WO2012148034A1 - Production method for nano silicon carbide using a thermal plasma - Google Patents

Production method for nano silicon carbide using a thermal plasma Download PDF

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WO2012148034A1
WO2012148034A1 PCT/KR2011/003850 KR2011003850W WO2012148034A1 WO 2012148034 A1 WO2012148034 A1 WO 2012148034A1 KR 2011003850 W KR2011003850 W KR 2011003850W WO 2012148034 A1 WO2012148034 A1 WO 2012148034A1
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silicon carbide
silicon
thermal plasma
fine powder
nano
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French (fr)
Korean (ko)
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전성덕
배일호
유연태
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주식회사 네오플랜트
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Definitions

  • the present invention relates to a method for producing nano-silicon carbide using thermal plasma, and more particularly, a) synthesizing microsilicon carbide (SiC) by mixing and calcining silicon fine powder and carbon source; b) relates to a method for preparing nanosilicon carbide using thermal plasma, which comprises the step of treating the microsilicon carbide with thermal plasma to produce nanosilicon carbide.
  • Silicon carbide is physically and chemically stable, has excellent heat resistance and high thermal conductivity, and has excellent high temperature stability, high temperature strength, and high wear resistance. Therefore, high temperature materials, high temperature semiconductors, jig for semiconductors, wear resistant materials, It is mainly used to manufacture corrosion resistant or chemical resistant parts or electronic parts of automobile parts, chemical plants.
  • the surface energy is higher than the micro-sized powder, and thus, the sintering property is excellent, so that a dense silicon carbide product can be manufactured even at low temperature, and has the advantage of being widely used as a reinforcing material for various nanocomposites.
  • SiC is considered to be used as a high-temperature / low-radiation structural material in the construction of a fusion reactor such as, for example, a fusion blanket blanket material and a plasma facing material.
  • SiC is advantageously produced in powder form that can be molded into tiled structural blocks for fusion reactors. Therefore, there is an increasing demand for the development of the synthesis technology of SiC nanopowders having the advantage of providing a very compact structural material during the molding process.
  • SiC nanopowders can be synthesized through various methods such as gas phase synthesis using plasma, laser and microwave, and sol-gel method.
  • the New Materials Research Group of the Japan Institute of New Technology has synthesized SiC nanopowders of 30-50 nm in size using RF thermal plasma.
  • Ethylene (C 2 H 4 ) gas is used as the carbon source and SiH is used as the raw material for Si. 4 gases were used.
  • SiC nanopowders having a size of tens of nm having excellent dispersibility have been produced, but have a problem in that operating costs of raw materials and RF plasma are high. Also, Prof.
  • the silica reduction method is mainly micro-sized powder, the yield of the nano powder is extremely insignificant, there is an environmental problem due to the generation of carbon monoxide in the manufacturing process, there is a problem that the economic efficiency is poor due to poor productivity.
  • toxic gas is generated during the decomposition of silane, and even a small amount of gas leakage can cause a fatal situation. Solvents, polymers, and products after the reaction cannot be recycled, resulting in environmental pollution.
  • the polysilicon and organosilicon materials are pulverized / classified of metal silicon lumps (lumps) so that particles having a size of 50-450 microns are used for the production of polysilicon as a product.
  • metal silicon lumps particle size 50-450 s
  • waste fine powder of high purity Si (98% or more) having a particle size of 100 ⁇ m or less is inevitably generated.
  • 150 tons / month generated in Korea alone it is estimated that 150 tons / month generated in Korea alone, and that the increase in the production of metal silicon powder will increase.
  • there is no proper treatment method for such high-purity waste fine powder so it is currently used for low value-added applications such as fillers.
  • the technical problem to be achieved by the present invention is to provide a method for relatively simple and economical synthesis of nano silicon carbide using silicon fine powder, in particular Si waste fine powder having a particle diameter of 100 ⁇ m or less generated during the metal silicon grinding / classification process, etc. It is to achieve high value-adding of silicon fine powder and at the same time to make nano silicon carbide in economical and environmentally friendly way.
  • the present invention comprises the steps of synthesizing micro silicon carbide (SiC) by mixing and firing silicon fine powder and a carbon source; It provides a method for producing nano-silicon carbide using a thermal plasma comprising the step of treating the micro-silicon carbide with thermal plasma to produce nano-silicon carbide.
  • SiC micro silicon carbide
  • the present invention provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the silicon fine powder is a waste fine powder having a particle diameter of 100 ⁇ m or less generated during the grinding / classification process of the metal silicon lump.
  • the present invention also provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the silicon fine powder is subjected to pickling and washing before firing in step a).
  • the present invention also provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the carbon source is at least one solid carbon source selected from the group consisting of activated carbon, carbon black and graphite.
  • the present invention provides a method for producing nano-silicon carbide using a thermal plasma, characterized in that the mixing of the step a) is carried out using a ball mill.
  • the present invention provides a method for producing nano-silicon carbide using a thermal plasma, characterized in that the ratio of silicon and carbon source in the mixing of step a) is made in the range of 1: 1.5 to 2.
  • the present invention provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the thermal plasma treatment of the micro silicon carbide is made in a continuous manner.
  • the method for producing nano silicon carbide using the thermal plasma according to the present invention provides a method for relatively easily and economically synthesizing nano silicon carbide using Si powder with a particle diameter of 100 ⁇ m or less generated during the metal silicon grinding / classification process. High value-added silicon fines can be achieved while nano-silicon carbide can be manufactured in an economical and environmentally friendly way.
  • Figure 3 is a photograph and a scanning electron microscope picture of the appearance of the activated carbon used in the embodiment of the present invention
  • Figure 4 is a photograph and observation electron micrographs of the characteristics of the activated carbon used in the embodiment of the present invention
  • FIG. 5 is a process flow chart for explaining a method for producing nano-silicon carbide using the thermal plasma of the present invention
  • the term 'silicone fine powder' means silicon having a particle size of 100 ⁇ m or less
  • micro silicon carbide refers to silicon carbide having an average particle diameter of 0.5 to 10 ⁇ m ( silicon carbide (SiC) powder
  • 'nano silicon carbide' refers to silicon carbide powder having an average particle diameter in the range of 10 to 500 nm.
  • the nano-silicon carbide manufacturing method using the thermal plasma of the present invention comprises the steps of: a) synthesizing the silicon fine powder and the carbon source and firing to synthesize micro silicon carbide (SiC); b) treating the microsilicon carbide with thermal plasma to produce nanosilicon carbide.
  • the silicon fine powder used in the method for producing nano-silicon carbide using the thermal plasma of the present invention is not particularly limited, but Si waste with a particle size of 100 ⁇ m or less generated in the grinding / classification process of metal silicon as described above from an economical point of view It is preferable to use fine powder. Scanning electron microscope (SEM) observation was performed to investigate the shape and size of Si waste fine powder generated during the grinding and classification of metal silicon at the applicant's workplace, and the results are shown in FIG. 1. The shape of the Si spent fine powder was in amorphous form with sharp angle and the size was about 10-50 ⁇ m.
  • Figure 2 is the result of performing the particle size analysis to investigate the exact particle size distribution of the waste powder.
  • the average particle diameter was 25-33 micrometers
  • the particle size of Si fine powder with a small particle diameter was 4-6 micrometers
  • it could be confirmed that the particle size of Si powder with a large particle diameter is 80-110 micrometers.
  • ICP analysis was performed for impurity analysis, and the results are summarized in Table 1 below. As can be seen from Table 1, many impurities after Fe were identified as Al, and the purity of Si waste fine powder was found to be 98.5 to 99%.
  • the silicon waste fine powder is used as the silicon fine powder, it is preferable to remove impurities by pretreatment before firing in order to reduce impurities.
