KR20110041647A - Thermal conductive composites consisting of carbon nanostructures and metal - Google Patents
Thermal conductive composites consisting of carbon nanostructures and metal Download PDFInfo
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- KR20110041647A KR20110041647A KR1020090098573A KR20090098573A KR20110041647A KR 20110041647 A KR20110041647 A KR 20110041647A KR 1020090098573 A KR1020090098573 A KR 1020090098573A KR 20090098573 A KR20090098573 A KR 20090098573A KR 20110041647 A KR20110041647 A KR 20110041647A
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- South Korea
- Prior art keywords
- metal
- carbon nanotube
- thermally conductive
- composite material
- silver
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- B22F1/0003—
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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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
Abstract
Description
본 발명은 탄소나노튜브-금속 열전도성 복합 소재에 관한 것으로, 보다 상세하게는 새로운 형태의 탄소나노튜브-금속 복합체와 금속의 혼합물 소재인 열전도성 복합소재에 관한 것이다.The present invention relates to a carbon nanotube-metal thermally conductive composite material, and more particularly, to a thermally conductive composite material which is a mixture material of a new type of carbon nanotube-metal composite and metal.
최근에 산업이 발전하면서 발열 전자제품이 많아지고 열전도성이 우수한 소재에 대한 기술이 매우 중요한 분야로 인식되고 있다. 개인컴퓨터의 발열부품, 발광다이오드(LED) 발열체, 서멀 사이클러(Thermal Cycler)의 열블럭(Thermal Block)부품 분야에서 중요성이 커지고 있으며, 특히 써멀 싸이클러는 유전자 진단에 필요한 기본 진단장비로 그 중요성이 증가하면서, 고속 진단을 위한 열전달체 기술이 크게 주목 받고 있다. Recently, with the development of the industry, a lot of heat generation electronic products and technology for excellent thermal conductivity material is recognized as a very important field. In the field of heating components of personal computers, LED heating elements, and thermal block components of thermal cyclers, the importance is increasing. Especially, the thermal cycler is a basic diagnostic equipment for gene diagnosis. With this increase, heat transfer technology for high-speed diagnosis has attracted much attention.
생명공학 분야, 특히 유전자 진단 분야에는 PCR(Polymerase Chain Reaction) 써멀 싸이클러(Thermal Cycler)가 가장 중요한 장치인데, PCR 반응이란 1983년 뮬리스 등(Mullis et al.)에 의해 개발된 중합효소연쇄반응(Polymerase Chain Reaction; PCR)이라는 DNA 복제기술이다. PCR은 효소를 이용하여 주형 DNA를 계속 복제하는 방법으로, PCR 단계는 복제할 대상인 이중가닥 주형 DNA(Template DNA)를 단일가닥으로 풀어주는 변성(Melting)단계, 풀어진 단일가닥에 반응이 시작될 곳을 지정하고 효소반응이 시작되는 것을 도와주는 수십 base의 프라이머(Primer)를 결합하는 어닐링(Annealing)단계, 그리고 프라이머가 붙은 위치로부터 DNA를 복제해서 완전한 이중 나선구조의 DNA를 만드는 연장(Extension)단계의 세 간계로 구분되어진다. 상기 세 단계를 진행하면 이론적으로 2배의 DNA 양이 증가하고, 이 과정을 반복적으로 n번 수행하면 DNA의 양은 이론적으로 2n배로 증가하게 된다. 일반적으로 PCR 써멀 싸이클러는 온도조절이 가능한 열블럭(Thermal Block)이 사용되며, 상기 열블럭은 일정한 시간 간격에 따른 온도의 변화를 반복하여 조절하며 수행된다. In biotechnology, especially in the field of genetic diagnosis, PCR (Polymerase Chain Reaction) Thermal Cycler is the most important device.The PCR reaction is a polymerase chain reaction developed by Mullis et al. In 1983. DNA replication technology called Polymer Chain Reaction (PCR). PCR is a method of continuously copying template DNA using an enzyme.The PCR step is a denting step of releasing a single-stranded template DNA (Template DNA) to be replicated. The annealing step that binds dozens of base primers to designate and help initiate the enzymatic reaction, and the extension step of replicating DNA from where the primers are attached to create a complete double helix DNA. It is divided into three tricks. In the three steps above, theoretically, the amount of DNA is doubled, and if this process is repeated n times, the amount of DNA is theoretically increased by 2 n times. In general, a PCR thermal cycler is used as a thermal block (Thermal Block) capable of temperature control, the thermal block is performed by repeatedly adjusting the temperature change over a predetermined time interval.
PCR(Polymerase Chain Reaction) 써멀 싸이클러(Thermal Cycler)의 핵심 부품은 열전도성이 우수한 열블럭(Thermal Block)이다. PCR의 특성에서 온도의 상승과 하강을 반복하게 되는데, 이 때 열전도가 우수한 열블럭이 요구되어진다. 지금까지의 열블럭은 알루미늄 금속으로 제작되며, 고속 PCR 써멀 싸이클러 장치의 경우 은(Silver) 금속이 사용되고 있다.The core component of the Polymer Chain Reaction (PCR) Thermal Cycler is a thermal block with excellent thermal conductivity. In the characteristics of PCR, the temperature rises and falls repeatedly. At this time, a heat block having excellent thermal conductivity is required. Until now, the thermal block is made of aluminum metal, and silver metal is used for the high-speed PCR thermal cycler device.
그러나 이러한 PCR 써멀 싸이클러에 사용되는 알루미늄의 열적 성능이 떨어져서 고속의 PCR 반응이 어려운 것이 현재의 가장 큰 문제이다. 그리고 은(Silver)을 사용하는 방법은 은이 고가이기 때문에 경제성에서 문제가 생기게 된다. 따라서 상기의 문제점을 해소하기 위한 다양한 열전도체 소재에 대한 연구가 지속되고 있다.However, the current problem is that high-speed PCR reactions are difficult due to the poor thermal performance of aluminum used in such PCR thermal cyclers. And since silver is expensive, silver has a problem in economics. Therefore, researches on various thermal conductor materials have been continued to solve the above problems.
