KR20100116399A - Graphene coating method and graphen nano-structure - Google Patents
Graphene coating method and graphen nano-structure Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- 238000000576 coating method Methods 0.000 title claims description 15
- 239000002086 nanomaterial Substances 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000010409 thin film Substances 0.000 claims abstract description 26
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- 239000002994 raw material Substances 0.000 claims description 26
- 229910002804 graphite Inorganic materials 0.000 claims description 13
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- 239000000443 aerosol Substances 0.000 claims description 12
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- 150000001875 compounds Chemical class 0.000 claims description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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Abstract
본 발명은 초고속으로 가속된 그래핀(graphene)을 기판 위에 증착시켜 종래의 그래핀 박막과는 다른 새로운 형태의 그래핀 박막을 형성시키는 방법과, 그 방법에 의해 제조된 그래핀 박막 구조체를 제공한다. 이러한 그래핀 박막 구조체는 의 바인더 수지를 포함하지 않고, 촉매를 사용하지 않고 형성되어, 그래핀-기판간, 인접한 그래핀간 직접결합 구조로 형성된다. 이러한 그래핀 박막 구조체는 투명전도막과 방열부분에 이용될 수 있다.The present invention provides a method for forming a graphene thin film of a new type different from the conventional graphene thin film by depositing graphene accelerated at an extremely high speed, and a graphene thin film structure manufactured by the method. . The graphene thin film structure does not include a binder resin of and is formed without using a catalyst, thereby forming a direct bond structure between graphene-substrate and adjacent graphene. The graphene thin film structure may be used for the transparent conductive film and the heat dissipation portion.
Description
본 발명은 그래핀 코팅 방법 및 그래핀 나노 구조체에 관한 것으로서, 더욱 자세하게는 그래핀 원료를 고속으로 기판에 충돌시켜 코팅하는 방법과, 이 방법을 통해 그래핀-기판간, 인접하는 그래핀간 직접 화학결합이 형성된 그래핀 나노 구조체에 관한 것이다.The present invention relates to a graphene coating method and a graphene nanostructure, and more particularly, a method of coating a graphene raw material on a substrate at a high speed, and through this method, the direct chemistry between graphene-substrate, adjacent graphene It relates to a graphene nanostructure formed bond.
종래 그래핀 박막을 제조하는 방법은 촉매를 이용하는 Chemical vapor deposition(CVD)이 유일하다. CVD법은 특정 촉매를 기판 위에 형성시키고 기판을 가열하여 하이드로 카본 전구체가 열적-화학적 작용에 의해 깨지면서 촉매부에서 그래핀 박막이 성장되도록 하는 방법이다. CVD법은 단층 혹은 2~3층 그래핀 제조에 매우 중요한 기술이며 차세대 고속 트랜지스터 제조에 핵심 기술로 평가받고 있다. 그러나 CVD법을 이용한 그래핀 박막은 연속적인 그래핀 박막 제조가 불가능하므로 군데군데 성장된 아일랜드 형태의 CVD 박막에 한정되고 있다. 따라서 현 시점에서 촉매지원 CVD법을 제외하고는 연속적인 그래핀 박막 제조기술은 기대하기 어려웠다.Conventional methods of producing a graphene thin film are chemical vapor deposition (CVD) using a catalyst. The CVD method is a method in which a specific catalyst is formed on a substrate and the substrate is heated to cause the graphene thin film to grow in the catalyst portion while the hydrocarbon precursor is broken by thermal-chemical action. CVD is a very important technology for the manufacture of single layer or two or three layers of graphene and has been regarded as a key technology for next generation high speed transistor manufacturing. However, since the graphene thin film using the CVD method is not capable of producing a continuous graphene thin film, it is limited to the island-shaped CVD thin film grown at various locations. Therefore, except for the catalyst-assisted CVD method, continuous graphene thin film manufacturing technology was difficult to expect at this point.
본 발명은 새로운 형태의 그래핀 나노구조체 또는 그래핀 나노구조체 박막을 새롭게 제공함으로서 투명전도막 분야, 방열분야, 나노 기능성 기판들을 저가로 손쉽게 제공함에 그 목적이 있다. An object of the present invention is to provide a new type of graphene nanostructure or graphene nanostructure thin film to provide a transparent conductive film, heat dissipation, and nano functional substrates at low cost.