  • the method of washing cleaning with an acid solution is used for removal of a metal component, it is preferable to carry out pickling and washing with water. Pickling and washing can remove about 80-90% or more of metallic impurities.
  • the carbon source is not particularly limited, and may be used in both solid, liquid and gaseous carbon sources such as carbon or hydrocarbons.
  • the carbon source at least one solid carbon source selected from the group consisting of activated carbon, carbon black and graphite is preferable.
  • the reactivity of the Si waste fine powder and the carbon source is very important, and this reactivity can be determined by the shape, crystal structure and particle size of the carbon source.
  • particle size, shape, and specific surface area were analyzed for two types of solid carbon sources: activated carbon and carbon black. 3 and 4 are SEM observations of activated carbon and carbon black, respectively.
  • the particle size was found to be 5-50 ⁇ m, but the specific surface area was about twice that of carbon black, showing 520 m 2 / g. In the case of carbon black, the particle diameter was very fine (1-5 ⁇ m), the specific surface area was 230 m 2 / g. Since activated carbon was in the form of granules, it was pulverized using induction to promote SiC synthesis.
  • the silicon fine powder and the carbon source are mixed and calcined to produce micro silicon carbide.
  • the mixing is preferably carried out using a ball mill to add a uniform grinding effect when using a solid carbon source.
  • the reaction for calcining the mixture of the silicon fine powder and the carbon source may be performed at a temperature and for a time sufficient to produce silicon carbide. In the preferred embodiment of the present invention, firing was performed at 1,200 ° C. Detailed conditions, such as the ball mill or the firing temperature is well known to those skilled in the art to which the present invention pertains, so no further detailed description will be given herein.
  • the silicon and the carbon source are preferably in a molar ratio of 1: 1.5 or more. This is because unreacted silicon is generated when the carbon source is lower than the ratio. If the ratio of the silicon and the carbon source is out of the above range because the unreacted silicon or unreacted carbon source is left, it must go through a separate separation process. However, when the amount of the carbon source is large, since the separation process of the unreacted carbon source after firing, the ratio of the silicon and the carbon source is preferably in the range of 1: 1.5 to 2 in molar ratio.
  • the silicon carbide produced after such firing is 'micro silicon carbide' with an average particle diameter of 0.5 to 5 microns.
  • the micro silicon carbide is subjected to a step of producing nano silicon carbide by treatment with thermal plasma.
  • Thermal plasma is converted to nano silicon carbide by supplying micro silicon carbide continuously by applying non-transfer plasma.
  • micro silicon carbide powder is put into the flame of non-conveying arc thermal plasma through a metering feeder, the silicon carbide powder is temporarily melted in the plasma space, and molten silicon carbide is released by argon and hydrogen gas which are ejected at high speed. The powder is scattered to nano size and simultaneously cooled to form nano size silicon carbide powder.
  • the silicon fine powder silicon waste fine powder generated when pulverizing / classifying the metal silicon lump at the applicant's workplace was used.
  • the silicon waste fine powder has a particle diameter of 100 m or less and contains impurities such as iron. Therefore, the silicon fine powder was pickled and washed with water before reacting with the solid carbon source.
  • the pickling process consists of a pickling tank and a washing tank, and the pickling tank is equipped with a heater, the particle size can be adjusted, and the temperature can be controlled up to 40 ⁇ 70 °C.
  • a pick-up pump was installed in the pickling and washing tanks to improve pickling efficiency, and a basket was used to hold a cuboid nonwoven fabric and a nonwoven fabric to contain waste fines.
  • the size of the pickling tank is 400W x 400L x 300H and 70l.
  • the size of the wash tub is 400W x 400L x 300H and 70l.
  • a pickling pump was installed in the pickling tank to circulate the pickling solution to increase the contact time and speed up the diffusion rate with the metal silicon fine powder in the nonwoven bag at 50 °C. Since the metal silicon fine powder is diffused in the water, a nonwoven fabric is produced, and the metal silicon fine powder is put in the pickling solution and pickled.
  • As the nonwoven fabric a nonwoven fabric having a thickness of 20 ⁇ m was used to prevent the metal silicon fine powder from leaching into the pickling liquid and the washing liquid.
  • a circulating pump was installed in the washing tank, and the washing liquid used was ultra pure water having an ultra pure water of 18.5M ⁇ .
  • the pickling solution used HCl to easily cope with future environmental problems and wastewater treatment.
  • the HCl concentration of the pickling solution was 0.1N, 0.3N, 0.5N and the temperature was immersed for 1 hour at 50 ° C.
  • the dilution water of the pickling solution was ultrapure water with ultrapure water of 18.5M ⁇ .
  • the nonwoven fabric was dried by heating to 50 ° C. in a drier, and the metal silicon fine powder was dried in 105 ° C. in a stainless steel container, and the contamination analysis was performed on the samples in each process.
  • the 7300DV pekin-elmer analyzer was used and the results are summarized in Table 2 below. As can be seen in Table 2, it can be seen that after cleaning, metal components such as Fe, Al, and Ca are removed. In addition, the Si purity of the metal silicon fine powder (dust collector fine powder) increased from 99.02%, 99.46%, and 99.74% to 0.1N, 0.3N, and 0.5N HCl, respectively.
  • a Si: C mixed sample was prepared.
  • the mixing ratio of the Si: C mixed sample was adjusted to an amount of carbon added within the range of 1 to 4.5 times the molar basis on the basis of 1 mol of Si.
  • Weighed Si and carbon powder was mixed in a 12 mL plastic container filled with zirconia balls to 1/3 volume for 12 hours.
  • the mixed sample was calcined at 1200 ° C. for 2 to 10 hours using a vertical tubular electric furnace. After firing, the synthesized SiC powder was subjected to one ultrasonic washing to remove unreacted carbon, and stored in an oven at 80 ° C. for 12 hours for drying.
  • Si: C mixed sample a sample having a mixing ratio of at least 1: 1.5 or more is required for the synthesis of SiC without an unreacted substance, and a raw material having a 1: 2 mixing ratio for synthesizing SiC at a faster reaction rate. It was found that is preferable.
  • the sample supply amount was 0.45 g / min
  • the flow rate of the powder transport gas was set to 1 L / min.
  • the output condition of the arc thermal plasma generator power source was a current of 250 A and a voltage of 40 V, and argon gas and hydrogen gas were used as gas for plasma flame formation.
  • 9 shows SEM photographs before and after plasma treatment of a synthetic SiC sample. As a result, it can be seen that the particle size of SiC before plasma treatment is 1-5 ⁇ m, and the particle size of SiC is converted to nanoparticles of 1 ⁇ m or less by plasma treatment.
  • FIG. 11 shows the results of XRD analysis on samples before and after plasma in order to confirm whether or not a phase change of SiC occurred by the plasma treatment.

Abstract

The present invention relates to a production method for nano silicon carbide using a thermal plasma, and, more specifically, relates to a production method for nano silicon carbide using a thermal plasma wherein the method comprises the steps of: a) synthesising micro silicon carbide (SiC) by mixing and then calcining a silicon fine powder and a carbon source; and b) producing nano silicon carbide by subjecting the micro silicon carbide to processing by means of a thermal plasma. The method which is provided makes it possible to achieve relatively straightforward and economic synthesis of a silicon carbide powder having a mean particle size in a range of from 10 to 500 nm by using a silicon waste fine powder having a particle size of no more than 100 μm which is created during a process such as grinding/grading metallic silicon, and thus a higher added value is given to silicon fine powder and at the same time nano silicon carbide fine powder can be produced in a way which is both economical and environmentally friendly.

