WO2016171490A1 - Gas barrier membrane using graphene oxide prepared by solution mixing method, and method for preparing same - Google Patents

Gas barrier membrane using graphene oxide prepared by solution mixing method, and method for preparing same Download PDF

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WO2016171490A1
WO2016171490A1 PCT/KR2016/004159 KR2016004159W WO2016171490A1 WO 2016171490 A1 WO2016171490 A1 WO 2016171490A1 KR 2016004159 W KR2016004159 W KR 2016004159W WO 2016171490 A1 WO2016171490 A1 WO 2016171490A1
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gas barrier
graphene oxide
solution
barrier membrane
present
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PCT/KR2016/004159
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French (fr)
Korean (ko)
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이중희
김남훈
라마 칸타 라익
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전북대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

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  • the present invention relates to a gas barrier membrane prepared by a solution mixing method and a method of manufacturing the same, and more particularly, a gas barrier membrane having improved gas barrier properties by including graphene oxide having an interlocking laminated structure manufactured by a solution mixing method and its It relates to a manufacturing method.
  • graphene oxide Graphene oxide
  • reduced graphene oxide rGO, reduced graphene oxide
  • the reduced graphene oxide sheet has a property of forming agglomerates in a liquid phase and most organic solvents, it is difficult to form a reduced graphene oxide based coating.
  • the inventors of the present invention found that the formation of graphene oxide having a laminated structure interlocked with each other improves the gas barrier property, thereby completing the gas barrier layer according to the present invention.
  • the present invention has been devised to solve the above problems, and an object of the present invention is to provide a gas barrier film having improved gas barrier properties and a method of manufacturing the same by including graphene oxide having a laminated structure engaged with each other.
  • the present invention provides a gas barrier membrane comprising a graphene oxide and a polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50.
  • hydrogen gas permeability when the thickness of the gas barrier membrane is 0.5 ⁇ m ⁇ 500 ⁇ m, hydrogen gas permeability may be 0.01 ⁇ 100 cc / m 2 atm day.
  • Another aspect of the present invention is a step of preparing a graphene oxide solution by dissolving the graphene oxide in water; Step 2 to increase the concentration by vacuum filtration of the graphene oxide solution; Preparing a mixed solution by mixing the polyvinyl alcohol solution with the graphene oxide having increased concentration; And applying a mixed solution prepared in step 3 to produce a gas barrier membrane. 4.
  • the concentration of the graphene oxide solution of the first step is 0.1 to 5 mg / ml, the concentration can be increased 1.5 to 20 times by vacuum filtration of graphene oxide in the second step. .
  • the graphene oxide and the polyvinyl alcohol solution in the third step may be mixed in a weight ratio of 50 ⁇ 99: 1 ⁇ 50.
  • the mixed solution in the step 4 may be applied using one method selected from the group consisting of spin coating method, spray coating method and dip coating method.
  • the gas barrier membrane according to the present invention can improve gas barrier properties by reducing gas permeability and transmission coefficient by up to 95 times or more.
  • FIG. 1 is a schematic view showing a method of manufacturing a gas barrier film according to an embodiment of the present invention.
  • Example 2 is a spectrum showing the FTIR results of Example 1 and Comparative Examples 2 to 3 of the present invention.
  • Example 3 is a graph showing the WAXS pattern of Example 1 and Comparative Examples 1 and 2 according to the present invention.
  • Figure 4 (a) and (b) is a field scanning electron microscope image of the cross-sectional view of Example 1 and Example 2 according to the present invention, (c) and (d) is Example 1 and according to the present invention Field emission scanning electron microscope image of the surface of Example 2.
  • FIG. 5 is a field emission scanning electron microscope image of a cross section of Comparative Example 2.
  • FIG. 6 is a field emission scanning electron microscope image of a cross section of Comparative Example 3.
  • Example 7 is a graph showing the coating film thickness of Example 1 and Comparative Examples 2 to 3.
  • Graphene oxide (GO, Graphene oxide) and reduced graphene oxide (rGO, reduced graphene oxide) (rGO) can be prepared in large quantities for the production of nanocomposites with improved gas barrier properties, the reduced graphene oxide sheet is a liquid and Since there is a property of forming agglomerates in most organic solvents, there is a problem that it is difficult to form a reduced graphene oxide based coating.
  • graphene oxide has a problem of less gas barrier properties than reduced graphene oxide because of many defects, but is easy to coat on a polymer substrate.