본 발명에서는 1) 별도의 바인더 수지를 포함하지 않고, 2) 촉매를 사용하지 않으며, 3) 그래핀-기판간, 그래핀-그래핀간 직접결합(화학결합)이 형성되어 있는 그래핀 나노 구조체를 제공함으로서, 종래의 그래핀 구조체(박막)가 갖고 있던 문제점들을 해소하고자 하였다.In the present invention, 1) does not include a separate binder resin, 2) does not use a catalyst, and 3) graphene nano-structures in which direct bonds (chemical bonds) between graphene-substrate and graphene-graphene are formed. To solve the problems of conventional graphene structures (thin films).
상기한 구조는 그래핀을 100m/s ~ 1000m/s로 가속시킨 상태로 기판에 충돌시킴으로서 그래핀 원료의 운동에너지가 소모되는 과정을 응용하여 형성시킬 수 있으며, 그래핀와 기판 간의 고속 충돌은 에어로졸 증착법, 콜드 스프레이법, 펄스 가속법 중 어느 하나를 선택적용할 수 있다. The above structure can be formed by applying a process in which the kinetic energy of the graphene raw material is consumed by colliding the substrate with the graphene accelerated to 100m / s ~ 1000m / s, the high-speed collision between the graphene and the substrate is aerosol deposition The cold spray method or the pulse acceleration method can be selectively used.
상기한 본 발명에 따르면 그래핀 원료를 고속으로 가속시켜 기판 위에 충돌시킴으로써 별도의 바인더 수지를 포함하지 않고 기판에 그래핀이 직접 부착된 그래핀 나노구조체를 손쉽게 제조할 수 있다. 이렇게 제조된 그래핀 나노 구조체는 투명전도막, 방열기판 등에 다양한 활용이 될 것으로 기대된다. According to the present invention as described above, by accelerating the graphene raw material at a high speed to impinge on the substrate, it is possible to easily prepare a graphene nanostructure in which graphene is directly attached to a substrate without a separate binder resin. The graphene nanostructures thus prepared are expected to be used in a variety of applications, such as transparent conductive film, heat radiation substrate.
Ⅰ. Ⅰ. 그래핀Graphene 코팅 방법 Coating method
본 발명은 (a) 그래핀 원료 제조 단계; 및 (b) 상기 그래핀 원료를 100m/s ~ 1000m/s 로 가속하여, 기판에 충돌시키는 단계; 로 이루어지는 그래핀 코팅방법을 제공한다.The present invention (a) graphene raw material manufacturing step; And (b) accelerating the graphene raw material at 100 m / s to 1000 m / s to impinge on the substrate; It provides a graphene coating method consisting of.
1. (a)단계1.step (a)
본 단계는 그래핀 원료 제조 단계이다. This step is a graphene raw material manufacturing step.
본 단계에서는 탄소-층간 화합물(CIC : carbon intercalated compounds)에 마이크로 웨이브 처리 또는 고온 열처리를 하여 팽창 흑연(expanded graphene)을 제조하고, 상기 팽창 흑연을 용매에 넣고 분산하는 과정을 통해 그래핀 원료를 제조할 수 있다. 상기 팽창 흑연은 단순히 기계적 방법으로 분쇄할 수도 있으나, 원료의 균일 분산 측면에서는 액상 초음파 분산법이 좋다. 즉, 제조된 팽창 흑연을 용매 속에 집어넣고 초음파 분쇄하여 그래핀 원료를 얻어내는 것이다.In this step, expanded graphene is prepared by microwave treatment or high temperature heat treatment of carbon intercalated compounds (CIC), and graphene raw materials are prepared by dispersing the expanded graphite in a solvent. can do. The expanded graphite may be simply pulverized by a mechanical method, but liquid ultrasonic dispersion is preferable in terms of uniform dispersion of raw materials. That is, the prepared expanded graphite is put in a solvent and ultrasonically pulverized to obtain a graphene raw material.
상기 탄소 층간 화합물(CIC)은 종래부터 제조법이 확립되어 있으며, 대표적으로는 발열황산이 흑연 분말의 그라파이트 층 사이에 들어가 있는 것이 상용화되어 있고 이는 매우 저가이다.The carbon interlayer compound (CIC) has been conventionally established in manufacturing methods, and typically, it is commercialized that exothermic sulfuric acid is interposed between graphite layers of graphite powder, which is very inexpensive.