Description

열플라즈마를 이용한 나노 탄화규소 제조방법Manufacturing method of nano silicon carbide using thermal plasma
본 발명은 열플라즈마를 이용한 나노 탄화규소 제조방법에 관한 것으로, 보다 상세하게는 a)실리콘 미분과 탄소원을 혼합 후 소성하여 마이크로 탄화규소(SiC)를 합성하는 단계 및; b)상기 마이크로 탄화규소를 열플라즈마로 처리하여 나노 탄화규소로 제조하는 단계를 포함한 열플라즈마를 이용한 나노 탄화규소 제조방법에 관한 것이다.The present invention relates to a method for producing nano-silicon carbide using thermal plasma, and more particularly, a) synthesizing microsilicon carbide (SiC) by mixing and calcining silicon fine powder and carbon source; b) relates to a method for preparing nanosilicon carbide using thermal plasma, which comprises the step of treating the microsilicon carbide with thermal plasma to produce nanosilicon carbide.
탄화규소(Silicon carbide, SiC)는 물리/화학적으로 안정하고 내열성과 열전도성이 좋아 고온 안정성과 고온 강도가 매우 우수하며 내마모성이 높은 특성을 가지고 있어 고온 재료, 고온 반도체, 반도체용 치구, 내마모성 재료, 자동차 부품, 화학공장의 내식성 또는 내약품성 부품 또는 전자부품 등을 제조하는데 주로 사용된다. 특히 나노 크기의 탄화규소 분말의 경우 마이크로 크기 분말 보다 표면 에너지가 높고, 이로 인해 소결성이 우수하여 저온에서도 치밀한 탄화규소 제품을 제조할 수 있으며, 각종 나노 복합재료의 강화재로 널리 사용되는 장점이 있다. 또한, SiC는 예를 들어 핵융합로 블랑켓 구조재료 및 플라즈마 대향재료 등 핵융합로의 건설에서 고온/저방사화 구조재료로 사용하기 위한 것으로 판단된다. 핵융합 용도에서, SiC는 핵융합로용 타일형 구조블록으로 몰딩 될수 있는 분말형태로 제조되어야 유리하다. 따라서 몰딩공정 중에 매우 컴팩트한 구조 재료를 제공하는 이점을 갖는 SiC 나노분말의 합성기술 개발 수요가 증대되고 있는 실정이다. Silicon carbide (SiC) is physically and chemically stable, has excellent heat resistance and high thermal conductivity, and has excellent high temperature stability, high temperature strength, and high wear resistance. Therefore, high temperature materials, high temperature semiconductors, jig for semiconductors, wear resistant materials, It is mainly used to manufacture corrosion resistant or chemical resistant parts or electronic parts of automobile parts, chemical plants. In particular, in the case of nano-sized silicon carbide powder, the surface energy is higher than the micro-sized powder, and thus, the sintering property is excellent, so that a dense silicon carbide product can be manufactured even at low temperature, and has the advantage of being widely used as a reinforcing material for various nanocomposites. In addition, SiC is considered to be used as a high-temperature / low-radiation structural material in the construction of a fusion reactor such as, for example, a fusion blanket blanket material and a plasma facing material. In fusion applications, SiC is advantageously produced in powder form that can be molded into tiled structural blocks for fusion reactors. Therefore, there is an increasing demand for the development of the synthesis technology of SiC nanopowders having the advantage of providing a very compact structural material during the molding process.
이전의 연구에 따르면, SiC 나노분말은 플라즈마, 레이저 및 마이크로파를 이용하는 기상반응 합성 및 졸겔법 등의 다양한 방법을 통해 합성할 수 있다. 일본의 신규기술연구소의 신재료연구그룹에서는 RF 열플라즈마를 이용하여 30~50 nm 크기의 SiC 나노분말을 합성하였는데, 탄소원으로는 에칠렌(C2H4) 가스가 사용되었으며 Si의 원료로는 SiH4 가스가 사용되었다. 분산성이 우수한 수십 nm 크기의 SiC 나노분말이 생성되었으나, 원료 및 RF 플라즈마의 가동 비용이 비싸다는 문제점을 가지고 있다. 또한, 미국의 UC Santa Barbara의 Prof. Eric McFarland는 저압 플라즈마 반응기를 이용하여 0.001~0.02 Torr의 고진공에서 tetramethylsilane(TMS)의 열플라즈마 분해에 의해 10nm 크기의 SiC 나노분말을 제조하였다. 현재 가장 많이 사용되고 있는 방법은 실리카환원법과 실란열분해법이다. 실리카 환원법은 대형 아치슨형 전기로에서 고순도 규사(99.5% SiO2)와 저유황 코크스를 2000-2500℃의 고온에서 반응시켜 제조하며, 이 때의 합성 반응은 [SiO2 + 3C=SiC+2CO]가 된다. 그러나, 실리카 환원법은 마이크로 크기 분말 위주이며, 나노분말의 수율이 극히 미비하고, 제조과정에서 일산화탄소의 발생으로 인한 환경문제가 있으며, 생산성이 좋지 않아 경제성이 떨어지는 문제가 있다. 실란열분해법은 초미립 β-SiC를 제조할 때 사용하는 방법으로 흑연 반응로에서 Silane을 열분해하여 제조하며 이 때의 합성 반응은 [CH3SiH3 = SiC+3H2]가 된다. 그러나, Silane 분해 시 유독가스 발생하며, 소량의 가스 누출로도 치명적인 상황이 발생할 수 있고, 용매, 고분자물질, 반응 후 생성물 등은 재활용이 불가하여 환경오염이 발생하는 문제가 있다.According to previous studies, SiC nanopowders can be synthesized through various methods such as gas phase synthesis using plasma, laser and microwave, and sol-gel method. The New Materials Research Group of the Japan Institute of New Technology has synthesized SiC nanopowders of 30-50 nm in size using RF thermal plasma. Ethylene (C 2 H 4 ) gas is used as the carbon source and SiH is used as the raw material for Si. 4 gases were used. SiC nanopowders having a size of tens of nm having excellent dispersibility have been produced, but have a problem in that operating costs of raw materials and RF plasma are high. Also, Prof. of UC Santa Barbara, USA Eric McFarland prepared a 10nm SiC nanopowder by thermal plasma decomposition of tetramethylsilane (TMS) in a high vacuum of 0.001-0.02 Torr using a low pressure plasma reactor. The most widely used methods are silica reduction and silane pyrolysis. Silica reduction method and is prepared by reacting a large arch seunhyeong electric furnace of high purity silica (99.5% SiO 2) in the low sulfur coke at a high temperature of 2000-2500 ℃, the synthetic reaction of this time, [SiO 2 + 3C = SiC + 2CO] is do. However, the silica reduction method is mainly micro-sized powder, the yield of the nano powder is extremely insignificant, there is an environmental problem due to the generation of carbon monoxide in the manufacturing process, there is a problem that the economic efficiency is poor due to poor productivity. Silane pyrolysis is a method used to prepare ultrafine β-SiC, which is prepared by pyrolyzing Silane in a graphite reactor, and the synthesis reaction at this time becomes [CH 3 SiH 3 = SiC + 3H 2 ]. However, toxic gas is generated during the decomposition of silane, and even a small amount of gas leakage can cause a fatal situation. Solvents, polymers, and products after the reaction cannot be recycled, resulting in environmental pollution.
