KR19990053890A - Carbon film manufacturing method - Google Patents

Carbon film manufacturing method Download PDF

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KR19990053890A
KR19990053890A KR1019970073593A KR19970073593A KR19990053890A KR 19990053890 A KR19990053890 A KR 19990053890A KR 1019970073593 A KR1019970073593 A KR 1019970073593A KR 19970073593 A KR19970073593 A KR 19970073593A KR 19990053890 A KR19990053890 A KR 19990053890A
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carbon film
carbon
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solution
temperature
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KR100325343B1 (en
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이종규
김장규
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신현준
재단법인 포항산업과학연구원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/04—Homopolymers or copolymers of nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/04—Homopolymers or copolymers of nitriles

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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
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  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

본 발명은 탄소막 제조 방법에 관한 것으로,The present invention relates to a carbon film production method,

폴리아크릴로니트릴탄소 섬유(PAN)를 디메틸포름아미드(DMF) 또는 N,N-디메킬아세트아미드(DMAc)로 부터 선택된 용매 3-4 부피비에 용해시킨 용액을 유리판위에 붓는 단계; 및Pouring a solution of polyacrylonitrile carbon fiber (PAN) in a solvent 3-4 volume ratio selected from dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc) onto a glass plate; And

상기 용액을 5-10℃/min의 승온 속도로 이산화탄소 분위기하에 400-500℃까지 열처리하는 단계;를 포함하는 탄소막 제조 방법이 제공된다.It provides a carbon film manufacturing method comprising the step of heat-treating the solution to 400-500 ℃ under a carbon dioxide atmosphere at a temperature rising rate of 5-10 ℃ / min.

본 발명에 의하면, 낮은 열처리 온도에서 기공 형성이 용이함과 동시에 취급성 및 경제성 면에서 우수한 탄소막을 제조할 수 있다.According to the present invention, it is possible to produce a carbon film which is easy in pore formation at low heat treatment temperature and excellent in handling and economical efficiency.

Description

탄소막 제조 방법Carbon film manufacturing method

본 발명은 탄소막 제조 방법에 관한 것으로, 낮은 열처리 온도에서도 메짐성(Brittle)을 없애면서 충분한 기공을 갖는 탄소막을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a carbon film, and to a method for producing a carbon film having sufficient pores while removing brittleness even at a low heat treatment temperature.

일반적으로 막은 크게 고분자를 원료로 하여 제조한 고분자막과 세라믹을 주원료로 하여 제조한 무기막으로 대별될 수 있다.In general, membranes can be roughly classified into polymer membranes made of polymers and inorganic membranes made of ceramics.

이중 고분자막에서 기체를 투과시키는 메카니즘으로는 기공 크기와 분리하고자 하는 기체 물질의 크기에 의한 분리와 막내부에서 분리하고자 하는 대상 물질의 확산 차이를 이용한 메카니즘이 주류를 이루고 있다.As the mechanism for permeating gas in the polymer membrane, the mainstreaming mechanisms include separation by pore size and size of gaseous material to be separated and diffusion of target material to be separated inside the membrane.

또한 고분자막은 고온의 기체를 분리하는데 있어서, 고분자가 견디는 온도 이상에서는 운전이 불가능하고 분리하고자 하는 기체의 구동력인 압력이 높아지면 찢어지는 경우가 있으므로 더욱 견고하면서 분리 성능이 우수한 막의 개발이 진행중이다.In addition, in the separation of high-temperature gas, the polymer membrane is impossible to operate above the temperature at which the polymer can endure, and may be torn when the pressure, which is the driving force of the gas to be separated, may be torn, thus developing a more robust and excellent separation performance.

미국 특허 출원 제 5,104,425는 흑연 디스크의 표면에 중합체 라텍스를 얇게 코팅하여 800-1000℃의 온도에서 질소 분위기하에 열처리하여 제조한 복합 막을 개시하면서, 그 온도와 승온 조건 및 성형 방법에 따른 막의 기공 크기 조절 조건을 함께 명시하고 있다.U.S. Patent Application No. 5,104,425 discloses a composite membrane prepared by thinly coating a polymer latex on the surface of a graphite disk and heat-treated under nitrogen atmosphere at a temperature of 800-1000 ° C. The conditions are also specified.

상기 방법은 지지체로서 흑연을 사용함으로써 표면에 매우 얇은 코팅을 제조할 수 있으나, 흑연의 본래 성질이 외부 충격에 약하므로 고압 조건하에서는 부적절한 막이다.The method can produce very thin coatings on the surface by using graphite as a support, but is inadequate under high pressure conditions because the inherent properties of graphite are susceptible to external impact.