상기 마이크로 웨이브 처리는 CIC에 마이크로 웨이브(예, 2450MHZ의 마이크로 웨이브)를 조사하는 것으로서, 마이크로웨이브가 조사되면 분자단위에서의 진동이 시작되고 이 진동에너지가 열에너지로 바뀌며 탄소층간에 들어가 있던 무수황산들이 이 열에너지를 받아 순식간에 기체화되어 날아간다. 이 과정에서 CIC의 탄소층 사이가 벌어지며 원래 부피보다 수백 배 부피가 커진 팽창 흑연이 된다. 이 과정은 공기 중에서 수행해도 되나 바람직하게는 불활성 기체, N2, Ar, He 등에서 수행하는 것이 좋다. 이러한 마이크로 웨이브 처리의 최종적인 메카니즘이 열에너지에 의해 수행되는 만큼 약 1,000 도 이상의 고온에서 수초 이상 열처리해주는 방법을 통해 팽창흑연을 제조하는 방법도 바람직하다.The microwave treatment is to irradiate microwaves (eg, 2450MHZ microwaves) to the CIC. When microwaves are irradiated, vibrations are initiated at the molecular level, and the vibration energy is converted into thermal energy. Receives this heat energy and gasifies instantly and flies away. In this process, the gap between the CIC's carbon layers is expanded, resulting in expanded graphite that is hundreds of times larger than its original volume. This process may be carried out in air, but it is preferably carried out in an inert gas, N 2, Ar, He or the like. Since the final mechanism of the microwave treatment is performed by thermal energy, a method of producing expanded graphite is also preferred through heat treatment for several seconds or more at a high temperature of about 1,000 degrees or more.
한편, 팽창 흑연을 용매에 집어넣고 분산(초음파 분쇄)시키는 단계는 층간 어느 정도 벌어져 있는 팽창 흑연들을 완전히 분산시키는 단계이다. 따라서 이 과정을 통하여 흑연층이 10층 이하인 그래핀 또는 흑연층이 10층 이상인 탄소 플레이크들이 만들어 질 수 있다. 이 과정에서는 기존 탄소나노튜브 분산 방법을 적용하여 산처리, 화학처리 및 바인더 첨가를 수행하여도 괜찮다.On the other hand, the step of putting the expanded graphite in the solvent and dispersing (ultrasound pulverization) is a step of completely dispersing the expanded graphite that is somewhat open between the layers. Therefore, through this process, graphene having a graphite layer of 10 layers or less or carbon flakes having 10 or more layers of graphite layers may be made. In this process, acid treatment, chemical treatment and binder addition may be performed by applying a conventional carbon nanotube dispersion method.
도 1은 분산액의 상층부를 TEM 그리드위에 올려 촬영한 단일 그래핀의 전자 현미경 사진이다. 도 1은 아주 얇은 형태의 그래핀이 성공적으로 제조되었음을 보여준다. 일반적으로 탄소층의 수가 10개 미만이면 그래핀 고유 전기전도물성이 발 휘된다고 알려져 있다. 그래핀의 이론적 전류밀도는 구리/ 은의 약 1,000 배이다. 탄소층의 개수가 10층 이상이면 그래핀 고유의 물성, 즉 전기전도도가 떨어지지만 2차원적인 면접촉으로 인하여 전기전도도 물성을 발휘할 수 있다. 이런 면접촉 효과는 기존 나노입자 사이의 점접촉과 CNT사이의 선접촉과는 전혀 다른 그래핀만의 고유 특성이다.FIG. 1 is an electron micrograph of single graphene photographed by placing an upper layer of a dispersion on a TEM grid. 1 shows that graphene in a very thin form was successfully prepared. In general, it is known that the number of carbon layers is less than 10, and thus the graphene electrical conductivity is exhibited. The theoretical current density of graphene is about 1,000 times that of copper / silver. When the number of carbon layers is 10 or more layers, graphene's inherent physical properties, ie, electrical conductivity, are inferior, but electrical conductivity may be exhibited due to two-dimensional surface contact. This surface contact effect is unique to graphene, which is completely different from point contact between existing nanoparticles and line contact between CNTs.
본 단계에서는 그래핀에 불순물(예, 보론(B), 인(P))을 도핑시키는 과정을 포함시킬 수 있다. 또한, 본 단계에서는 그래핀 원료에 나노파티클형(nanoparticle), 나노선형(Nanowire), 나노로드형(Nanorod), 나노벨트형(Nanobelt) 및 분말형 중 어느 한 유형 이상의 탄소원료를 혼입시키는 과정을 더 포함시킬 수 있으며, 마찬가지로 그래핀 원료에 탄소나노튜브를 혼입시키는 과정을 더 포함시킬 수 있다.In this step, the graphene may include a step of doping impurities (eg, boron (B), phosphorus (P)). In addition, in this step, a process of incorporating a carbon raw material of at least one type of nanoparticles, nanowires, nanorods, nanobelts, and powders into the graphene raw material is carried out. It may be further included, and likewise can further include the process of incorporating carbon nanotubes into the graphene raw material.