한편, 폴리실리콘 및 유기실리콘 재료인 메탈실리콘 파우더(입도50-450ㅅ)는 메탈실리콘 럼프(lump)를 분쇄/분급하여 50-450 미크론 크기의 입자는 제품으로 폴리실리콘 제조에 사용된다. 그런데, 메탈실리콘 럼프의 분쇄과정이나 폴리실리콘 제조과정 등에서는 필연적으로 입경 100 ㎛ 이하 고순도 Si(98%이상)의 폐미분이 발생하게 된다. 현재, 이러한 폐미분은 국내에서만도 150톤/월 발생을 추정하고 있으며 메탈실리콘 파우더의 생산량이 증가함에 폐미분도 증가될 것이다. 그러나, 아직까지 이러한 고순도 폐미분에 대한 적절한 처리방법이 개발되어 있지 않아 필러 등의 저부가가치 용도로 사용되고 있는 실정이다.Meanwhile, the polysilicon and organosilicon materials, metal silicon powder (particle size 50-450 s), are pulverized / classified of metal silicon lumps (lumps) so that particles having a size of 50-450 microns are used for the production of polysilicon as a product. By the way, in the grinding process of the metal silicon lump or the polysilicon manufacturing process, waste fine powder of high purity Si (98% or more) having a particle size of 100 μm or less is inevitably generated. At present, it is estimated that 150 tons / month generated in Korea alone, and that the increase in the production of metal silicon powder will increase. However, there is no proper treatment method for such high-purity waste fine powder, so it is currently used for low value-added applications such as fillers.
따라서, 본 발명이 이루고자 하는 기술적 과제는 실리콘 미분, 특히 메탈실리콘 분쇄/분급과정 등에서 발생하는 입경 100 ㎛ 이하 Si 폐미분을 이용하여 나노 탄화규소를 비교적 간단하고 경제적으로 합성할 수 있는 방법을 제공하여 실리콘 미분의 고부가가치화를 달성하고 동시에 나노 탄화규소를 경제성있고 친환경적인 방법으로 제조할 수 있도록 하는 것이다.Therefore, the technical problem to be achieved by the present invention is to provide a method for relatively simple and economical synthesis of nano silicon carbide using silicon fine powder, in particular Si waste fine powder having a particle diameter of 100 ㎛ or less generated during the metal silicon grinding / classification process, etc. It is to achieve high value-adding of silicon fine powder and at the same time to make nano silicon carbide in economical and environmentally friendly way.
상기 기술적 과제를 달성하기 위하여, 본 발명은 실리콘 미분과 탄소원을 혼합 후 소성하여 마이크로 탄화규소(SiC)를 합성하는 단계 및; 상기 마이크로 탄화규소를 열플라즈마로 처리하여 나노 탄화규소로 제조하는 단계를 포함한 열플라즈마를 이용한 나노 탄화규소 제조방법을 제공한다.In order to achieve the above technical problem, the present invention comprises the steps of synthesizing micro silicon carbide (SiC) by mixing and firing silicon fine powder and a carbon source; It provides a method for producing nano-silicon carbide using a thermal plasma comprising the step of treating the micro-silicon carbide with thermal plasma to produce nano-silicon carbide.
또한, 본 발명은 상기 실리콘 미분이 메탈실리콘 럼프의 분쇄/분급과정에서 발생한 입경 100 ㎛ 이하인 폐미분인 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법을 제공한다.In another aspect, the present invention provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the silicon fine powder is a waste fine powder having a particle diameter of 100 ㎛ or less generated during the grinding / classification process of the metal silicon lump.
또한, 본 발명은 상기 실리콘 미분이 상기 a)단계의 소성 전 산세척 및 수세를 거친 것임을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법을 제공한다.The present invention also provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the silicon fine powder is subjected to pickling and washing before firing in step a).
또한, 본 발명은 상기 탄소원이 활성탄, 카본블랙 및 흑연으로 이루어진 군으로부터 선택된 1종 이상인 고상 탄소원인 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법을 제공한다.The present invention also provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the carbon source is at least one solid carbon source selected from the group consisting of activated carbon, carbon black and graphite.
또한, 본 발명은 상기 a)단계의 혼합이 볼밀(ball mill)을 이용하여 수행되는 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법을 제공한다.In addition, the present invention provides a method for producing nano-silicon carbide using a thermal plasma, characterized in that the mixing of the step a) is carried out using a ball mill.
또한, 본 발명은 상기 a)단계의 혼합에서 실리콘과 탄소원의 비율이 몰비로 1:1.5 내지 2 범위에서 이루어진 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법을 제공한다.In another aspect, the present invention provides a method for producing nano-silicon carbide using a thermal plasma, characterized in that the ratio of silicon and carbon source in the mixing of step a) is made in the range of 1: 1.5 to 2.
또한, 본 발명은 상기 마이크로 탄화규소의 열플라즈마 처리가 연속식으로 이루어지는 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법을 제공한다.In addition, the present invention provides a method for producing nano-silicon carbide using thermal plasma, characterized in that the thermal plasma treatment of the micro silicon carbide is made in a continuous manner.
본 발명에 따른 열플라즈마를 이용한 나노 탄화규소 제조방법은 메탈실리콘 분쇄/분급과정 등에서 발생하는 입경 100 ㎛ 이하 Si 폐미분을 이용하여 나노 탄화규소를 비교적 간단하고 경제적으로 합성할 수 있는 방법을 제공하여 실리콘 미분의 고부가가치화를 달성하고 동시에 나노 탄화규소를 경제성있고 친환경적인 방법으로 제조할 수 있다.The method for producing nano silicon carbide using the thermal plasma according to the present invention provides a method for relatively easily and economically synthesizing nano silicon carbide using Si powder with a particle diameter of 100 μm or less generated during the metal silicon grinding / classification process. High value-added silicon fines can be achieved while nano-silicon carbide can be manufactured in an economical and environmentally friendly way.
도 1은 본 발명의 실시예에 사용된 메탈실리콘 럼프의 분쇄/분급 과정에서 발생한 실리콘 폐미분의 성상을 관찰한 사진 및 주사전자현미경 사진1 is a photograph and a scanning electron microscope photograph of the characteristics of the silicon waste fine powder generated during the grinding / classification process of the metal silicon lump used in the embodiment of the present invention
도 2는 도 1의 실리콘 폐미분에 대한 입도분석결과2 is a particle size analysis result of the silicon waste fine powder of FIG.
도 3은 본 발명의 실시예에서 사용된 활성탄의 성상을 관찰한 사진 및 주사전자현미경 사진Figure 3 is a photograph and a scanning electron microscope picture of the appearance of the activated carbon used in the embodiment of the present invention
도 4는 본 발명의 실시예에서 사용된 활성탄의 성상을 관찰한 사진 및 주사전자현미경 사진Figure 4 is a photograph and observation electron micrographs of the characteristics of the activated carbon used in the embodiment of the present invention
도 5는 본 발명의 열플라즈마를 이용한 나노 탄화규소 제조방법을 설명하기 위한 공정흐름도 5 is a process flow chart for explaining a method for producing nano-silicon carbide using the thermal plasma of the present invention
도 6은 Si:C = 1:1 혼합시료의 합성시간별 SEM 사진 및 XRD 결과FIG. 6 shows SEM photographs and XRD results of Si: C = 1: 1 mixed samples.
도 7은 Si:C = 1:1.5 혼합시료의 합성시간별 SEM 사진 및 XRD 결과FIG. 7 shows SEM images and XRD results of Si: C = 1: 1.5 mixed samples.