이에 본 발명자들은 탄소나노튜브와 금속을 결합한 나노복합체를 제조하는 방법을 대한민국 출원특허 제2007-0072669호 및 대한민국 출원특허 제2008-0049464호에 제조방법이 개시한 바 있으며, 상기 제조방법으로 제조된 나노복합체와 금속을 포함하는 복합소재가 놀라운 열전도성을 가지는 것을 발견하고 본 발명을 완성하였다.Accordingly, the present inventors have disclosed a method for manufacturing a nanocomposite combining carbon nanotubes and a metal in Korean Patent Application No. 2007-0072669 and Korean Patent Application No. 2008-0049464, which are prepared by the above method. The composite material comprising a nanocomposite and a metal was found to have a surprising thermal conductivity and completed the present invention.
본 발명의 목적은 열전도성이 우수한 새로운 형태의 탄소나노튜브-금속 복합체와 금속의 혼합물 소재인 열전도성 복합소재를 제공하기 위한 것이다.It is an object of the present invention to provide a thermally conductive composite material which is a mixture material of a carbon nanotube-metal composite and a metal having a high thermal conductivity.
본 발명의 또 다른 목적은 상기 열전도성 복합소재를 이용하여 충격강도 및 물리적 기계적 특성이 향상되고 우수한 열전도성을 가지는 PCR 써멀 싸이클러(Thermal Cycler) 열블럭(Thermal Block)을 제공하기 위한 것이다.Still another object of the present invention is to provide a PCR thermal cycler thermal block having improved thermal strength and excellent thermal conductivity by using the thermally conductive composite material.
본 발명은 상기의 목적을 달성하기 위하여, 탄소나노튜브-금속 복합체 및 금속을 포함하는 것을 특징으로 하는 열전도성 복합소재를 제공한다.The present invention provides a thermally conductive composite material comprising a carbon nanotube-metal composite and a metal in order to achieve the above object.
본 발명은 상기 열전도성 복합소재를 소결 또는 다이캐스팅(die casting) 하여 제조되는 것을 특징으로 하는 열전도성 성형물을 제공한다.The present invention provides a thermally conductive molded article prepared by sintering or die casting the thermally conductive composite material.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 열전도성 복합소재는 탄소나노튜브에 수 nm 내지 수백 nm의 금속입자가 균일하게 분산되고, 탄소나노튜브에 결합되어 있는 금속입자 크기가 균일한, 탄소나노튜브-금속 복합체에 금속을 혼합하여 열전도도의 흐름 경로를 확보하는 것을 특징으로 하며, 탄소나노튜브에 결합되는 금속 입자를 크기를 조절함으로써 보다 작고 균일한 크기의 금속 나노입자가 탄소나노튜브에 균일하게 분산되도록 하여 제조되는 것을 특징으로 한다.In the thermally conductive composite material according to the present invention, metal particles of several nm to hundreds of nm are uniformly dispersed in carbon nanotubes, and metals in the carbon nanotube-metal composite having uniform metal particle sizes bonded to the carbon nanotubes are formed. It is characterized in that to ensure a flow path of thermal conductivity by mixing, by manufacturing the metal nanoparticles of smaller and uniform size is uniformly dispersed in the carbon nanotubes by controlling the size of the metal particles bonded to the carbon nanotubes It features.
상기 탄소나노튜브-금속의 복합체는 환원성 용매에 분산시킨 탄소나노튜브의 분산액과 금속 전구체를 혼합하고 열처리하여 제조되는 것을 특징으로 하며, 5 내지 200 ㎚의 구형 금속 입자 및 탄소나노튜브로 이루어진 것을 특징으로 한다.The carbon nanotube-metal complex is characterized in that the carbon nanotube dispersion dispersed in a reducing solvent and a metal precursor is prepared by mixing and heat treatment, characterized in that consisting of 5 to 200 nm spherical metal particles and carbon nanotubes It is done.
본 발명은 열전도성 복합소재로 탄소나노튜브-금속 복합체 및 금속을 포함하는 것을 특징으로, 상기 함유되는 금속은 은(Ag), 구리(Cu), 알루미늄(Al), 주석(Sn), 비스무스(Bi) 및 안토모니(Sb)로부터 선택되는 어느 하나 이상인 금속인 것을 특징으로 한다.The present invention is characterized in that it comprises a carbon nanotube-metal composite and a metal as a thermally conductive composite, the metal contained is silver (Ag), copper (Cu), aluminum (Al), tin (Sn), bismuth ( It is characterized in that the metal is any one or more selected from Bi) and anthony (Sb).
본 발명에 따른 탄소나노튜브-금속 복합체는 탄소나노튜브를 환원성 용매에 분산시켜 분산액을 제조하고, 상기 분산액에 금속 전구체를 가하여 혼합액을 제조한 후, 상기 혼합액을 열처리하여 금속 전구체를 환원시켜 탄소나노튜브-금속 복합체를 제조하여 수득되며, 상기 탄소나노튜브-금속 복합체는 분산액에 안정제를 더 포함하여 혼합하고 열처리하여 제조될 수 있다.In the carbon nanotube-metal composite according to the present invention, a carbon nanotube is dispersed in a reducing solvent to prepare a dispersion, a metal precursor is added to the dispersion to prepare a mixed solution, and the mixed solution is heat treated to reduce the metal precursor to carbon nanotubes. Obtained by preparing a tube-metal composite, the carbon nanotube-metal composite may be prepared by further mixing and heat-treating a stabilizer in the dispersion.
본 발명에 따른 탄소나노튜브-금속 복합체는 탄소나노튜브와 금속이 결합된 것이며, 상기 탄소나노튜브는 단일벽 탄소나노튜브(single wall carbon nanotube), 이중벽 탄소나노튜브(double wall carbon nanotube), 다중벽 탄소나노튜브(multi wall carbon nanotube), 또는 이들의 혼합물로부터 선택될 수 있으며, 보다 바람직하게는 다중벽 탄소나노튜브(multi wall carbon nanotube)를 사용할 수 있다. Carbon nanotube-metal composite according to the present invention is a carbon nanotube and a metal is combined, the carbon nanotube is a single wall carbon nanotube (single wall carbon nanotube), double wall carbon nanotube (double wall carbon nanotube), multiple It may be selected from multi wall carbon nanotubes, or mixtures thereof, and more preferably, multi wall carbon nanotubes may be used.