Hiroaki Hatori등은 탄소 전구체와 폴리이미드 필름을 3℃/min의 승온 속도에서 열처리하여 난흑연화성 탄소를 만들어 세공 구조 해석 및 투과도를 조사하였다. 이와 같이 탄소막을 제조하기 위해서는 현재까지는 고가의 중합체를 사용하여 막을 제조하는 단점이 있고, 또한 700-1000℃의 고온하에서 열처리함으로써 불균일한 기공을 형성하고 메짐성(brittle)을 가지므로 취급하기가 매우 어렵다.Hiroaki Hatori et al. Investigated the pore structure analysis and permeability by heat-treating the carbon precursor and the polyimide film at a temperature increase rate of 3 ° C./min to form non-graphitizable carbon. In order to manufacture a carbon film as described above, there is a disadvantage in that a film is manufactured by using an expensive polymer, and heat treatment is performed at a high temperature of 700-1000 ° C. to form uneven pores and have brittleness. it's difficult.

Chery W. Jones 및 William J. Koros들은 중공-섬유 폴리이미드, 셀룰로오스 아세테이트, 폴리아라미드 등을 열분해하여 탄소막을 제조하는 방법을 제시한 바 있다. 그 열분해 온도는 각각 500, 550℃하에 진공 조건(<1torr)에서 전처리한 다음 13.3℃, 0.25℃의 승온 속도로 열처리한다. 그러나 상기 막의 기공 조절을 위하여 승온 속도를 각 단계별로 지정하는 것은 재현성에 있어 문제가 있고, 또한 최종 생성물의 메짐성은 여전히 잔류하므로 제조시 어려움이 있다.Chery W. Jones and William J. Koros have presented a method for producing carbon films by pyrolysing hollow-fiber polyimide, cellulose acetate, polyaramid and the like. The pyrolysis temperature was pretreated under vacuum conditions (<1torr) under 500 and 550 ° C, respectively, followed by heat treatment at a temperature increase rate of 13.3 ° C and 0.25 ° C. However, specifying the temperature increase rate in each step for pore control of the membrane has a problem in reproducibility, and also has difficulty in manufacturing because the brittleness of the final product still remains.

이에 본 발명의 목적은 고분자막 제조시 300-400℃에서 열처리함으로써 탄소막이 갖는 메짐성은 없애고 충분한 기공을 갖는 탄소막을 제조하는 방법을 제공하고자 한다.Accordingly, an object of the present invention is to provide a method for producing a carbon film having sufficient pores by removing the brittleness of the carbon film by heat treatment at 300-400 ° C during polymer film production.

도 1은 400℃까지 열처리한 본 발명의 방법에 의해 제조된 탄소막의 주사 전자 현미경 사진,1 is a scanning electron micrograph of a carbon film prepared by the method of the present invention heat-treated to 400 ℃,

도 2는 500℃까지 열처리한 본 발명의 방법에 의해 제조된 다른 탄소막의 주사 전자 현미경 사진,2 is a scanning electron micrograph of another carbon film prepared by the method of the present invention heat-treated to 500 ℃,

도 3은 500℃까지 열처리시킨 또다른 탄소막의 주사 전자 현미경 사진 및3 is a scanning electron micrograph of another carbon film heat-treated to 500 ℃

도 4는 본 발명의 온도 범위에서 벗어난 800℃까지 열처리시켜 제조된 탄소막의 주사 전자 현미경 사진이다.4 is a scanning electron micrograph of a carbon film prepared by heat treatment to 800 ℃ outside the temperature range of the present invention.

폴리아크릴로니트릴탄소 섬유(PAN)를 디메틸포름아미드(DMF) 또는 N,N-디메킬아세트아미드(DMAc)로 부터 선택된 용매 3-4 부피비에 용해시킨 용액을 유리판위에 붓는 단계; 및Pouring a solution of polyacrylonitrile carbon fiber (PAN) in a solvent 3-4 volume ratio selected from dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc) onto a glass plate; And

상기 용액을 5-10℃/min의 승온 속도로 이산화탄소 분위기하에 400-500℃까지 열처리하는 단계;를 포함하는 탄소막 제조 방법이 제공된다.It provides a carbon film manufacturing method comprising the step of heat-treating the solution to 400-500 ℃ under a carbon dioxide atmosphere at a temperature rising rate of 5-10 ℃ / min.

이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.

폴리아크릴로니트릴탄소 섬유(PAN)를 디메틸포름아미드(DMF)나 N,N-디메킬아세트아미드(DMAc)용매 3-4 부피비에 용해시킨다.Polyacrylonitrile carbon fibers (PAN) are dissolved in 3-4 volume ratios of dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc) solvent.