도 8은 Si:C = 1:2 혼합시료의 합성시간별 SEM 사진 및 XRD 결과8 is a SEM photograph and XRD results of Si: C = 1: 2 mixed sample according to the synthesis time
도 9는 Si:C = 1:2 mole 예비소성 SiC 분말로부터 합성된 SiC 나노분말의 SEM 사진9 is a SEM photograph of the SiC nanopowder synthesized from Si: C = 1: 2 mole prefired SiC powder
도 10은 Si:C = 1:2 mole 예비소성 SiC 분말로부터 합성된 SiC 나노분말의 TEM 사진10 is a TEM photograph of SiC nanopowder synthesized from Si: C = 1: 2 mole prefired SiC powder
도 11은 그림 4-26. Si:C = 1:2 mole 예비소성 SiC 분말로부터 합성된 SiC 나노분말의 XRD 결과11 is Figure 4-26. XRD results of SiC nanopowders synthesized from Si: C = 1: 2 mole prefired SiC powder
이하에서 본 명세서에 첨부된 도면을 참조하여 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
본 명세서에서 별도의 언급이 없는 한 '실리콘 미분'의 용어는 입경이 100 ㎛ 이하의 실리콘(silicone)을 의미하고, '마이크로 탄화규소'의 표현은 평균입경이 0.5 내지 10 ㎛ 범위의 탄화규소(silicone carbide, SiC) 분말을 의미하며, '나노 탄화규소'의 용어는 10 내지 500 nm 범위의 평균 입경을 갖는 탄화규소 분말을 의미한다. Unless stated otherwise in the present specification, the term 'silicone fine powder' means silicon having a particle size of 100 μm or less, and the expression “micro silicon carbide” refers to silicon carbide having an average particle diameter of 0.5 to 10 μm ( silicon carbide (SiC) powder, and the term 'nano silicon carbide' refers to silicon carbide powder having an average particle diameter in the range of 10 to 500 nm.
도 5는 본 발명의 열플라즈마를 이용한 나노 탄화규소 제조방법을 설명하기 위한 공정흐름도이다. 도 5에 도시된 바와 같이, 본 발명의 열플라즈마를 이용한 나노 탄화규소 제조방법은 a)실리콘 미분과 탄소원을 혼합 후 소성하여 마이크로 탄화규소(SiC)를 합성하는 단계 및; b)상기 마이크로 탄화규소를 열플라즈마로 처리하여 나노 탄화규소로 제조하는 단계를 포함한다.5 is a process flow chart for explaining a method for producing nano silicon carbide using the thermal plasma of the present invention. As shown in Figure 5, the nano-silicon carbide manufacturing method using the thermal plasma of the present invention comprises the steps of: a) synthesizing the silicon fine powder and the carbon source and firing to synthesize micro silicon carbide (SiC); b) treating the microsilicon carbide with thermal plasma to produce nanosilicon carbide.
본 발명의 열플라즈마를 이용한 나노 탄화규소 제조방법에 사용되는 실리콘 미분의 경우 특별히 제한되는 것은 아니며, 다만 경제적 관점에서 전술한 바와 같이 메탈실리콘의 분쇄/분급 과정 등에서 발생하는 입경 100 ㎛ 이하의 Si 폐미분을 사용하는 것이 바람직하다. 본 출원인의 사업장에서 메탈실리콘의 분쇄, 분급과정에서 발생하는 Si 폐미분의 형상 및 크기를 조사하기 위하여 주사전자현미경(SEM) 관찰을 수행하였고, 그 결과를 도 1에 나타내었다. Si 폐미분의 형상은 날카로운 각을 가지고 있는 무정형 형태이고 그 크기는 약 10 - 50 ㎛ 크기를 나타내었다. 도 2는 폐미분의 정확한 입도분포를 조사하기 위하여 입도분석을 실시한 결과이다. 이결과로부터 평균 입경은 25∼33 ㎛ 이고, 입경이 작은 Si 미분의 입경은 4∼6 ㎛ 이며 입경이 큰 Si 분말의 입경은 80∼110 ㎛ 임을 확인할 수 있었다. 또한, 불순물 분석을 위해 ICP 분석을 실시하였고, 하기 표 1에 그 결과를 정리하였다. 표 1로부터 알 수 있듯이 Fe 다음으로 많은 불순물은 Al 으로 확인되었고, Si 폐미분의 순도는 98.5∼99%인 것을 알 수 있다. In the case of the silicon fine powder used in the method for producing nano-silicon carbide using the thermal plasma of the present invention is not particularly limited, but Si waste with a particle size of 100 μm or less generated in the grinding / classification process of metal silicon as described above from an economical point of view It is preferable to use fine powder. Scanning electron microscope (SEM) observation was performed to investigate the shape and size of Si waste fine powder generated during the grinding and classification of metal silicon at the applicant's workplace, and the results are shown in FIG. 1. The shape of the Si spent fine powder was in amorphous form with sharp angle and the size was about 10-50 μm. Figure 2 is the result of performing the particle size analysis to investigate the exact particle size distribution of the waste powder. From this result, the average particle diameter was 25-33 micrometers, the particle size of Si fine powder with a small particle diameter was 4-6 micrometers, and it could be confirmed that the particle size of Si powder with a large particle diameter is 80-110 micrometers. In addition, ICP analysis was performed for impurity analysis, and the results are summarized in Table 1 below. As can be seen from Table 1, many impurities after Fe were identified as Al, and the purity of Si waste fine powder was found to be 98.5 to 99%.
표 1
Figure PCTKR2011003850-appb-T000001
 Table 1
Figure PCTKR2011003850-appb-T000001
따라서, 상기 실리콘 미분으로 실리콘 폐미분을 사용하는 경우에는 불순물을 줄이기 위해 소성 전 전처리로 불순물을 제거하는 것이 바람직하다. 통상 금속 성분의 제거에는 산(acid)용액으로 세정을 하는 방법이 사용되므로, 산세 및 수세를 하는 것이 바람직하다. 산세 및 수세를 통해 금속성분 불순물을 약 80 내지 90% 이상 제거할 수 있다.Therefore, when the silicon waste fine powder is used as the silicon fine powder, it is preferable to remove impurities by pretreatment before firing in order to reduce impurities. Usually, since the method of washing | cleaning with an acid solution is used for removal of a metal component, it is preferable to carry out pickling and washing with water. Pickling and washing can remove about 80-90% or more of metallic impurities.
또한, 상기 탄소원은 특별히 제한되는 것은 아니며 탄소 또는 탄화수소류 등 고상, 액상 및 기상 탄소원 모두를 이용할 수 있다. 상기 탄소원의 바람직한 예로는 활성탄, 카본블랙 및 흑연으로 이루어진 군으로부터 선택된 1종 이상인 고상 탄소원이 바람직하다. 본 발명의 실시예에서는 고상 반응에 의한 SiC 합성을 시도하기 때문에, Si 폐미분과 탄소원의 반응성이 매우 중요하고, 이 반응성은 탄소원의 형상, 결정구조 및 입경에 의해 결정될 수 있다. 본 연구에서는 활성탄, 카본블랙 두 가지 종류의 고상 탄소원에 대하여 입경, 형상, 비표면적을 분석하였다. 도 3 및 4는 각각 활성탄과 카본블랙에 대한 SEM 관찰 결과이다. 상업용 활성탄은 그래뉼 형태로 판매되고 있기 때문에 입경은 5 - 50 ㎛ 으로 다소 큰 것으로 조사되었지만 비표면적은 카본블랙의 약 두 배 정도 커서 520 m2/g을 나타내었다. 카본블랙의 경우 입경은 1 - 5 ㎛로 매우 미세하였고, 비표면적은 230 m2/g를 보였다. 활성탄의 경우 그래뉼 형태로 되어 있었기 때문에 SiC 합성반응의 촉진을 위하여 유발을 이용하여 분쇄하여 사용하였다. In addition, the carbon source is not particularly limited, and may be used in both solid, liquid and gaseous carbon sources such as carbon or hydrocarbons. As a preferable example of the carbon source, at least one solid carbon source selected from the group consisting of activated carbon, carbon black and graphite is preferable. In the embodiment of the present invention, since SiC synthesis by solid phase reaction is attempted, the reactivity of the Si waste fine powder and the carbon source is very important, and this reactivity can be determined by the shape, crystal structure and particle size of the carbon source. In this study, particle size, shape, and specific surface area were analyzed for two types of solid carbon sources: activated carbon and carbon black. 3 and 4 are SEM observations of activated carbon and carbon black, respectively. Since commercial activated carbon is sold in granule form, the particle size was found to be 5-50 μm, but the specific surface area was about twice that of carbon black, showing 520 m 2 / g. In the case of carbon black, the particle diameter was very fine (1-5 ㎛), the specific surface area was 230 m 2 / g. Since activated carbon was in the form of granules, it was pulverized using induction to promote SiC synthesis.