상기 탄소나노튜브를 분산시키기 위한 환원성 용매는 다가알코올, 글리콜 에테르류 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것으로, 보다 상세하게는 다가알코올은 하기 화학식 1의 글리콜류, 글리세린, 트레이톨, 아라비톨, 글루코스, 만니톨, 갈락티톨 및 솔비톨로 이루어진 군으로부터 선택되고, 상기 글리콜 에테르류는 하기 화학식 2의 화합물로부터 선택되어 제조될 수 있다.The reducing solvent for dispersing the carbon nanotubes is selected from the group consisting of polyhydric alcohols, glycol ethers, and mixtures thereof. More specifically, the polyhydric alcohols are glycols of the general formula (1), glycerin, traceol, arabitol , Glucose, mannitol, galactitol and sorbitol, and the glycol ethers may be prepared by selecting from the compound of
[화학식 1][Formula 1]
H-(OR1)n-OHH- (OR 1 ) n -OH
[화학식 2][Formula 2]
R4-(OR2)m-OR3 R 4- (OR 2 ) m -OR 3
(상기 화학식에서 R1 및 R2는 독립적으로 C2~C10의 직쇄 또는 분지쇄의 알킬렌으로부터 선택되고; R3는 수소원자, 알릴, C1~C10의 알킬, C5~C20의 아릴, 또는 C6~C30의 아르알킬기고; R4는 알릴, C1~C10의 알킬, C5~C20의 아릴, C6~C30의 아르알킬기, 또는 C2~C10의 알킬카르보닐기로부터 선택되며 상기 알킬카르보닐기의 알킬은 탄소사슬에 이중결합을 포함할 수 있고; n 및 m은 독립적으로 1 내지 100의 정수이다.)(In the above formula, R 1 and R 2 are independently selected from C2-C10 linear or branched alkylene; R 3 is hydrogen atom, allyl, C1-C10 alkyl, C5-C20 aryl, or C6 ~ C 4 is an aralkyl group; R 4 is selected from allyl, C 1 -C 10 alkyl, C 5 -C 20 aryl, C 6 -C 30 aralkyl group, or C 2 -C 10 alkylcarbonyl group, wherein the alkyl of the alkyl carbonyl group is A bond; n and m are independently an integer from 1 to 100.)
또한, 상기 글리콜류는 에틸렌 글리콜(Ethylene glycol), 디에틸렌 글리콜(Diethylene Glycol), 트리에틸렌 글리콜(Triethylene Glycol), 테트라에틸렌 글리콜(Tetraethylene Glycol), 폴리에틸렌 글리콜(Polyethylene Glycol), 프로필렌 글리콜(Propylene Glycol), 디프로필렌 글리콜(Dipropylene Glycol), 폴리프로필렌 글리콜(Polypropylene Glycol), 헥실렌 글리콜(Hexylene Glycol) 등을 예로 들 수 있으며, 에틸렌 글리콜이 보다 바람직하나 반드시 이에 한정하는 것은 아니다.In addition, the glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and propylene glycol. , Dipropylene Glycol, Polypropylene Glycol, Hexylene Glycol, etc. may be exemplified, but ethylene glycol is more preferred, but is not necessarily limited thereto.
마지막으로 글리콜 에테르류에 포함되는 화합물로는 메틸 글리콜(Methyl Glycol), 메틸 디글리콜(Methyl Diglycol), 메틸 트리글리콜(Methyl Triglycol), 메틸 폴리글리콜(Methyl Polyglycol), 에틸 글리콜(Ethyl Glycol), 에틸 디글리콜(Ethyl Diglycol), 부틸 글리콜(Butyl Glycol), 부틸 디글리콜(Butyl Diglycol), 부틸 트리글리콜(Butyl Triglycol), 부틸 폴리글리콜(Butyl Polyglycol), 헥실 글리콜(Hexyl Glycol), 헥실 디글리콜(Hexyl Diglycol), 에틸헥실 글리콜(Ethyl Hexyl Glycol), 에틸헥실 디글리콜(Ethyl Hexyl Diglycol), 아릴 글리콜(Allyl Glycol), 페닐 글리콜(Phenyl Glycol), 페닐 디글리콜(Phenyl Diglycol), 벤질 글리콜(Benzil Glycol), 벤질 디글리콜(Benzil Diglycol), 메틸 프로필렌 글리콜(Methyl Propylene Glycol), 메틸 프로필렌 디글리콜(Methyl Propylene Diglycol), 메틸 프로필렌 트리글리콜(Methyl Propylene Triglycol), 프로필 프로필렌 글리콜(Propyl Propylene Glycol), 프로필 프로필렌 디글리콜(Propyl Propylene Diglycol), 부틸 프로필렌 글리콜(Butyl Propylene Glycol), 부틸 프로필렌 디글리콜(Butyl Propylene Diglycol), 페닐 프로필렌 글리콜(Phenyl Propylene Glycol), 메틸 프로필렌 글리콜 아세테이트(Methyl Propylene Glycol Acetate), 폴리 메틸 글리콜 등을 예로 들 수 있으나, 반드시 이에 한정하는 것은 아니다. 본 발명에 따른 환원성 용매로 상기 글리콜류를 사용하여 글리콜에테르류와 혼합하여 사용하는 것이 보다 바람직하고, 구체적으로 글리콜류와 메틸 폴리 글리콜을 혼합하여 사용하는 것이 더 바람직하다.Finally, the compounds included in the glycol ethers include methyl glycol, methyl diglycol, methyl triglycol, methyl polyglycol, ethyl glycol, and ethyl. Ethyl Diglycol, Butyl Glycol, Butyl Diglycol, Butyl Triglycol, Butyl Polyglycol, Hexyl Glycol, Hexyl Diglycol Diglycol, Ethyl Hexyl Glycol, Ethyl Hexyl Diglycol, Allyl Glycol, Phenyl Glycol, Phenyl Diglycol, Benzyl Glycol , Benzyl Diglycol, Methyl Propylene Glycol, Methyl Propylene Diglycol, Methyl Propylene Triglycol, Propylene Propylene Glycol ropyl Propylene Glycol, Propyl Propylene Diglycol, Butyl Propylene Glycol, Butyl Propylene Diglycol, Phenyl Propylene Glycol, Methyl Propylene Glycol Acetate Glycol Acetate), poly methyl glycol, and the like, but are not limited thereto. As the reducing solvent according to the present invention, it is more preferable to use the glycols and mix them with glycol ethers, and more preferably, mix glycols and methyl poly glycol.