  • the present invention provides a gas barrier membrane comprising a graphene oxide and a polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50.
  • the gas barrier membrane may block hydrogen gas and oxygen gas, and the gas barrier membrane may be improved as the thickness of the gas barrier membrane increases, and thus the gas barrier membrane may be applied to a substrate, a hydrogen storage tank, and used for various purposes and uses.
  • the present invention will be described in more detail by component.
  • the gas barrier membrane according to the present invention includes graphene oxide and polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50.
  • the graphene oxide may be formed in a layered structure interlocked with each other to improve gas barrier properties, and polyvinyl alcohol is added to serve as a binder resin.
  • the graphene oxide and the polyvinyl alcohol solution may be mixed in a weight ratio of 50 to 99: 1 to 50, and more preferably in a weight ratio of 80 to 99: 1 to 20.
  • the graphene oxide and the polyvinyl alcohol solution are mixed at a weight ratio of less than 50:50, gas barrier properties are difficult to be sufficiently improved, and when mixed at a weight ratio of 99: 1, it is difficult to form a coating layer. have.
  • hydrogen gas permeability when the thickness of the gas barrier membrane according to the present invention is 0.5 ⁇ m ⁇ 500 ⁇ m, hydrogen gas permeability may be 0.01 ⁇ 100 cc / m 2 atm day.
  • the hydrogen gas permeability when the thickness of the coating film is 0.5 ⁇ m to 3 ⁇ m, the hydrogen gas permeability may be 1 to 25 cc / m 2 atm day, and when the thickness of the gas barrier film is 0.5 ⁇ m to 2 ⁇ m, the hydrogen gas permeability is 1 to It may be 15 cc / m 2 atm day, more preferably, when the thickness of the coating film is 0.5 ⁇ m ⁇ 1 ⁇ m, hydrogen gas permeability may be 1 ⁇ 10 cc / m 2 atm day.
  • the transmission coefficient of hydrogen gas may be 0.1 ⁇ 2.5 cc mm / m 2 atm day.
  • the transmission coefficient may be 0.1 ⁇ 2 cc mm / m 2 atm day, more preferably, when the thickness of the gas barrier membrane is 0.5 ⁇ m ⁇ 1 ⁇ m,
  • the modulus may be between 0.1 and 1 cc mm / m 2 atm day.
  • the gas barrier membrane according to the present invention has an oxygen gas permeability of 0.1 to 1 cc / m 2 atm day and a transmission coefficient when the thickness of the substrate is 100 ⁇ m to 120 ⁇ m, and the thickness of the gas barrier membrane is 0.5 ⁇ m to 1 ⁇ m. May be 0.01 to 0.1 cc mm / m 2 atm day.
  • Gas barrier membrane according to the invention can be prepared by the following manufacturing method.
  • the present invention is a step of preparing a graphene oxide solution by dissolving the graphene oxide in water; Step 2 to increase the concentration by vacuum filtration of the graphene oxide solution; Preparing a mixed solution by mixing the polyvinyl alcohol solution with the graphene oxide having increased concentration; And forming a gas barrier layer by coating the mixed solution prepared in step 3 on the substrate to form a gas barrier layer, thereby forming graphene oxide having a laminated structure interlocked with each other. It provides a gas barrier membrane and a method for manufacturing the same improved gas barrier properties.
  • the present invention will be described in more detail step by step.
  • the first step is to prepare a graphene oxide solution by dissolving the graphene oxide in water, wherein the graphene oxide solution is at this time, the graphene oxide solution of The concentration may be 0.1-5 mg / ml.
  • the graphene oxide may be prepared using a Hummer's method or a modified Hummer's method as a known method, but is not particularly limited thereto.
  • a Hummer's method or a modified Hummer's method as a known method, but is not particularly limited thereto.
  • the second step is to increase the concentration by vacuum filtration of the graphene oxide solution.
  • Graphene oxide has fewer gas barrier properties than reduced graphene oxide because of many defects, but has an advantage of easy coating on a polymer substrate. Therefore, the graphene oxide with the increased concentration as described above is formed in a layered structure interlocked with each other in the solution to improve the gas barrier properties can be produced a gas barrier film excellent in gas barrier properties.
  • the concentration of 1.5 to 20 times by vacuum filtration of graphene oxide in the second step preferably 5 to 10 times, and more preferably 8 to 10 times.