또한, 본 단계에서는 그래핀 코팅단계(박막형성 단계 또는 두꺼운 막 형성단계 - 즉, 후술할 (b)단계)에서 일부 화학반응을 유도하기 위한 반응성 가스 도입과정을 더 포함시킬 수 있다.In addition, this step may further include a reactive gas introduction process for inducing some chemical reaction in the graphene coating step (thin film forming step or thick film forming step-that is, step (b) to be described later).
또한, 본 단계에서는 그래핀 원료를 물리적으로 변형시키거나, 화학적으로 전처리하여 표면 개질하는 과정을 포함시킬 수 있다. 표면 개절의 한 예로는 볼밀링을 들 수가 있다. In addition, this step may include the step of physically modifying the graphene raw material, or chemically pre-treated surface modification. One example of surface modification is ball milling.
2. (b)단계2. Step (b)
본 단계는 상기 그래핀 원료를 100m/s ~ 1000m/s로 가속하여, 기판에 충돌시키는 단계이다. This step is to accelerate the graphene raw material to 100m / s to 1000m / s, impinging on the substrate.
고속으로 가속된 그래핀 원료를 기판에 충돌시키는 과정은 고압고온 노즐 분사(콜드 스프레이법) 또는 펄스형 팽창 원리(펄스 가속법) 또는 에어로졸화된 그래핀의 진공팽창 원리(에어로졸 증착법)에 의하여 달성될 수 있다 . The process of colliding the graphene raw material accelerated at high speed to the substrate is achieved by high pressure high temperature nozzle spray (cold spray method) or pulsed expansion principle (pulse acceleration method) or vacuum expansion principle of aerosolized graphene (aerosol deposition method). Can be.
상기 콜드 스프레이법은 통상적으로 금속 분말의 배선에 많이 이용되는 방법이다. 본 발명에서는 콜드 스프레이의 초음속 속도를 최대한 활용한다. 본 발명에서의 콜드 스프레이법은 그래핀 원료를 노즐을 통해 고온/고압 압축 공기와 함께 기판에 고속으로 분사하여 코팅물을 얻는 방법이다. 이때 고압가스를 얻기 위하여 압축가스 용기를 수백도로 가열할 수 있다.The cold spray method is a method commonly used for wiring of metal powder. In the present invention, to maximize the supersonic speed of the cold spray. The cold spray method in the present invention is a method of obtaining a coating by spraying the graphene raw material to the substrate at high speed with a high temperature / high pressure compressed air through a nozzle. At this time, the compressed gas container may be heated to several hundred degrees to obtain a high pressure gas.
상기 펄스 가속법은 기체를 펄스 혹은 초단파로 진공중에 분사함으로서 103 - 104 m/s를 가속력을 얻을 수 있는 방법이다. 이 방법은 보통 서브 나노미터 재료 혹은 클러스터 분자빔을 기상에서 얻어내고 분광학적 기법을 이용하여 이들을 연구하는데 이용되어 왔다. 이러한 펄스 가속법을 사용하는 이유는 고진공 유지를 위해서이다. 고진공이 유지된 상태로 간헐적으로 들어오는 캐리어 기체는 압력차 및 펌프 의 펌핑 스피드에 의하여 최고의 가속력을 얻을 수 있다. 만일 콜드 스프레이법에서처럼 많은 양의 가스가 들어오면 진공 유지가 불가능하다. 이런 원리를 통하여 그래핀을 고속으로 기판에 분사시킬 수 있다.The acceleration pulse is injected by method 10 3 in a vacuum or very high frequency pulses in a gas - is how to 10 4 m / s to obtain the acceleration. This method is commonly used to obtain sub-nanometer materials or clustered molecular beams in the gas phase and to study them using spectroscopic techniques. The reason for using this pulse acceleration method is to maintain high vacuum. Carrier gas that enters intermittently while maintaining high vacuum can obtain the best acceleration due to the pressure difference and the pumping speed of the pump. If a large amount of gas enters, as in the cold spray method, it is impossible to maintain a vacuum. Through this principle, graphene can be sprayed onto the substrate at high speed.