상기 탄소나노튜브 분산액에 가하는 금속 전구체는 은(Ag), 구리(Cu), 알루미늄(Al), 주석(Sn), 비스무스(Bi) 및 안토모니(Sb)로부터 선택되는 어느 하나 이상인 금속 성분을 포함하는 화합물 또는 이들의 혼합물로부터 선택되는 것으로, 상기 금속은 탄소나노튜브에 대하여 5 내지 90중량% 함유하는 것이 열용량 성능에서 효과적으로 나타낼 수 있다. 5 중량%보다 적으면 탄소나노튜브가 너무 많아 성형을 위한 가공이 어렵고, 90 중량%를 넘으면 탄소나노튜브 함량이 너무 낮아 탄소나노튜브로 인한 열용량 효과가 적은 문제점이 있다.The metal precursor added to the carbon nanotube dispersion includes at least one metal component selected from silver (Ag), copper (Cu), aluminum (Al), tin (Sn), bismuth (Bi), and anthography (Sb). It is selected from the compound or a mixture thereof, the metal containing 5 to 90% by weight relative to the carbon nanotube can be effectively exhibited in the heat capacity performance. If less than 5% by weight is too much carbon nanotubes difficult to process for molding, if more than 90% by weight carbon nanotube content is too low there is a problem of less heat capacity effect due to carbon nanotubes.
보다 구체적으로는 질산은(Silver Nitrate), 은 아세틸아세토네이트(Silver Acetylacetonate), 은 아세테이트(Silver Acetate), 은 카보네이트(Silver Carbonate), 은 클로라이드(Silver Chloride), 알루미늄 하이드록시드(Aluminum hydroxide), 알루미늄 클로라이드(Aluminum Chloride), 알루미늄 아세틸아세토네이트(Aluminum Acetylacetonate), 알루미늄 아세테이트(Aluminum Acetate), 알루미늄 니트레이트(Aluminum Nitrate), 구리 아세틸아세토네이트(Copper Acetylacetonate, 구리 아세테이트(Copper Acetate), 주석 클로라이드(Tin Chloride), 주석 아세테이트(Tin Acetate), 안티모니 클로라이드(Antimony Chloride), 안티모니 아세테이트(Antimony Acetate), 비스무스 아세데이트(Bismuth Acetate), 비스무스 클로라이드(Bismuth Chloride) 및 이들의 수화물로부터 선택되어 사용될 수 있다.More specifically, silver nitrate, silver acetylacetonate, silver acetate, silver carbonate, silver carbonate, silver chloride, aluminum hydroxide, aluminum Aluminum Chloride, Aluminum Acetylacetonate, Aluminum Acetate, Aluminum Nitrate, Copper Acetylacetonate, Copper Acetate, Tin Chloride ), Tin acetate (Tin Acetate), antimony chloride (Antimony Chloride), antimony acetate (Antimony Acetate), bismuth acetate (Bismuth Acetate), bismuth chloride (Bismuth Chloride) and hydrates thereof can be used.
본 발명에 따른 탄소나노튜브-금속 복합체는 안정제를 더 포함하여 제조될 수 있으며, 상기 안정제는 계면활성제, 수용성 고분자, 아민류 및 이들의 혼합물로부터 선택되는 것으로, 구체적인 예시로 수용성고분자는 폴리비닐피롤리 돈(polyvinyl pyrrolidone)을 들 수 있으며, 아민류는 l차아민, 2차아민, 3차아민, 방향족아민 및 이들의 혼합물로부터 선택될 수 있으며, 보다 구체적인 예시로는 올레일아민(Oleylamine)을 들 수 있다.The carbon nanotube-metal composite according to the present invention may be prepared by further including a stabilizer, wherein the stabilizer is selected from surfactants, water-soluble polymers, amines, and mixtures thereof. Polyvinyl pyrrolidone, and the amines may be selected from primary amines, secondary amines, tertiary amines, aromatic amines, and mixtures thereof, and more specific examples thereof include oleylamine. have.
상기 제조방법으로 제조된 탄소나노튜브-금속 복합체는 탄소나노튜브와 금속의 분산성이 균일한 것이 장점이다. 그리고 탄소나노튜브-금속 복합체 분말을 다른 금속 분말과 혼합시에 분산성이 우수하고, 가공시에 첨가한 금속과 결합력이 좋아 가공후에 균일한 성형물을 얻을 수 있다. The carbon nanotube-metal composite prepared by the above manufacturing method has an advantage of uniform dispersibility of carbon nanotubes and metals. In addition, the carbon nanotube-metal composite powder is excellent in dispersibility when mixed with other metal powders, and has good bonding strength with the metal added during processing, so that a uniform molded product can be obtained after processing.
본 발명에 따른 탄소나노튜브-금속 복합체는 탄소나노튜브-은, 탄소나노튜브-구리, 탄소나노튜브-알루미늄, 탄소나노튜브-주석, 탄소나노튜브-안티모니, 탄소나노튜브-비스무스 또는 이들의 혼합물로부터 선택되는 탄소나노튜브-금속 복합체이며, 이는 써머 사이클러(Thermal cycler)의 열블럭(Thermal block)에 사용하기 위함이다. Carbon nanotube-metal composite according to the present invention is carbon nanotube-silver, carbon nanotube-copper, carbon nanotube-aluminum, carbon nanotube-tin, carbon nanotube-antimony, carbon nanotube-bismuth or It is a carbon nanotube-metal composite selected from the mixture, which is intended for use in the thermal block of the thermal cycler.