  • concentration is increased to less than 1.5 times, there is a problem that it is difficult to form a layered structure, when the concentration is increased by more than 20 times, graphene oxide may aggregate to form agglomeration, and become a gel state rather than a solution. There is this.
  • the third step is to prepare a mixed solution by mixing the polyvinyl alcohol solution to the graphene oxide having increased concentration, the polyvinyl alcohol solution is a graphene oxide It can serve as a binder for fixing.
  • the graphene oxide and the polyvinyl alcohol solution in the third step may be mixed in a weight ratio of 50 to 99: 1 to 50, more preferably 80 to 99: 1 to 20 by weight ratio.
  • the graphene oxide and the polyvinyl alcohol solution are mixed at a weight ratio of less than 50:50, gas barrier properties are difficult to be sufficiently improved, and when mixed at a weight ratio of 99: 1, it is difficult to form a coating layer. have.
  • the fourth step is to prepare a gas barrier membrane by applying the mixed solution prepared in step 3, wherein the mixed solution prepared in step 3 is a substrate or a tank for storing hydrogen It is possible to improve the gas barrier properties by applying to the surface, such as to form a coating film.
  • the substrate may be any commercially available polymer substrate, and is not particularly limited.
  • the substrate is a polyethylene substrate, polypropylene, polyethylene terephthalate, polyethylene terephthalate glycol, polycarbonate, polystyrene, polyamide, poly It may include at least one substrate selected from the group consisting of butylene terephthalate, polymethyl pentene, polyvinyl chloride, nylon and copolymers thereof, more preferably polyethylene substrate, polypropylene, polyethylene terephthalate, nylon And one or more substrates selected from the group consisting of copolymers thereof.
  • the coating film may control the thickness of the coating film by adjusting the volume of the mixed solution to be applied, it is preferable to apply 0.5 ⁇ 3 ml per unit area (cm 2 ), more preferably per unit area (cm 2 ) It is recommended to apply 1.5 to 3 ml.
  • a coating film of 0.5 ⁇ m ⁇ 3 ⁇ m thick When applied as described above may be prepared a coating film of 0.5 ⁇ m ⁇ 3 ⁇ m thick.
  • the mixed solution in the step 4 may be used any method as long as it is a commercial method for applying to the substrate, preferably one method selected from the group consisting of spin coating method, spray coating method and dip coating method It can apply
  • Graphene oxide was prepared using a modified human method. 100 mL of graphene oxide at a concentration of 1 mg / mL was concentrated to 8 mg / ml using a vacuum filter. A polyvinyl alcohol (PVA, sigma aldrich) solution was mixed with the concentrated graphene oxide solution at a weight ratio of 8: 2 to prepare a GO / PVA mixed solution.
  • PVA polyvinyl alcohol
  • a gas barrier film was prepared in the same manner as in Example 1, except that 6 ml of the GO / PVA mixed solution was coated on a substrate to form a coating film having a thickness of 1.56 ⁇ m.
  • a gas barrier film was prepared in the same manner as in Example 1 except that 9 ml of the GO / PVA mixed solution was coated on a substrate to form a coating film having a thickness of 2.56 ⁇ m.
  • PET polyethylene terephthalate
  • the gas barrier membrane was manufactured by the method.
  • a gas barrier film was prepared in the same manner as in Example 1 except that the PVA was applied by a spin coating method.
  • Example 1 and Comparative Examples 2 to 3 prepared according to the present invention was measured by Fourier transform infrared spectroscopy (FTIR) to measure the interaction between the graphene side and polyvinyl alcohol, the results are shown in FIG.
  • FTIR Fourier transform infrared spectroscopy
  • the PVA has a broad peak at 3445 cm ⁇ 1 , which is manifested by the intermolecular interaction of the —OH group bound to the H-group, while the peak at 3410 cm ⁇ 1 for graphene oxide for the same bond Appears.
  • the GO / PVA nanocomposite has a peak at 3432 cm ⁇ 1 , unlike the peaks of GO and PVA, respectively, and the width of the peak is also relatively narrow.
  • PVA has a peak for unhydrated ester groups at 1730 cm -1
  • GO has a peak at 1718 cm -1 for COOH groups.
  • GO / PVA nanocomposites can be seen that has a peak at 1724 cm -1 .
  • the intermolecular H-bonds between the GO sheet or PVA chain disappears and new bonds are formed in the GO and PVA molecules.