탄소 섬유용 공중합체인 폴리아크릴로니트릴 탄소 섬유(PAN)에 대하여 용매를 3-4배로 용해시키는 이유는 이 양을 초과하면 폴리아크릴로니트릴 용액의 점도가 지나치게 높아지므로 후속 단계로 열처리 공정시 용매가 휘발될 때 막 내부에서 수축과 팽창으로 인하여 주름이 잡히고, 기공 형성을 어려워지게 되며, 용매의 양이 부족하면 열처리시 대부분의 용매가 휘발되어 최종 생성된 막은 찢어지는 경향을 보인다.The reason for dissolving the solvent 3-4 times in polyacrylonitrile carbon fiber (PAN), which is a copolymer for carbon fiber, is that the viscosity of the polyacrylonitrile solution becomes too high when this amount is exceeded. When volatilized, it becomes wrinkled due to shrinkage and expansion inside the membrane, making pore formation difficult, and when the amount of solvent is insufficient, most of the solvent is volatilized during heat treatment, resulting in a tendency to tear the final film.

이와 같이 용매의 양을 조절함으로써 열처리시 용매의 휘발 속도와 PAN의 결합을 조절하게 되어 기공을 형성하면서 균일하고도 얇은 막을 제조할 수 있다.As such, by controlling the amount of the solvent, the rate of volatilization of the solvent and the binding of the PAN during the heat treatment may be controlled to form uniform and thin films while forming pores.

이와 같이 용해된 용액을 유리판위에 붓고 5-10℃/min의 승온 속도로 이산화탄소 분위기하에 열처리시켜 탄소막을 제조한다.The solution thus dissolved is poured onto a glass plate and heat treated in a carbon dioxide atmosphere at a temperature rising rate of 5-10 ° C./min to produce a carbon film.

상기 열치리시 승온 속도는 용매의 휘발 속도와도 매우 긴밀한 상관 관계를 가지고 있는데, 승온 속도가 10℃/min 보다 빠른 경우에는 용매만 휘발될 뿐 기공 형성과는 거의 무관하며, 승온 속도가 5℃/min보다 낮은 경우에는 용매는 휘발되나 내부에 잔존하게 되어 기공이 형성될 시간이 없다.The temperature increase rate during thermal treatment has a very close correlation with the volatilization rate of the solvent. When the temperature increase rate is faster than 10 ° C./min, only the solvent is volatilized, which is almost independent of pore formation, and the temperature increase rate is 5 ° C. If it is lower than / min, the solvent volatilizes but remains inside, and there is no time for pores to form.

또한 본 발명과 같은 저온 열처리시 분위기는 N2보다는 CO2분위기가 바람직하다.In addition, the atmosphere at low temperature heat treatment as in the present invention is preferably a CO 2 atmosphere rather than N 2 .

상기 최종 열처리 온도는 400-500℃가 적절하며, 400℃보다 낮게 되면, 용매의 휘발 속도가 낮아 기공 형성이 이루어지지 않으며, 또한 고분자로서의 약한 성질을 가지며, 온도가 500℃를 초과하는 경우에는 무기막으로서의 본래의 성질인 메짐성으로 인하여 취급하기가 어려워진다.The final heat treatment temperature is appropriately 400-500 ℃, if it is lower than 400 ℃, the volatilization rate of the solvent is not low because the formation of pores, also has a weak property as a polymer, when the temperature exceeds 500 ℃ inorganic The brittleness inherent in the membrane makes it difficult to handle.

이와 같은 방식으로 제조된 탄소막은 기공 형성이 우수하고 취급성이 우수하다.The carbon film prepared in this manner has excellent pore formation and excellent handleability.

이하, 실시예를 통하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.

실시예 1Example 1

탄소 섬유용 공중합체인 폴리아크릴로니트릴 탄소 섬유(PAN)를 N,N-디메틸아세트아미드(DMAc) 용매 3부피비에 용해시킨 용액을 유리판 위에 적당량을 붓는다. 이산화탄소 분위기하에서 5℃/min의 승온 속도에서 400℃까지 열처리하고 제조된 탄소막을 찍어 도 1에 도시하였다.An appropriate amount is poured onto a glass plate of a solution obtained by dissolving polyacrylonitrile carbon fiber (PAN), which is a copolymer for carbon fibers, in 3 parts by volume of N, N-dimethylacetamide (DMAc) solvent. The carbon film was heat-treated to 400 ° C. at a temperature increase rate of 5 ° C./min in a carbon dioxide atmosphere, and the resulting carbon film was shown in FIG. 1.