본 발명에 따른 열전도성 복합소재는 탄소나노튜브-금속 복합체 및 금속 혼합물로서, 상기 혼합하는 금속은 탄소나노튜브-금속 복합체에 대하여 10 내지 90 중량%, 바람직하게는 40 내지 70 중량%로 포함하는 것을 특징으로 한다. The thermally conductive composite material according to the present invention is a carbon nanotube-metal composite and a metal mixture, wherein the metal to be mixed contains 10 to 90% by weight, preferably 40 to 70% by weight, based on the carbon nanotube-metal composite. It is characterized by.
상기 혼합하는 금속은 은(Ag), 구리(Cu), 알루미늄(Al), 주석(Sn), 비스무스(Bi) 및 안토모니(Sb)로부터 선택되는 어느 하나 이상인 금속이며, 탄소나노튜브-금속 복합체내 금속과는 동일하거나 서로 상이할 수 있으며, 충격강도 및 물리적 기계적 특성이 향상된 우수한 열전도성 복합소재를 제조하기 위해 중요한 의미를 가진다.The metal to be mixed is any one or more metals selected from silver (Ag), copper (Cu), aluminum (Al), tin (Sn), bismuth (Bi) and anthography (Sb), and a carbon nanotube-metal composite The metals in the body may be the same or different from each other, and have an important meaning for producing an excellent thermally conductive composite having improved impact strength and physical mechanical properties.
본 발명에 따른 탄소나노튜브-금속 복합체 및 금속을 포함하는 열전도성 복합소재의 소결 가공 공정은 도 3을 참조한다.See the sintering process of the carbon nanotube-metal composite and the thermally conductive composite material including the metal according to the present invention.
본 발명은 탄소나노튜브-금속 복합체 및 금속을 포함하는 열전도성 복합소재를 소결 또는 다이캐스팅(die casting) 하여 제조되는 열전도성 성형물을 제공한다.The present invention provides a thermally conductive molding prepared by sintering or die casting a thermally conductive composite material comprising a carbon nanotube-metal composite and a metal.
상기 열전도성 성형물은 써멀 사이클러(Thermal cycler)의 열블럭(Thermal block)인 것으로, 도 4를 참조한다.The thermally conductive molding is a thermal block of a thermal cycler, see FIG. 4.
본 발명에 따른 열전도성 복합소재는 금속 단독으로 사용되고 있는 상용 제품과 비교하여 낮은 부피열용량 및 우수한 열전도성을 가지고 있으며, 금속분말의 함량 감소에 따른 원가절감과 경량화를 동시에 달성할 수 있는 효과가 있다.The thermally conductive composite material according to the present invention has a low volumetric heat capacity and excellent thermal conductivity as compared to a commercial product which is used as a metal alone, and has the effect of achieving cost reduction and weight reduction at the same time as the content of the metal powder is reduced. .
본 발명에 따른 열전도성 복합소재는 충격강도 및 물리적 기계적 특성이 향상된 우수한 열전도성 복합소재로 써멀 사이클러(Thermal cycler)의 열블럭(Thermal block)으로 이용시 생명공학 분야, 특히 유전자 진단 분야에 크게 기여할 것이다.The thermally conductive composite material according to the present invention is an excellent thermally conductive composite having improved impact strength and physical and mechanical properties, and when used as a thermal block of a thermal cycler, it may greatly contribute to the biotechnology field, particularly in the field of genetic diagnosis. will be.
이하, 하기 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 하지만, 본 발명은 하기 실시예에 의해 한정되는 것은 아니며, 본 발명의 사상과 범위 내에서 여러 가지 변형 또는 수정할 수 있음은 이 분야에서 당업자에게는 명백한 것이다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples, and various modifications or changes can be made within the spirit and scope of the present invention to those skilled in the art.
이때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명 및 첨부 도면에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
[[ 제조예Production Example 1] 탄소나노튜브-은 복합체 제조 1] Preparation of carbon nanotube-silver composite
500 ㎖ 둥근 플라스크에 얇은 다중벽 탄소나노튜브(나노텍, Thin Multi-wall CNT grade) 0.3 g을 넣고, 에틸렌 글리콜(EG) 280 ㎖를 둥근 플라스크 반응기에 투입하였다. 교반기를 장착하여 30분간 교반하고, 반응기를 초음파 세척기에 넣고 초음파를 이용하여 3시간 탄소나노튜브를 에틸렌 글리콜에 분산시켰다. 이 때 반응기의 온도는 50℃가 넘지 않도록 하였다. 초음파 처리가 끝나면 교반기를 다시 장착하고, 온도계와 냉각용 콘덴서를 연결하였다. 반응기를 교반하면서 PVP(Poly vinylpyrrolidone, 제조사: Fluka, 평균분자량(Mw): 40,000) 1.68 g, 올레일아민(Oleylamine) 5.6 ㎖를 투입하고, 이어서 질산은(Silver Nitrate; AgNO3) 1.102 g을 투입하였다.0.3 g of thin multi-walled carbon nanotubes (Nanotech, Thin Multi-wall CNT grade) was put into a 500 ml round flask, and 280 ml of ethylene glycol (EG) was charged into a round flask reactor. The mixture was stirred for 30 minutes, the reactor was placed in an ultrasonic cleaner, and the carbon nanotubes were dispersed in ethylene glycol for 3 hours using ultrasonic waves. At this time, the temperature of the reactor did not exceed 50 degreeC. After the sonication, the stirrer was mounted again, and a thermometer and a cooling condenser were connected. While stirring the reactor, 1.68 g of poly vinylpyrrolidone (manufactured by Fluka, average molecular weight (Mw): 40,000) and 5.6 mL of oleylamine were added thereto, followed by 1.102 g of silver nitrate (AgNO 3 ). .