본 발명에서는 상기 실리콘 미분과 탄소원을 혼합 및 소성하여 마이크로 탄화규소를 제조하게 된다. 상기 혼합은 고상 탄소원을 사용하는 경우 균일한 분쇄효과를 더하기 위해 볼밀을 이용하여 수행되는 것이 바람직하다. 또한, 상기 실리콘 미분과 탄소원의 혼합물을 소성하는 반응은 탄화규소가 생성되기에 충분한 온도 및 시간에서 수행되면 된다. 본 발명의 바람직한 태양인 실시예에서는 1,200℃에서 소성을 수행하였다. 상기 볼밀이나 소성온도 등의 상세한 조건은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게는 공지의 기술이므로 본 명세서에서 더 이상의 상세한 설명은 하지 않기로 한다. In the present invention, the silicon fine powder and the carbon source are mixed and calcined to produce micro silicon carbide. The mixing is preferably carried out using a ball mill to add a uniform grinding effect when using a solid carbon source. In addition, the reaction for calcining the mixture of the silicon fine powder and the carbon source may be performed at a temperature and for a time sufficient to produce silicon carbide. In the preferred embodiment of the present invention, firing was performed at 1,200 ° C. Detailed conditions, such as the ball mill or the firing temperature is well known to those skilled in the art to which the present invention pertains, so no further detailed description will be given herein.
상기 실리콘과 탄소원의 혼합 및 소성에 있어서, 상기 실리콘과 탄소원(혼합시 탄소원 중 포함된 탄소만의 몰비로 계산)은 몰비로 1:1.5 이상의 비율로 하는 것이 바람직하다. 탄소원이 상기 비율보다 낮게 되면 미반응 실리콘이 발생하기 때문이다. 상기 실리콘과 탄소원의 비율이 상기 범위를 벗어나게 되면 미반응 실리콘 또는 미반응 탄소원이 잔류하게 되어 별도의 분리공정을 더 거쳐야 하기 때문이다. 다만, 탄소원의 양이 많은 경우에는 소성 후 미반응 탄소원의 분리과정을 거쳐야 하기 때문에, 상기 실리콘과 탄소원의 비율이 몰비로 1:1.5 내지 2 범위인 것이 바람직하다. 상기 범위에서 양 성분의 혼합이 이루어지는 경우에는 미반응 성분의 잔류가 적어 별도의 분리과정을 거칠 필요가 없기 때문이다. 이러한 소성 후 생성된 탄화규소는 '마이크로 탄화규소'로 평균입경이 0.5 내지 5 미크론 범위이다.In the mixing and firing of the silicon and the carbon source, the silicon and the carbon source (calculated by the molar ratio of only carbon contained in the carbon source at the time of mixing) are preferably in a molar ratio of 1: 1.5 or more. This is because unreacted silicon is generated when the carbon source is lower than the ratio. If the ratio of the silicon and the carbon source is out of the above range because the unreacted silicon or unreacted carbon source is left, it must go through a separate separation process. However, when the amount of the carbon source is large, since the separation process of the unreacted carbon source after firing, the ratio of the silicon and the carbon source is preferably in the range of 1: 1.5 to 2 in molar ratio. This is because when the mixing of the two components in the above range is less residual of the unreacted components do not need to go through a separate separation process. The silicon carbide produced after such firing is 'micro silicon carbide' with an average particle diameter of 0.5 to 5 microns.
상기 마이크로 탄화규소는 열플라즈마로 처리하여 나노 탄화규소로 제조하는 단계를 거치게 된다. 열플라즈마는 비이송식 플라즈마를 적용하여 마이크로 탄화규소를 연속적으로 공급하여 나노 탄화규소로 전환시키게 된다. 마이크로 탄화규소 분말을 정량공급기를 통해 비이송식 아크 열플라즈마의 불꽃 속에 투입하게 되면 탄화규소 분말은 플라즈마 공간 내에서 일시적으로 용융 상태에 이르게 되고 이때 고속으로 분출하는 아르곤 및 수소 가스에 의해 용융 탄화규소 분말은 나노 사이즈로 흩어짐과 동시에 냉각되어 나노 크기의 탄화규소 분말을 형성하게 된다.The micro silicon carbide is subjected to a step of producing nano silicon carbide by treatment with thermal plasma. Thermal plasma is converted to nano silicon carbide by supplying micro silicon carbide continuously by applying non-transfer plasma. When micro silicon carbide powder is put into the flame of non-conveying arc thermal plasma through a metering feeder, the silicon carbide powder is temporarily melted in the plasma space, and molten silicon carbide is released by argon and hydrogen gas which are ejected at high speed. The powder is scattered to nano size and simultaneously cooled to form nano size silicon carbide powder.
이하 본 발명의 바람직한 실시예를 통하여 본 발명을 더욱 상세히 설명하기로 한다. Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention.
실시예 1(실리콘 미분의 산세 및 수세)Example 1 (pickling and washing of silicon fine powder)
우선, 실리콘 미분으로는 본 출원인의 사업장에서 메탈실리콘 럼프를 분쇄/분급할 때 발생한 실리콘 폐미분을 사용하였다. 전기한 바와 같이, 상기 실리콘 폐미분은 입경이 100 ㎛ 이하이고 철 등 불순물을 함유하고 있다. 따라서, 상기 실리콘 미분을 고상 탄소원과 반응시키기 전에 산세 및 수세를 하였다. 산세 공정은 산세조 와 수세조로 구성되어 있으며 산세조는 히터가 부착 되어져 있고 입도를 조절할수 있으며, 온도를 40~70℃까지 제어 가능 하다. 산세, 수세조에 순환펌프을 설치하여 산세 효율을 높였으며 폐미분을 담아 줄 수 있는 직육면체 부직포와 부직포를 담을수 있는 바스켓을 이용하였다. 산세조의 크기는 400W x 400L x 300H로 70ℓ용량이며 수세조의 크기는 400W x 400L x 300H로 70ℓ용량이다. 산세조에는 순환 펌프를 설치하여 산세액을 순환시켜 50℃ 온도에서 부직포 bag속의 메탈 실리콘 미분과 접촉시간을 길게하고 확산속도를 빠르게 하도록 설계를 하였다. 메탈실리콘 미분은 물속에서 확산 되어지므로 부직포를 제작하여 그 속에 메탈실리콘 미분을 넣어 산세액에 침지시켜 산세한다. 부직포는 메탈실리콘 미분이 산세액 및 수세액으로 침출되지 않도록 하기 위하여 20㎛의 부직포를 사용하였다. 수세조에는 순환펌프를 설치하였고 수세액은 초순수급 18.5㏁의 수질을 갖는 초순수를 사용하였다. 산세액은 향후 환경문제 및 산폐수 처리에 용이하게 대처하도록 HCl을 사용하였다. 산세액의 HCl농도는 0.1N, 0.3N, 0.5N 과 온도는 50℃에서 1시간동안 침지하여 산세를 하였고 산세액의 희석수는 초순수급 18.5㏁의 수질을 갖는 초순수이다. 수세는 1시간동안 상온에서 수세를 행한 후 부직포를 건조기에 50℃로 가열하여 건조시켰으며 이 메탈실리콘 미분을 스테인레스 용기에 담아 105℃에 건조시켜 각각의 공정에서 시료에 대해 오염도 분석을 ICP-OES 7300DV pekin-elmer 분석기로 실시하였고, 그 결과를 하기 표 2에 정리하였다. 표 2에서 볼 수 있는 바와 같이, 세정 후 Fe, Al, Ca 등의 금속성분이 제거되어짐을 알 수 있다. 또한, 0.1N, 0.3N, 0.5N HCl의 산세액 농도에 따라 메탈실리콘 미분(집진기미분)의 Si 순도 98.59%에서 각각 99.02%, 99.46%, 99.74%로 증가하였다.   