실시예 2Example 2

탄소 섬유용 공중합체인 폴리아크릴로니트릴 탄소 섬유(PAN)를 디메틸포름아미드 (DMF) 용매 4부피비에 용해시킨 용액을 유리판 위에 적당량을 붓는다. 이산화탄소 분위기하에서 5℃/min의 승온 속도에서 500℃까지 열처리하고 제조된 탄소막을 찍어 도 2에 도시하였다.A suitable amount of a solution obtained by dissolving polyacrylonitrile carbon fiber (PAN), a copolymer for carbon fibers, in 4 parts by volume of dimethylformamide (DMF) solvent is poured onto a glass plate. The carbon film was heat-treated to 500 ° C. at a temperature increase rate of 5 ° C./min in a carbon dioxide atmosphere, and the resulting carbon film was shown in FIG. 2.

실시예 3Example 3

탄소 섬유용 공중합체인 폴리아크릴로니트릴 탄소 섬유(PAN)를 N,N-디메틸아세트아미드(DMAc) 용매 3부피비에 용해시킨 용액을 유리판 위에 적당량을 붓는다. 이산화탄소 분위기하에서 10℃/min의 승온 속도에서 500℃까지 열처리하고 제조된 탄소막을 찍어 도 3에 도시하였다.An appropriate amount is poured onto a glass plate of a solution obtained by dissolving polyacrylonitrile carbon fiber (PAN), which is a copolymer for carbon fibers, in 3 parts by volume of N, N-dimethylacetamide (DMAc) solvent. The carbon film was heat-treated to 500 ° C. at a temperature increase rate of 10 ° C./min in a carbon dioxide atmosphere, and the carbon film thus obtained was shown in FIG. 3.

이와 같이 제조된 탄소막은 육안으로 관찰시 찢어진 부분이 없을 뿐더러, 도 1-3에서 보듯이 기공 형성이 잘 이루어져 있음을 알 수 있다.The carbon film thus prepared has no torn portion when visually observed, and it can be seen that pores are well formed as shown in FIGS. 1-3.

비교예Comparative example

탄소 섬유용 공중합체인 폴리아크릴로니트릴 탄소 섬유(PAN)를 디메틸포름아미드 (DMF) 용매 3부피비에 용해시킨 용액을 유리판 위에 적당량을 붓는다. 이산화탄소 분위기하에서 5℃/min의 승온 속도에서 800℃까지 열처리하고 제조된 탄소막을 찍어 도 4에 도시하였다.A suitable amount of a solution obtained by dissolving polyacrylonitrile carbon fiber (PAN), which is a copolymer for carbon fiber, in a 3 volume ratio of dimethylformamide (DMF) solvent is poured onto a glass plate. The carbon film was heat-treated to 800 ° C. at a temperature increase rate of 5 ° C./min in a carbon dioxide atmosphere, and the carbon film thus prepared was shown in FIG. 4.

도 4에서 보듯이, 탄소막은 기공이 생기기 전에 PAN 필름이 국부적으로 전소하여 형성된 입자들이 분포하며, 주름진 불균일한 형태임을 알 수 있다.As shown in FIG. 4, the carbon film has particles formed by locally burning the PAN film before porosity, and it can be seen that the carbon film has a wrinkled non-uniform shape.

상기한 바에 따르면, 고분자를 주원료로 하여 용매에 용해시켜 탄소막을 제조하는 본 발명에서는 낮은 열처리 온도에서 기공 형성이 용이함과 동시에 취급성 및 경제성 면에서 우수한 탄소막을 제조할 수 있다.According to the above, in the present invention in which the polymer is used as a main raw material to be dissolved in a solvent to produce a carbon film, it is possible to form a carbon film having excellent porosity and low handleability and economical efficiency at low heat treatment temperature.

Claims (1)

폴리아크릴로니트릴탄소 섬유(PAN)를 디메틸포름아미드(DMF) 또는 N,N-디메킬아세트아미드(DMAc)로 부터 선택된 용매 3-4 부피비에 용해시킨 용액을 유리판위에 붓는 단계; 및Pouring a solution of polyacrylonitrile carbon fiber (PAN) in a solvent 3-4 volume ratio selected from dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc) onto a glass plate; And 상기 용액을 5-10℃/min의 승온 속도로 이산화탄소 분위기하에 400-500℃까지 열처리하는 단계;를 포함하는 탄소막 제조 방법Heat treating the solution to 400-500 ° C. under a carbon dioxide atmosphere at an elevated temperature rate of 5-10 ° C./min.
KR1019970073593A 1997-12-24 1997-12-24 Process for producing carbon membrane KR100325343B1 (en)

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JPS60179102A (en) * 1984-02-27 1985-09-13 Toray Ind Inc Carbon membrane and its preparation
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JPS6426723A (en) * 1987-07-17 1989-01-30 Mitsubishi Rayon Co Finely porous hollow carbon membrane fiber and production thereof
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