  • GO had a peak at 1622 cm ⁇ 1 for unoxidized graphite or inserted water molecules, which shifted to 1634 cm ⁇ 1 in the GO / PVA complex.
  • GO sheets are known to exhibit a highly ordered structure with a space between two layers that are highly adjacent.
  • the GO / PVA composite can be seen that the diffraction peak shifts to a lower angle than when measured by the GO sheet alone, and it can be inferred that the space between the GO sheets is expanded by introducing PVA into the space between the GO sheets. have.
  • Comparative Examples 2 to 3 it was confirmed that the coating film is formed in a thin thickness compared to Example 1. This is because the density of the PVA is smaller than the GO, so that the PVA penetrates into the GO, and therefore, in Comparative Example 3 in which only the PVA is coated, the coating film is formed in a relatively thin thickness compared to Comparative Example 2 in which only the GO is coated.
  • Example 1 0.82 110.82 21 2.32
  • Example 2 1.56 111.56 14 1.56
  • Example 3 2.56 112.56 5 0.56 Comparative Example 1 - 110 122 13.42 Comparative Example 2 0.52 110.52 69 7.62 Comparative Example 3 0.280 110.28 110 12.40
  • Example 1 0.82 110.82 0.78 0.086 Comparative Example 1 - 110 21.2 2.23
  • the gas barrier film is 0.5 ⁇ m to 3 ⁇ m
  • the hydrogen gas permeability is 1 to 25 cc / m 2 atm day
  • the transmission coefficient is It can be seen that 0.1 ⁇ 2.5 cc mm / m 2 atm day.
  • the thickness of the gas barrier membrane may be 0.5 to 3 ⁇ m, preferably 1 to 3 ⁇ m, more preferably 2 to 3 ⁇ m. It can be seen that the hydrogen permeability and the coefficient of permeability decrease according to the thickness of the coating film. When the thickness of the coating film is 2.56 ⁇ m, it was confirmed that the hydrogen transmittance is reduced by 96% compared to Comparative Example 1 without the coating film, it was confirmed that the transmission coefficient is also reduced to 95%.
  • the thickness of the substrate is 100 ⁇ m ⁇ 120 ⁇ m
  • the thickness of the coating film is 0.5 ⁇ m ⁇ 1 ⁇ m
  • the oxygen gas permeability is 0.1 ⁇ 1 cc / m 2 atm day
  • the transmission coefficient is 0.01 ⁇ 0.1 cc mm / m 2 atm day
  • the gas barrier membrane according to the present invention was confirmed that the hydrogen gas and oxygen gas blocking ability is remarkably excellent.

Abstract

The present invention relates to a gas barrier membrane prepared by a solution mixing method, and a method for preparing the same and, more particularly, to a gas barrier membrane having an improved gas barrier property by comprising a graphene oxide which is prepared by a solution mixing method and has an interdigitated layered structure; and a method for preparing the same. More specifically, the present invention provides a method for preparing a gas barrier membrane, comprising: a first step of preparing graphene oxide according to a solution process; a second step of vacuum-filtering the graphene oxide prepared according to the solution process to thereby increase the concentration thereof; a third step of mixing a polyvinylalcohol solution with the concentration-increased graphene oxide to thereby prepare a mix solution; and a fourth step of applying the mix solution prepared in the third step on a substrate to thereby prepare a gas barrier membrane.

Description

용액혼합법으로 제조된 그래핀 옥사이드를 이용한 가스차단막 및 이의 제조방법Gas barrier membrane using graphene oxide prepared by the solution mixing method and its preparation method
본 발명은 용액혼합법으로 제조된 가스차단막 및 이의 제조방법에 관한 것으로서, 보다 상세하게는 용액혼합법으로 제조되는 서로 맞물린 적층 구조를 갖는 그래핀 옥사이드를 포함함으로써 기체차단 특성이 향상된 가스차단막 및 이의 제조방법에 관한 것이다. The present invention relates to a gas barrier membrane prepared by a solution mixing method and a method of manufacturing the same, and more particularly, a gas barrier membrane having improved gas barrier properties by including graphene oxide having an interlocking laminated structure manufactured by a solution mixing method and its It relates to a manufacturing method.