에어로졸 증착법은 상기 펄스 가속법과 같은 엄청난 가속력을 얻지는 못하지만 아음속에서도 좋은 증착막을 얻어낼 수 있다. 고속 가속에 의한 박막형성원리는 에어로졸 증착원리에 의하여 설명이 가능하다. 통상적인 에어로졸 증착법에 의하면 고속으로 가속되는 입자들이 기판에 충돌할 경우 막대한 충돌에너지가 발생하며 이 충돌에너지의 일부가 결합형성(bond formation)을 하는데 소모되어 입자-기판, 입자-입자간 직접적인 결합이 가능해짐을 설명하고 있다. 일반적인 에어로졸 증착법에서는 충돌 속도가 50m/s 근처에서도 직접적인 결합 형성이 가능하여 하드(hard)한 세라믹 박막 제조가 가능하다. The aerosol deposition method does not obtain tremendous acceleration as the pulse acceleration method, but can obtain a good deposition film even at subsonic speed. The principle of thin film formation by rapid acceleration can be explained by the principle of aerosol deposition. According to the conventional aerosol deposition method, when the particles accelerated at high speed collide with the substrate, enormous collision energy is generated, and a part of the collision energy is consumed to bond formation. It explains that it is possible. In the general aerosol deposition method, a direct bond can be formed even at a collision speed of about 50 m / s, thereby making a hard ceramic thin film.
Ⅱ. II. 그래핀Graphene 나노 구조체 Nano structure
본 발명은 상기한 그래핀 박막 코팅 방법에 의해 제조되며, 바인더 및 촉매 없이 그래핀-기판간, 인접한 그래핀간 직접결합이 형성된 것을 특징으로 하는 그래핀 박막 구조체를 함께 제공한다.The present invention is prepared by the above-described graphene thin film coating method, and provides a graphene thin film structure, characterized in that a direct bond between graphene-substrate and adjacent graphene is formed without a binder and a catalyst.
도 2는 그래핀이 기판에 증착된 모습을 나타낸 SEM 사진이다. 도 2는 10초 동안의 짧은 증착으로 아주 얇은 그래핀 박막이 형성된 예로서, 기판 군데군데 코팅이 안 된 모습이 관찰되고, 단층에서부터 수층의 그래핀이 증착되어 있는 부분들도 관찰된다.2 is a SEM photograph showing the state that graphene is deposited on a substrate. FIG. 2 is an example in which a very thin graphene thin film is formed by a short deposition for 10 seconds, and the uncoated state of the substrate is observed in several places, and the portions where the graphene of several layers are deposited from a single layer are also observed.
이 때, 그래핀 에어로졸의 속도는 200(±100) m/s 이며 증착에 소요된 시간은 10초였다. 에어로졸 챔버의 압력은 500~700 torr이고 증착챔버의 압력은 5~10 torr였다. At this time, the velocity of the graphene aerosol was 200 (± 100) m / s, and the deposition time was 10 seconds. The pressure in the aerosol chamber was 500-700 torr and the pressure in the deposition chamber was 5-10 torr.
도 3은 본 발명에 따른 그래핀 나노 구조체 실시예의 하나로서 실제 그래핀이 기판에 증착된 모습을 나타낸 SEM 사진이다. 도 4는 그래핀이 두껍게 연속적으로 적층되어 있는 모습을 보여준다. FIG. 3 is a SEM photograph showing a state in which actual graphene is deposited on a substrate as one example of the graphene nanostructure according to the present invention. Figure 4 shows the graphene is stacked in a continuous thick.
이 때, 그래핀 에어로졸의 속도는 200~300m/s 였으며, 이에 소요된 시간은 5분이다. 이 때 도입된 가스의 압력은 2기압이고 증착 챔버의 압력은 5~20Torr였다. 펄스 가속법을 사용하였고 펄스 주기는 5초(4초 휴지 기간, 1초 증착 기간)로 하였고, 휴지기간 동안 증착 챔버는 진공상태로 항상 유지시켰다.At this time, the speed of the graphene aerosol was 200 ~ 300m / s, this time is 5 minutes. The pressure of the introduced gas was 2 atm and the pressure of the deposition chamber was 5 to 20 Torr. The pulse acceleration method was used and the pulse period was 5 seconds (4 second rest period, 1 second deposition period), and the deposition chamber was always kept in vacuum during the rest period.