상기 반응기에 진공 펌프를 연결하여, 반응기 내부의 공기를 제거하고 질소로 치환시켰다. 질소를 계속 투입하며 질소가 반응기 내부를 통하여 외부로 흐르게 하여 산소 유입을 막았다. 플라스크 하부에 맨틀을 설치하고 반응기 내부 온도를 200℃까지 40분에 걸쳐 승온하고, 1시간 동안 반응시켰다. 환원 반응이 종료되면 3시간에 걸쳐 반응기 온도를 상온까지 서서히 내려 탄소나노튜브-은 복합체를 합성 하였다. 상기 합성된 탄소나노튜브-은 복합체를 여과지를 이용하여 여과하고 에틸아세테이트(Ethyl acetate)와 헥산(Hexane)으로 수회 세척하여 탄소나노튜브-은 복합체를 수득하였다. A vacuum pump was connected to the reactor to remove air inside the reactor and replace with nitrogen. Nitrogen was continuously added and nitrogen was allowed to flow through the inside of the reactor to prevent the inflow of oxygen. A mantle was installed at the bottom of the flask, and the temperature inside the reactor was raised to 200 ° C. over 40 minutes and allowed to react for 1 hour. After the reduction reaction, the reactor temperature was slowly lowered to room temperature over 3 hours to synthesize a carbon nanotube-silver complex. The synthesized carbon nanotube-silver complex was filtered using filter paper and washed several times with ethyl acetate and hexane to obtain a carbon nanotube-silver complex.
상기 수득된 탄소나노튜브-은 복합체를 주사전자현미경(SEM)으로 촬영한 결과, 도 1에서도 확인할 수 있듯이 은 입자가 탄소나노튜브에 고르게 분산되어 있는 것을 확인할 수 있었다.As a result of photographing the obtained carbon nanotube-silver complex with a scanning electron microscope (SEM), it was confirmed that the silver particles were evenly dispersed in the carbon nanotubes.
[[ 제조예Production Example 2] 탄소나노튜브-구리 복합체 제조 2] carbon nanotube-copper composite
500 ㎖ 둥근 플라스크에 탄소나노튜브(한화나노텍, CM-95) 0.3 g을 넣고, 트리에틸렌 글리콜(TEG) 128 ㎖를 반응기에 투입하였다. 교반기를 장착하여 30분간 교반하고, 반응기를 초음파 세척기에 넣고 초음파를 이용하여 3시간 탄소나노튜브를 분산시켰다. 이 때 반응기의 온도는 50℃가 넘지 않도록 하였다. 초음파 처리가 끝나면 교반기를 다시 장착하고, 온도계와 냉각용 콘덴서를 연결하였다. 반응기 용액을 교반하면서 메틸 폴리 글리콜(MPG, CH3(OCH2CH2)nOH, n=4~5, 한농화성, 제품명:MPG) 4.26 ㎖를 플라스크 반응기에 투입하고 이어서 구리 아세틸아세토네이트 4.04 g을 추가로 투입하였다. 0.3 g of carbon nanotubes (Hananotech, CM-95) were put into a 500 mL round flask, and 128 mL of triethylene glycol (TEG) was added to the reactor. Equipped with a stirrer and stirred for 30 minutes, the reactor was placed in an ultrasonic cleaner to disperse carbon nanotubes for 3 hours using ultrasonic waves. At this time, the temperature of the reactor did not exceed 50 degreeC. After the sonication, the stirrer was mounted again, and a thermometer and a cooling condenser were connected. While stirring the reactor solution, 4.26 ml of methyl polyglycol (MPG, CH 3 (OCH 2 CH 2 ) nOH, n = 4-5, concentrating, product name: MPG) was added to the flask reactor, followed by 4.04 g of copper acetylacetonate. Additionally added.
상기 반응기에 진공 펌프를 연결하여, 반응기 내부의 공기를 제거하고 질소로 치환시켰다. 질소를 계속 투입하며 질소가 반응기 내부를 통하여 외부로 흐르게 하여 산소 유입을 막았다. 플라스크 하부에 맨틀을 설치하고 반응기 내부 온도를 280℃까지 1시간에 걸쳐 승온하고, 30분 동안 반응시켰다. 환원 반응이 종료되면 3 시간에 걸쳐 반응기 온도를 상온까지 서서히 내려, 탄소나노튜브-구리 복합체를 합성하였다. 기 합성된 탄소나노튜브-구리 복합체를 여과지를 이용하여 여과하고 에탄올로 수회 세척하여 탄소나노튜브-구리 복합체를 수득하였다.A vacuum pump was connected to the reactor to remove air inside the reactor and replace with nitrogen. Nitrogen was continuously added and nitrogen was allowed to flow through the inside of the reactor to prevent the inflow of oxygen. A mantle was installed at the bottom of the flask, and the temperature inside the reactor was raised to 280 ° C. over 1 hour and allowed to react for 30 minutes. After the reduction reaction was completed, the reactor temperature was gradually lowered to room temperature over 3 hours to synthesize a carbon nanotube-copper composite. The synthesized carbon nanotube-copper composite was filtered using a filter paper and washed several times with ethanol to obtain a carbon nanotube-copper composite.
상기 수득된 탄소나노튜브-구리 복합체를의 주사전자현미경(SEM)으로 촬영한 결과 도 2에서도 확인할 수 있듯이, 구리 입자는 구형에 가까우며 일정한 크기로 균일하게 탄소나노튜브에 분산되어 있는 것을 확인할 수 있었다.As a result of photographing the obtained carbon nanotube-copper composite with a scanning electron microscope (SEM), as shown in FIG. 2, it was confirmed that the copper particles were dispersed in the carbon nanotubes uniformly in a certain size. .
[[ 실시예Example 1] 탄소나노튜브-은 복합체의 성형물 제조 1] Preparation of molding of carbon nanotube-silver composite
상기 제조예 1에서 제조한 탄소나노튜브-은 복합체를 방전 플라즈마 소결 장치(Spark Plasma Sintering)에서 소결하여 성형물을 제조하였다. 흑연(graphite)으로 되어 있는 몰드(내부 중심 직경 12.6 mm)에서 상하부 펀지 사이에 탄소나노튜브-은 복합체 분말 1.2 g을 넣고, 방전 플라즈마 소결 장치(SPS-9.40MK-VII; 일본 Sumitomo Coal Mining)에 탄소나노튜브-은 복합체가 들어 있는 몰드를 수직 가압 구조의 전극 사이에 장착한 후, 유압실린터로 가압하고 진공분위기에서 소결하였다. The carbon nanotube-silver composite prepared in Preparation Example 1 was sintered in a spark plasma sintering apparatus (Spark Plasma Sintering) to prepare a molded product. 1.2 g of carbon nanotube-silver composite powder was put between the upper and lower punches in a mold made of graphite (inner center diameter of 12.6 mm) and placed in a discharge plasma sintering apparatus (SPS-9.40MK-VII; Sumitomo Coal Mining, Japan). A mold containing a carbon nanotube-silver composite was mounted between electrodes of a vertical pressurized structure, pressurized with a hydraulic cylinder, and sintered in a vacuum atmosphere.