현시대의 주요한 난제 중 하나는 종래의 천연에너지원을 대체할 수 있는 수소와 같은 대체 에너지원을 발명하는 것이다. 수소 에너지를 유용하기 위하여, 수소의 고가열성 특성 및 중량 대비 부피비가 높은 점 등으로 인하여 수소 가스의 안전한 저장을 위한 연구가 주요 이슈로 부각되고 있다. One of the major challenges of the present age is to invent alternative energy sources, such as hydrogen, which can replace conventional natural energy sources. In order to use hydrogen energy, research for safe storage of hydrogen gas has emerged as a major issue due to the high heating properties and high volume to weight ratio of hydrogen.
현재까지는, 고압의 중금속 탱크가 수소의 저장 및 운송을 위하여 이용되고 있다. 그러나 이로 인해 더 많은 에너지가 이용되고 있고, 비용 또한 증가하는 문제점이 있다. 따라서 상기와 같은 문제점을 해결하기 위하여 수소를 저장하기 위한 경량의 탱크를 제조하는 것에 대한 필요성이 대두되고 있다. To date, high pressure heavy metal tanks have been used for the storage and transportation of hydrogen. However, because of this, more energy is used, and cost also increases. Therefore, there is a need to manufacture a lightweight tank for storing hydrogen in order to solve the above problems.
이러한 문제들은 고분자를 통해 해결될 수 있는데, 수소 가스를 저장하기 위한 탱크는 고분자성 물질이 수소 가스의 높은 차단특성을 나타내어야 한다. 그러나 상용의 고분자가 가지는 수소 차단 특성은 수소 가스의 투과를 충분히 방지할 정도로 우수하지 않은 문제점이 있다. 그러므로, 단일 고분자 차단막의 수소 차단 특성을 향상시키기 위한 노력이 요구되고 있다. 이러한 목적은 불투과성 필러를 이용하여 고분자 나노복합체를 제조함으로써 해결될 수 있고, 산업적 공학적 용도를 위한이에 대한 다양한 연구가 진행되고 있다. These problems can be solved through polymers. In the tank for storing hydrogen gas, the polymeric material must exhibit high barrier properties of hydrogen gas. However, there is a problem that the hydrogen blocking property of the commercial polymer is not excellent enough to prevent the permeation of hydrogen gas. Therefore, efforts to improve the hydrogen barrier properties of a single polymer barrier film are required. This object can be solved by manufacturing a polymer nanocomposite using an impermeable filler, and various studies on it for industrial engineering applications are underway.
최근, 그래핀의 가스 차단 특성을 높이기 위하여 그래핀을 고분자매트릭스와 결합하는 방식이나 그래핀을 고분자 기판 상에 표면 코팅하는 방식으로 그래핀 및 고분자 나노복합체에 대한 연구가 활발히 진행되고 있다. 그래핀은 이차원 탄소나노물질로서, 높은 종횡비(aspect ratio)를 가지고, 우수한 기계적 강도 및 전기전도도를 가지는 특성이 있다. 분자단위의 실험 및 연구에 따르면, 그래핀은 모든 가스 분자를 차단할 수 있다. 그러나 불투과성 그래핀은 결함이 없다. 화학적 기상 증착법(CVD, chemical vapor deposition) 및 물리적으로 박리되어 제조된 그래핀은 결함은 적으나 복합체를 제조하기 위해서는 현저히 많은 양이 필요하고, 종래의 방법으로는 이에 필요한 정도의 양을 제조하기는 어려운 문제점이 있다. Recently, research has been actively conducted on graphene and polymer nanocomposites by combining graphene with a polymer matrix or surface coating on a polymer substrate in order to increase the gas barrier property of graphene. Graphene is a two-dimensional carbon nano material, has a high aspect ratio, and has excellent mechanical strength and electrical conductivity. According to molecular experiments and studies, graphene can block all gas molecules. However, impermeable graphene is not defective. Graphene manufactured by chemical vapor deposition (CVD) and physical exfoliation has few defects, but it requires a considerable amount to produce a composite, and conventional methods do not produce the required amount. There is a difficult problem.
한편, 그래핀 옥사이드(GO, Graphene oxide) 및 환원된 그래핀 옥사이드(rGO, reduced graphene oxide)은 나노복합체를 제조하기 위해 대량으로 제조될 수 있다. 환원된 그래핀 옥사이드 시트는 액상 및 대부분의 유기 용매에서 덩어리를 형성하는 특성이 있으므로, 환원된 그래핀 옥사이드 기반의 코팅을 형성시키기 어려운 문제점이 있다. On the other hand, graphene oxide (GO, Graphene oxide) and reduced graphene oxide (rGO, reduced graphene oxide) may be prepared in large quantities to produce a nanocomposite. Since the reduced graphene oxide sheet has a property of forming agglomerates in a liquid phase and most organic solvents, it is difficult to form a reduced graphene oxide based coating.
