는 본 발명의 제조된 헤링본 구조 모델이다.2 is a manufactured herringbone structural model of the present invention.
도 3은 본 발명의 헤링본 타입의 탄소나노섬유의 투과현미경 사진이다.3 is a transmission micrograph of a herringbone type carbon nanofiber of the present invention.
도 4는 본 발명의 고전도성 탄소나노섬유를 이용한 전도성 고분자 복합재 제조공정도이다.Figure 4 is a manufacturing process chart of the conductive polymer composite using high conductivity carbon nanofibers of the present invention.
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| KR20160104162A (en) * | 2015-02-25 | 2016-09-05 | 주식회사 카본나노텍 | Anode material for lithium secondary battery and manufacturing method thereof |
| CN117887224A (en) * | 2024-03-15 | 2024-04-16 | 江阴纳力新材料科技有限公司 | Polymer composite membrane, preparation method thereof, composite current collector and application |
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| KR20160104162A (en) * | 2015-02-25 | 2016-09-05 | 주식회사 카본나노텍 | Anode material for lithium secondary battery and manufacturing method thereof |
| CN117887224A (en) * | 2024-03-15 | 2024-04-16 | 江阴纳力新材料科技有限公司 | Polymer composite membrane, preparation method thereof, composite current collector and application |
| CN117887224B (en) * | 2024-03-15 | 2024-05-28 | 江阴纳力新材料科技有限公司 | Polymer composite membrane, preparation method thereof, composite current collector and application |
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