First, as the silicon fine powder, silicon waste fine powder generated when pulverizing / classifying the metal silicon lump at the applicant's workplace was used. As described above, the silicon waste fine powder has a particle diameter of 100 m or less and contains impurities such as iron. Therefore, the silicon fine powder was pickled and washed with water before reacting with the solid carbon source. The pickling process consists of a pickling tank and a washing tank, and the pickling tank is equipped with a heater, the particle size can be adjusted, and the temperature can be controlled up to 40 ~ 70 ℃. A pick-up pump was installed in the pickling and washing tanks to improve pickling efficiency, and a basket was used to hold a cuboid nonwoven fabric and a nonwoven fabric to contain waste fines. The size of the pickling tank is 400W x 400L x 300H and 70ℓ. The size of the wash tub is 400W x 400L x 300H and 70ℓ. A pickling pump was installed in the pickling tank to circulate the pickling solution to increase the contact time and speed up the diffusion rate with the metal silicon fine powder in the nonwoven bag at 50 ℃. Since the metal silicon fine powder is diffused in the water, a nonwoven fabric is produced, and the metal silicon fine powder is put in the pickling solution and pickled. As the nonwoven fabric, a nonwoven fabric having a thickness of 20 μm was used to prevent the metal silicon fine powder from leaching into the pickling liquid and the washing liquid. A circulating pump was installed in the washing tank, and the washing liquid used was ultra pure water having an ultra pure water of 18.5㏁. The pickling solution used HCl to easily cope with future environmental problems and wastewater treatment. The HCl concentration of the pickling solution was 0.1N, 0.3N, 0.5N and the temperature was immersed for 1 hour at 50 ° C. The dilution water of the pickling solution was ultrapure water with ultrapure water of 18.5㏁. After washing with water at room temperature for 1 hour, the nonwoven fabric was dried by heating to 50 ° C. in a drier, and the metal silicon fine powder was dried in 105 ° C. in a stainless steel container, and the contamination analysis was performed on the samples in each process. The 7300DV pekin-elmer analyzer was used and the results are summarized in Table 2 below. As can be seen in Table 2, it can be seen that after cleaning, metal components such as Fe, Al, and Ca are removed. In addition, the Si purity of the metal silicon fine powder (dust collector fine powder) increased from 99.02%, 99.46%, and 99.74% to 0.1N, 0.3N, and 0.5N HCl, respectively.
표 2
Figure PCTKR2011003850-appb-T000002
 TABLE 2
Figure PCTKR2011003850-appb-T000002
실시예 2(SiC 마이크로 분말의 제조)Example 2 (Preparation of SiC Micro Powder)
상기 실시례 1에서 세정을 한 Si 미분과 탄소의 반응성 및 적정 탄소 첨가 비율을 조사하기 위하여 Si:C 혼합시료를 제조하였다. Si:C 혼합시료의 혼합비는 Si 1몰 기준으로 하여 1∼4.5 배 몰 범위 내에서 탄소 첨가량을 조절하였다. 계량된 Si 및 탄소 분말은 1/3 부피가 되도록 지르코니아 볼을 채운 200 mL의 플라스틱 용기에 담아 12 시간동안 혼합을 실시하였다. 혼합시료는 수직 튜브형 전기로를 이용하여 1200 ℃에서 2∼10 시간 동안 소성처리 되었다. 소성 후 합성된 SiC 분말은 미반응 탄소의 제거를 위하여 1회 초음파 세척을 실시하였고, 건조를 위하여 80℃ 오븐에서 12 시간동안 보관되었다. In order to investigate the reactivity and the appropriate carbon addition ratio of the Si fine powder and carbon washed in Example 1, a Si: C mixed sample was prepared. The mixing ratio of the Si: C mixed sample was adjusted to an amount of carbon added within the range of 1 to 4.5 times the molar basis on the basis of 1 mol of Si. Weighed Si and carbon powder was mixed in a 12 mL plastic container filled with zirconia balls to 1/3 volume for 12 hours. The mixed sample was calcined at 1200 ° C. for 2 to 10 hours using a vertical tubular electric furnace. After firing, the synthesized SiC powder was subjected to one ultrasonic washing to remove unreacted carbon, and stored in an oven at 80 ° C. for 12 hours for drying.
Si 폐미분과 활성탄의 반응시간에 따른 SiC 반응 특성을 조사하기 위하여, 전기로에서 고상합성을 시도하였다. Si 폐미분과 활성탄의 혼합 몰비는 1:1, 1:1.5 및 1:2로 변화시켰고, 소성온도 1200℃에서 열처리 시간을 2 시간에서 10 시간까지 변화시켜 SiC 합성에 대한 반응성을 조사하였다. 도 6은 혼합 몰 비가 Si:C = 1:1 인 혼합시료에 대한 결과로, 합성된 SiC의 입경은 0.5 - 3 ㎛ 정도로 판단되지만, Si로 판단되는 10 ㎛ 이상의 대형 분말도 존재함을 알 수 있다. XRD 분석 결과로부터 열처리 시간이 짧을수록 미반응 실리콘의 잔류량은 증가하였고, 10 시간의 반응조건에서도 상당량의 미반응 Si 가 잔류한다는 사실을 알았다. 도 7은 Si:C = 1:1.5 혼합시료에 대한 결과이고, 합성된 SiC의 입경은 0.5 - 2 ㎛ 정도를 보였지만 Si:C = 1:1 혼합시료에서와 같이 미반응 실리콘의 대형 분말은 혼재해 있지 않음을 알 수 있다. 따라서 XRD 분석 결과 미반응 Si 도 열처리 시간이 짧은 2시간 조건에서 매우 적은 피크가 관찰되었고 그 이상의 열처리 시간에서는 미반응 Si의 피크는 사라졌다. In order to investigate the SiC reaction characteristics according to the reaction time of Si waste fine powder and activated carbon, solid phase synthesis was attempted in an electric furnace. The mixing molar ratio of the Si fine powder and the activated carbon was changed to 1: 1, 1: 1.5 and 1: 2, and the reactivity to SiC synthesis was investigated by changing the heat treatment time from 2 hours to 10 hours at a firing temperature of 1200 ° C. FIG. 6 shows that the mixed molar ratio of Si: C = 1: 1 indicates that the particle size of the synthesized SiC is about 0.5 to 3 μm, but there is also a large powder of 10 μm or more, which is determined to be Si. have. As a result of XRD analysis, the shorter the heat treatment time, the more the residual amount of unreacted silicon increased, and it was found that a considerable amount of unreacted Si remained even under the reaction conditions of 10 hours. FIG. 7 shows results of Si: C = 1: 1.5 mixed sample, and the particle size of the synthesized SiC showed about 0.5-2 ㎛, but large powder of unreacted silicon was mixed as in Si: C = 1: 1 mixed sample. It can be seen that it is not done. Therefore, as a result of XRD analysis, very small peaks were observed even in the unreacted Si at a short heat treatment time of 2 hours.