이에, 본 발명의 발명자들은 서로 맞물린 적층 구조를 갖는 그래핀 옥사이드를 형성하면 기체 차단 특성이 향상되는 것을 알게되어 본 발명에 따른 가스차단막을 완성하였다. Thus, the inventors of the present invention found that the formation of graphene oxide having a laminated structure interlocked with each other improves the gas barrier property, thereby completing the gas barrier layer according to the present invention.
본 발명은 상기와 같은 문제점을 안출하기 위하여 고안된 것으로서, 본 발명의 목적은 서로 맞물린 적층 구조를 갖는 그래핀 옥사이드를 포함함으로써 기체차단 특성이 향상된 가스차단막 및 이의 제조방법을 제공하는 데 있다. The present invention has been devised to solve the above problems, and an object of the present invention is to provide a gas barrier film having improved gas barrier properties and a method of manufacturing the same by including graphene oxide having a laminated structure engaged with each other.
이에, 본 발명은 그래핀 옥사이드 및 폴리비닐알코올 바인더 수지를 50 ~ 99: 1 ~ 50의 중량비로 포함하는 가스차단막을 제공한다.Accordingly, the present invention provides a gas barrier membrane comprising a graphene oxide and a polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50.
본 발명의 바람직한 일실시예에 있어서, 상기 가스차단막의 두께가 0.5 ㎛ ~ 500 ㎛일 때, 수소가스 투과도가 0.01 ~ 100 cc/m2 atm day일 수 있다. In a preferred embodiment of the present invention, when the thickness of the gas barrier membrane is 0.5 ㎛ ~ 500 ㎛, hydrogen gas permeability may be 0.01 ~ 100 cc / m 2 atm day.
본 발명의 다른 태양은 그래핀 옥사이드를 물에 녹여 그래핀옥사이드 용액을 제조하는 1단계; 상기 그래핀 옥사이드 용액을 진공여과하여 농도를 증가시키는 2단계; 상기 농도가 증가된 그래핀 옥사이드에 폴리비닐알코올 용액을 혼합하여 혼합용액을 제조하는 3단계; 및 상기 3단계에서 제조된 혼합용액을 도포하여 가스차단막을 제조하는 4단계;를 포함하는 것을 특징으로 하는 가스차단막의 제조방법을 제공한다.Another aspect of the present invention is a step of preparing a graphene oxide solution by dissolving the graphene oxide in water; Step 2 to increase the concentration by vacuum filtration of the graphene oxide solution; Preparing a mixed solution by mixing the polyvinyl alcohol solution with the graphene oxide having increased concentration; And applying a mixed solution prepared in step 3 to produce a gas barrier membrane. 4.
본 발명의 바람직한 일실시예에 있어서, 상기 1단계의 그래핀 옥사이드 용액의 농도는 0.1 ~ 5 mg/ml이고, 상기 2단계에서 그래핀 옥사이드를 진공여과하여 농도를 1.5 ~ 20배 증가시킬 수 있다. In a preferred embodiment of the present invention, the concentration of the graphene oxide solution of the first step is 0.1 to 5 mg / ml, the concentration can be increased 1.5 to 20 times by vacuum filtration of graphene oxide in the second step. .
본 발명의 바람직한 일실시예에 있어서, 상기 3단계에서 그래핀 옥사이드와 폴리비닐알코올 용액은 50 ~ 99:1 ~ 50의 중량비로 혼합될 수 있다. In a preferred embodiment of the present invention, the graphene oxide and the polyvinyl alcohol solution in the third step may be mixed in a weight ratio of 50 ~ 99: 1 ~ 50.
본 발명의 바람직한 일실시예에 있어서, 상기 4단계에서 혼합용액을 스핀 코팅법, 스프레이 코팅법 및 딥 코팅법으로 이루어진 군으로부터 선택되는 1종의 방법을 이용하여 도포할 수 있다. In a preferred embodiment of the present invention, the mixed solution in the step 4 may be applied using one method selected from the group consisting of spin coating method, spray coating method and dip coating method.