상기 소결에 사용한 전원은 직류펄스 전원으로, 가압 압력 56 Mpa, 소결온도는 850℃, 유지시간 5분의 조건으로 소결하였다. 소결한 시편을 레이저 플래시법 열분석기(Xenon Flash Instrument LFA 447; NETZSCH)를 사용하여 분석하였고, 분석 결과는 하기 표 1에 나타내었다.The power source used for the sintering was a DC pulse power source, the pressurization pressure was 56 Mpa, the sintering temperature was sintered under the conditions of 850 ° C. and a holding time of 5 minutes. The sintered specimens were analyzed using a laser flash method thermal analyzer (Xenon Flash Instrument LFA 447; NETZSCH), and the analysis results are shown in Table 1 below.
그 결과 하기 표 1에서도 확인 할 수 있듯이, 열전도도(Heat Conductivity) 3.564 W/(m K), 열용량(Heat Capacity) 0.412 J/(g K) 및 부피 열용량(Volumetric Heat Capacity) 1.234 J/(cm3 K)로 기존 은 분말만을 단독으로 사용하였을 때 보다 부피 열용량이 우수한 것을 확인할 수 있었다. As a result, as can be seen in Table 1 below, the heat conductivity is 3.564 W / (m K), the heat capacity is 0.412 J / (g K) and the volumetric heat capacity is 1.234 J / (cm 3 K) was confirmed that the volumetric heat capacity is better than the conventional silver powder alone.
[[ 실시예Example 2-7] 탄소나노튜브-은 복합체 및 은 분말 성형물 제조 2-7] Preparation of Carbon Nanotube-Silver Composite and Silver Powder Molding
상기 제조예 1에서 제조한 탄소나노튜브-은 복합체 1.05 g과 은 분말 0.35 g(실시예 2: 75 중량%), 탄소나노튜브-은 복합체 0.8g과 은 분말 0.8 g(실시예 3; 50 중량%), 탄소나노튜브-은 복합체 0.64 g과 은 분말 0.96 g(실시예 4; 40 중량%), 탄소나노튜브-은 복합체 0.51 g과 은 분말 1.19 g(실시예 5; 30 중량%), 탄소나노튜브-은 복합체 0.36g과 은 분말 1.44 g(실시예 6; 20 중량%), 탄소나노튜브-은 복합체 0.19 g과 은 분말 1.71 g(실시예7; 10 중량%)을 혼합하여 사용하는 것을 제외하고는 상기 실시예 1과 동일한 조건으로 방전 플라즈마 소결을 진행하여 탄소나노튜브-은 및 은 혼합물 복합체 시편을 제조하였다. 소결까지의 성형공정을 개략적으로 도3의 (b)에 나타내었다. 제조된 시편은 상기 실시예 1과 동일한 조건으로 열분석을 하였으며, 그 분석 결과를 하기 표 1에 나타내었다. 1.05 g of carbon nanotube-silver composite prepared in Preparation Example 1 and 0.35 g of silver powder (Example 2: 75 wt%), 0.8 g of carbon nanotube-silver composite and 0.8 g of silver powder (Example 3; 50 wt% %), 0.64 g of carbon nanotube-silver composite and 0.96 g of silver powder (Example 4; 40 wt%), 0.51 g of carbon nanotube-silver composite and 1.19 g of silver powder (Example 5; 30 wt%), carbon 0.36 g of the nanotube-silver composite, 1.44 g of silver powder (Example 6; 20 wt%), 0.19 g of the carbon nanotube-silver composite and 1.71 g of silver powder (Example 7, 10 wt%) Except for discharge plasma sintering under the same conditions as in Example 1 to prepare a carbon nanotube-silver and silver mixture composite specimen. The molding process until sintering is schematically shown in FIG. The prepared specimens were subjected to thermal analysis under the same conditions as in Example 1, and the analysis results are shown in Table 1 below.
그 결과 상기 표 1에서도 확인 할 수 있듯이, 열전도도(Heat Conductivity) , 열용량(Heat Capacity) 및 부피 열용량(Volumetric Heat Capacity) 모두 비교예 1의 은 분말만을 단독으로 사용하였을 때 보다 우수한 것을 확인할 수 있었다.As a result, as can be seen in Table 1, the heat conductivity, heat capacity, heat capacity, and volumetric heat capacity were all superior to the case of using only silver powder of Comparative Example 1 alone. .
[실시예 8-10] 탄소나노튜브-구리 복합체 및 구리 분말 성형물 제조Example 8-10 Preparation of Carbon Nanotube-Copper Composite and Copper Powder Molding
상기 제조예 2에서 제조한 탄소나노튜브-구리 복합체 1.05 g과 구리 분말 0.0.35 g(실시예 8; 75 중량%), 탄소나노튜브-구리 복합체 0.8 g과 구리 분말 0.8 g(실시예 9; 50 중량%), 탄소나노튜브-구리 복합체 0.45 g과 구리 분말 1.35 g(실시예 10; 25 중량%)을 혼합하여 사용하는 것을 제외하고는 실시예 1와 동일한 조건으로 방전 플라즈마 소결을 진행하여 탄소나노튜브-구리 및 구리 혼합물 복합체 시편을 제조하였다. 제조된 시편은 상기 실시예 1과 동일한 조건으로 열분석을 하였으며, 그 결과는 하기 표 2에 나타내었다.1.05 g of carbon nanotube-copper composite prepared in Preparation Example 2 and 0.0.35 g of copper powder (Example 8; 75 wt%), 0.8 g of carbon nanotube-copper composite and 0.8 g of copper powder (Example 9; 50% by weight), carbon nanotube-copper composite 0.45 g and copper powder 1.35 g (Example 10; 25% by weight) except that a mixture of the discharge plasma sintering under the same conditions as in Example 1 Nanotube-copper and copper mixture composite specimens were prepared. The prepared specimens were thermally analyzed under the same conditions as in Example 1, and the results are shown in Table 2 below.