도 8은 Si:C = 1:2 혼합시료에 대한 결과이고, SiC의 입경은 0.5 - 4 ㎛ 정도로 C의 합량에 관계없이 5 ㎛ 이하의 SiC가 얻어짐을 알 있다. XRD 분석결과 열처리 시간이 가장 짧은 2 시간의 조건에서도 미반응 실리콘은 관찰되지 않아 실리콘 원료 전량이 SiC로 합성되었음을 확인할 수 있었다. 이상의 Si:C 혼합시료의 경우, 미반응 물질이 존재하지 않는 SiC 합성을 위해서는 적어도 1:1.5 이상의 혼합비를 갖는 시료가 필요하고, 보다 빠른 반응속도로 SiC를 합성하기 위해서는 1:2 혼합비를 갖는 원료가 바람직하다는 사실을 알 수 있었다. FIG. 8 shows results of a Si: C = 1: 2 mixed sample, and it is understood that SiC of 5 µm or less is obtained regardless of the total amount of C at a particle diameter of Si-4. As a result of XRD analysis, unreacted silicon was not observed even under the condition of the shortest heat treatment time of 2 hours, indicating that the entire silicon raw material was synthesized by SiC. In the case of the above Si: C mixed sample, a sample having a mixing ratio of at least 1: 1.5 or more is required for the synthesis of SiC without an unreacted substance, and a raw material having a 1: 2 mixing ratio for synthesizing SiC at a faster reaction rate. It was found that is preferable.
실시예 3(나노 탄화규소의 제조)Example 3 (Preparation of Nano Silicon Carbide)
다음은 혼합 몰 비가 Si:C=1:2 인 혼합분말 시료를 이용하여 1200℃에서 예비 소성하여 합성한 SiC 분말을 플라즈마 반응기에 공급하여 SiC 나노분말의 합성을 시도한 결과이다. 이때 시료 공급량은 0.45 g/min 으로 하였고, 분말 운송 가스의 유량은 1 L/min으로 설정하였다. 또한 아크 열플라즈마 발생장치 전원의 출력 조건은 전류가 250 A 이고 전압은 40 V 이었으며, 플라즈마 불꽃 형성을 위한 가스로는 아르곤 가스와 수소 가스가 사용되었다. 도 9는 합성 SiC 시료에 대한 플라즈마 처리 전후의 SEM 사진을 나타내고 있다. 이 결과에서 플라즈마 처리 전 SiC의 입경은 1-5 ㎛ 이고, 플라즈마 처리에 의해 SiC 의 입경은 1 ㎛ 이하의 나노 분말로 전환됨을 알 수 있다.  The following is a result of attempting the synthesis of SiC nanopowder by supplying a SiC powder synthesized by prebaking at 1200 ° C using a mixed powder sample having a mixed molar ratio of Si: C = 1: 2 to a plasma reactor. At this time, the sample supply amount was 0.45 g / min, and the flow rate of the powder transport gas was set to 1 L / min. In addition, the output condition of the arc thermal plasma generator power source was a current of 250 A and a voltage of 40 V, and argon gas and hydrogen gas were used as gas for plasma flame formation. 9 shows SEM photographs before and after plasma treatment of a synthetic SiC sample. As a result, it can be seen that the particle size of SiC before plasma treatment is 1-5 μm, and the particle size of SiC is converted to nanoparticles of 1 μm or less by plasma treatment.
플라즈마 처리 후 시료에 대하여 정확인 입경 및 입상 변화를 조사하기 위하여, TEM 관찰을 시도하였고 그 결과를 도 10에 나타내었다. 이 TEM 결과로부터 플라즈마 처리에 의하여 SiC 분말의 미세화가 이루어졌음을 확인할 수 있었다. 그러나, 200 nm 이상의 대형 나노입자와 20-30 nm 정도의 소형 나노입자가 혼합되어 있었다.   In order to investigate the exact particle size and grain change of the sample after the plasma treatment, TEM observation was attempted and the results are shown in FIG. 10. From this TEM result, it was confirmed that the SiC powder was refined by the plasma treatment. However, large nanoparticles of 200 nm or more and small nanoparticles of 20-30 nm were mixed.
도 11에는 플라즈마 처리에 의해 SiC의 상 변화가 일어났는지의 유무를 확인하기 위하여, 플라즈마 전후의 시료에 대하여 XRD 분석을 행한 결과를 나타내었다. 이 결과에서 플라즈마 처리 후 나노 SiC 분말의 구성 성분 및 결정구조는 플라즈마 처리 전 상태와 달라져 있지 않음을 확인할 수 있다. FIG. 11 shows the results of XRD analysis on samples before and after plasma in order to confirm whether or not a phase change of SiC occurred by the plasma treatment. As a result, it can be seen that the constituents and crystal structure of the nano SiC powder after the plasma treatment are not different from the state before the plasma treatment.
앞에서 설명된 본 발명의 실시예는 본 발명의 기술적 사상을 한정하는 것으로 해석 되어서는 안 된다. 본 발명의 보호범위는 청구범위에 기재된 사항에 의하여만 제한되고, 본 발명의 기술 분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상을 다양한 형태로 개량 변경하는 것이 가능하다. Embodiment of the present invention described above should not be construed as limiting the technical idea of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those skilled in the art can change and change the technical idea of the present invention in various forms.

Claims (7)

  1. a)실리콘 미분과 탄소원을 혼합 후 소성하여 마이크로 탄화규소(SiC) 분말를 합성하는 단계 및;a) synthesizing the micro silicon carbide (SiC) powder by mixing and firing the silicon fine powder and the carbon source;
    b)상기 마이크로 탄화규소 분말을 열플라즈마로 처리하여 나노 탄화규소로 제조하는 단계를 포함한 열플라즈마를 이용한 나노 탄화규소 제조방법.b) a method for producing nano-silicon carbide using thermal plasma comprising the step of treating the micro-silicon carbide powder with thermal plasma to produce nano-silicon carbide.
  2. 제1항에 있어서,The method of claim 1,
    상기 실리콘 미분은 메탈실리콘 럼프의 분쇄/분급과정에서 발생한 입경 100 ㎛ 이하인 폐미분인 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법.The silicon fine powder is a nano-silicon carbide manufacturing method using thermal plasma, characterized in that the fine powder of the particle diameter of 100 ㎛ or less generated during the pulverization / classification process of the metal silicon lump.
  3. 제2항에 있어서,The method of claim 2,
    상기 실리콘 미분은 상기 a)단계의 소성 전 산세척 및 수세를 거친 것임을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법. The silicon fine powder is nano-silicon carbide manufacturing method using a thermal plasma, characterized in that after the pickling and washing with water before the firing step a).
  4. 제1항에 있어서,The method of claim 1,
    상기 탄소원은 활성탄, 카본블랙 및 흑연으로 이루어진 군으로부터 선택된 1종 이상의 고상 탄소원인 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법.The carbon source is a method for producing nano-silicon carbide using thermal plasma, characterized in that at least one solid carbon source selected from the group consisting of activated carbon, carbon black and graphite.
  5. 제1항에 있어서,The method of claim 1,
    상기 a)단계의 혼합은 볼밀(ball mill)을 이용하여 수행되는 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법.Mixing of step a) is a method for producing nano-silicon carbide using a thermal plasma, characterized in that performed using a ball mill (ball mill).
  6. 제1항에 있어서,The method of claim 1,
    상기 a)단계의 혼합은 실리콘과 탄소원의 비율이 몰비로 1:1.5 내지 2 범위에서 이루어진 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법.The mixing of the step a) is a method of manufacturing silicon nano-carbon using thermal plasma, characterized in that the ratio of silicon and carbon source is made in the range of 1: 1.5 to 2.
  7. 제1항에 있어서,The method of claim 1,
    상기 마이크로 탄화규소의 열플라즈마 처리는 연속식으로 이루어지는 것을 특징으로 하는 열플라즈마를 이용한 나노 탄화규소 제조방법.The thermal plasma treatment of the micro silicon carbide is a nano-silicon carbide production method using a thermal plasma, characterized in that the continuous.
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