도 4는 탄소나노튜브(CNT)와 그래핀을 5:5 무게비로 혼합한 후 증착한 모습을 보여주는 SEM 사진이다. 도 4는 아주 짧은 시간(5초) 동안 증착한 후의 모습이다. 그래핀/CNT 혼합 에어로졸의 속도는 200(±100) m/s 였으며, 에어로졸 챔버의 압력은 500~700torr이고 증착챔버의 압력은 5~10torr였다. 4 is a SEM photograph showing carbon nanotube (CNT) and graphene mixed at a weight ratio of 5: 5 and then deposited. 4 is a view after the deposition for a very short time (5 seconds). The rate of graphene / CNT mixed aerosol was 200 (± 100) m / s, the pressure in the aerosol chamber was 500 ~ 700torr and the pressure in the deposition chamber was 5 ~ 10torr.
상기한 실험예들을 통해 그래핀 충돌 속도 200 m/s는 그래핀-기판, 그래핀-그래핀 사이의 직접적인 결합을 가능케 하는 충분한 에너지원이 됨을 알 수 있다. 도 2 내지 도 4에 도시된 형태의 박막은 기존의 방법 CVD법에서 얻어지는 그래핀 박막과는 그 생성 메카니즘과 박막구조가 전혀 다르다.Through the above experimental examples, it can be seen that the graphene collision speed 200 m / s is a sufficient energy source to enable direct bonding between graphene-substrate and graphene-graphene. The thin film of the type shown in FIGS. 2 to 4 is completely different from the graphene thin film obtained by the conventional method CVD method and its thin film structure.
도 1은 단일 그래핀의 TEM 사진이다.1 is a TEM photograph of a single graphene.
도 2는 본 발명에 의해 제조된 그래핀 박막의 SEM 사진이다.2 is an SEM photograph of the graphene thin film prepared according to the present invention.
도 3은 본 발명에 따른 그래핀 코팅 방법을 시행하여 두꺼운 막으로 기판에 코팅된 그래핀 나노 구조체의 SEM 사진이다.3 is an SEM photograph of a graphene nanostructure coated on a substrate with a thick film by the graphene coating method according to the present invention.
도 4는 그래핀에 탄소나노튜브를 혼입한 원료를 고속으로 가속하여 기판에 충돌시킴으로서 형성된 박막의 SEM 사진이다.FIG. 4 is a SEM photograph of a thin film formed by accelerating a raw material mixed with carbon nanotubes into graphene at a high speed to collide with a substrate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101281881B1 (en) * | 2011-07-12 | 2013-07-05 | 성균관대학교산학협력단 | Electrodeposition of graphene layer from doped graphite |
| KR101339441B1 (en) * | 2011-10-31 | 2013-12-06 | 성균관대학교산학협력단 | Multiple layer complex of graphene and conducting polymer through electrochemical deposition and method thereof |
| KR101485833B1 (en) * | 2013-10-30 | 2015-01-28 | 이재호 | Nano-micro particles manufacturing method and device |
| WO2021186157A2 (en) | 2020-03-16 | 2021-09-23 | Vozyakov Igor | Method and apparatus for monomolecular layers |
| KR20220060376A (en) * | 2020-11-04 | 2022-05-11 | 넥센타이어 주식회사 | Tires equipped with reinforcing members with heat dissipation performance |
| KR20220060363A (en) * | 2020-11-04 | 2022-05-11 | 넥센타이어 주식회사 | Tires with heat dissipation performance |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101281881B1 (en) * | 2011-07-12 | 2013-07-05 | 성균관대학교산학협력단 | Electrodeposition of graphene layer from doped graphite |
| US9133562B2 (en) | 2011-07-12 | 2015-09-15 | Research & Business Foundation Sungkyunkwan University | Electrodeposition of graphene layer from doped graphite |
| KR101339441B1 (en) * | 2011-10-31 | 2013-12-06 | 성균관대학교산학협력단 | Multiple layer complex of graphene and conducting polymer through electrochemical deposition and method thereof |
| KR101485833B1 (en) * | 2013-10-30 | 2015-01-28 | 이재호 | Nano-micro particles manufacturing method and device |
| WO2015065033A1 (en) * | 2013-10-30 | 2015-05-07 | 이재호 | Method for producing nano-micro particles through continuous collision mode of two-way pulses, and apparatus therefor |
| WO2021186157A2 (en) | 2020-03-16 | 2021-09-23 | Vozyakov Igor | Method and apparatus for monomolecular layers |
| KR20220060376A (en) * | 2020-11-04 | 2022-05-11 | 넥센타이어 주식회사 | Tires equipped with reinforcing members with heat dissipation performance |
| KR20220060363A (en) * | 2020-11-04 | 2022-05-11 | 넥센타이어 주식회사 | Tires with heat dissipation performance |
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