그 결과 상기 표 2에서도 확인 할 수 있듯이, 그 결과 상기 표 2에서도 확인 할 수 있듯이, 열전도도(Heat Conductivity), 열용량(Heat Capacity) 및 부피 열용량(Volumetric Heat Capacity) 모두 비교예 2의 구리 분말만을 단독으로 사용하였을 때 보다 우수한 것을 확인할 수 있었다.As a result, as can be seen in Table 2, as a result, as shown in Table 2, only the copper powder of Comparative Example 2 in both heat conductivity, heat capacity, and volumetric heat capacity When used alone it was confirmed that the superior.
[[ 실시예Example 11] 탄소나노튜브-은 복합체 및 안티모니 분말 성형물 제조 11] Preparation of carbon nanotube-silver composite and antimony powder molding
상기 제조예 1에서 제조한 탄소나노튜브-은 복합체 0.51 g과 안티모니 분말 1.19 g을 혼합(70 중량%)하여 소결온도를 500℃로 소결하는 것을 제외하고는 상기 실시예 1과 동일한 조건으로 방전 플라즈마 소결을 진행하여 탄소나노튜브-은 및 안티모니 혼합물 복합체 시편을 제조하였다. 제조된 시편은 상기 실시예 1과 동일한 조건으로 열분석을 하였으며 그 결과, 열전도도(Heat Conductivity) 5.055 W/(m K), 열용량(Heat Capacity) 0.378 J/(g K)이며, 부피 열용량(Volumetric Heat Capacity) 1.532 J/(cm3 K)로 상기 비교예 1의 은 분말만을 단독으로 사용하였을 때 보다 우수한 것을 확인할 수 있었다.Discharge under the same conditions as in Example 1 except that 0.51 g of the carbon nanotube-silver composite prepared in Preparation Example 1 and 1.19 g of antimony powder were mixed (70 wt%) to sinter the sintering temperature at 500 ° C. Plasma sintering was performed to prepare carbon nanotube-silver and antimony mixture composite specimens. The prepared specimens were thermally analyzed under the same conditions as in Example 1, and as a result, the heat conductivity was 5.055 W / (m K), the heat capacity was 0.378 J / (g K), and the volumetric heat capacity ( Volumetric Heat Capacity) 1.532 J / (cm 3 K) was confirmed to be superior to when using only the silver powder of Comparative Example 1 alone.
[[ 실시예Example 12] 탄소나노튜브-은 복합체 및 주석 분말 성형물 제조 12] Preparation of carbon nanotube-silver composite and tin powder molding
상기 제조예 1에서 제조한 탄소나노튜브-은 복합체 0.51 g과 주석 분말 1.19 g을 혼합(70 중량%)하여 소결온도 180℃로 소결하는 것을 제외하고는 상기 실시예 1과 동일한 조건으로 방전 플라즈마 소결을 진행하여 탄소나노튜브-은 및 주석 혼합물 복합체 시편을 제조하였다. 제조된 시편은 상기 실시예 1과 동일한 조건으로 열분석을 하였다. 그 결과, 열전도도(Heat Conductivity) 2.158 W/(m K), 열용량(Heat Capacity) 0.305 J/(g K) 및 부피 열용량(Volumetric Heat Capacity) 1.322 J/(cm3 K)로 상기 비교예 1의 은 분말만을 단독으로 사용하였을 때 보다 우수한 것을 확인할 수 있었다.Discharge plasma sintering under the same conditions as in Example 1 except that 0.51 g of the carbon nanotube-silver composite prepared in Preparation Example 1 and 1.19 g of tin powder were mixed (70 wt%) and sintered at a sintering temperature of 180 ° C. Proceed to prepare a carbon nanotube-silver and tin mixture composite specimen. The prepared specimen was thermally analyzed under the same conditions as in Example 1. As a result, Comparative Example 1 with a heat conductivity of 2.158 W / (m K), a heat capacity of 0.305 J / (g K), and a volumetric heat capacity of 1.322 J / (cm 3 K). When only the silver powder of was used alone was confirmed to be superior.
도 1은 본 발명에 따른 탄소나노튜브-은 복합체를 주사전자현미경(SEM)으로 관찰한 사진이고,1 is a photograph of a carbon nanotube-silver complex according to the present invention observed with a scanning electron microscope (SEM),
도 2는 발명에 따른 탄소나노튜브-구리 복합체를 주사전자현미경(SEM)으로 관찰한 사진이고,Figure 2 is a photograph of the carbon nanotube-copper composite according to the invention observed with a scanning electron microscope (SEM),
도 3은 본 발명에 따른 탄소나노튜브-금속 복합체 및 금속을 포함하는 열전도성 복합소재의 소결 가공 공정을 개략적으로 도시한 도면이고,3 is a view schematically showing a sintering process of a thermally conductive composite material including a carbon nanotube-metal composite and a metal according to the present invention;
도 4는 본 발명에 따른 열전도성 복합소재를 소결 또는 다이캐스팅(die casting) 하여 제조한 써멀 사이클러 열블럭의 입체도면을 보여주는 도면이다.Figure 4 is a view showing a three-dimensional view of the thermal cycler thermal block produced by sintering or die casting (die casting) the thermally conductive composite material according to the present invention.
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| CN110387281A (en) * | 2019-06-26 | 2019-10-29 | 包头协同纳米新材科技有限公司 | Carbon nanotube/zero dimensional nanometer materials composite material and its preparation method and application |
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2010
- 2010-10-11 WO PCT/KR2010/006935 patent/WO2011046330A2/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013137673A1 (en) * | 2012-03-15 | 2013-09-19 | (주)바이오니아 | Heating paste and heating element comprising same |
| KR20160075081A (en) | 2014-12-19 | 2016-06-29 | 김정기 | Attached to the high hyongyul ESS system using nanomaterials and natural energy generator vessel |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011046330A3 (en) | 2011-09-15 |
| WO2011046330A2 (en) | 2011-04-21 |
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