본 발명에 따르면, 그래핀 옥사이드를 폴리비닐알콜 고분자 바인더 내에 서로 맞물린 적층 구조를 가지도록 형성하여 기판상에 코팅함으로써 가스차단막을 제조하면 기체 차단 특성을 향상시킬 수 있고, 보다 상세하게는 코팅되지 않은 기판에 비해 본 발명에 따른 가스차단막은 가스투과도 및 투과계수가 최대 95배 이상 감소하여 기체차단 특성을 향상시킬 수 있다. According to the present invention, by forming a graphene oxide to have a laminated structure that is interlocked with each other in a polyvinyl alcohol polymer binder and coating on a substrate to produce a gas barrier film can improve the gas barrier properties, more specifically uncoated Compared to the substrate, the gas barrier membrane according to the present invention can improve gas barrier properties by reducing gas permeability and transmission coefficient by up to 95 times or more.
도 1은 본 발명의 바람직한 일실시예에 따른 가스차단막의 제조방법을 나타낸 개략도이다.1 is a schematic view showing a method of manufacturing a gas barrier film according to an embodiment of the present invention.
도 2는 본 발명의 실시예 1 및 비교예 2 ~ 3의 FTIR 결과를 나타낸 스펙트럼이다.2 is a spectrum showing the FTIR results of Example 1 and Comparative Examples 2 to 3 of the present invention.
도 3은 본 발명에 따른 실시예 1 및 비교예1 ~ 2의 WAXS 패턴을 나타낸 그래프이다.3 is a graph showing the WAXS pattern of Example 1 and Comparative Examples 1 and 2 according to the present invention.
도 4(a) 및 (b)는 본 발명에 따른 실시예 1 및 실시예 2의 단면을 관찰한 전계방사주사전자현미경 이미지이고, (c) 및 (d)는 본 발명에 따른 실시예 1 및 실시예 2의 표면을 관찰한 전계방사주사전자현미경 이미지이다. Figure 4 (a) and (b) is a field scanning electron microscope image of the cross-sectional view of Example 1 and Example 2 according to the present invention, (c) and (d) is Example 1 and according to the present invention Field emission scanning electron microscope image of the surface of Example 2.
도 5는 비교예 2의 단면을 관찰한 전계방사주사전자현미경 이미지이다.5 is a field emission scanning electron microscope image of a cross section of Comparative Example 2. FIG.
도 6은 비교예 3의 단면을 관찰한 전계방사주사전자현미경 이미지이다.6 is a field emission scanning electron microscope image of a cross section of Comparative Example 3. FIG.
도 7은 실시예 1 및 비교예 2 ~ 3의 코팅막 두께를 나타낸 그래프이다.7 is a graph showing the coating film thickness of Example 1 and Comparative Examples 2 to 3.
도 8은 코팅용액의 양에 따른 코팅막의 질량을 나타낸 그래프이다.8 is a graph showing the mass of the coating film according to the amount of the coating solution.
도 9는 본 발명에 따른 실시예 1 ~ 3 및 비교예 1의 수소가스투과도 및 투과계수를 나타낸 그래프이다.9 is a graph showing the hydrogen gas permeability and transmission coefficient of Examples 1 to 3 and Comparative Example 1 according to the present invention.
그래핀 옥사이드(GO, Graphene oxide) 및 환원된 그래핀 옥사이드(rGO, reduced graphene oxide)는 가스차단특성이 향상된 나노복합체를 제조하기 위한 대량으로 제조될 수 있으나, 환원된 그래핀 옥사이드 시트는 액상 및 대부분의 유기 용매에서 덩어리를 형성하는 특성이 있으므로, 환원된 그래핀 옥사이드 기반의 코팅을 형성시키기 어려운 문제점이 있다. 그러나, 그래핀 옥사이드는 결함이 많기 때문에 환원된 그래핀 옥사이드에 비하여 기체 차단 특성이 적은 문제점이 있으나, 고분자 기판상에 코팅하기에 용이하다. Graphene oxide (GO, Graphene oxide) and reduced graphene oxide (rGO, reduced graphene oxide) (rGO) can be prepared in large quantities for the production of nanocomposites with improved gas barrier properties, the reduced graphene oxide sheet is a liquid and Since there is a property of forming agglomerates in most organic solvents, there is a problem that it is difficult to form a reduced graphene oxide based coating. However, graphene oxide has a problem of less gas barrier properties than reduced graphene oxide because of many defects, but is easy to coat on a polymer substrate.
이에, 본 발명은 그래핀 옥사이드 및 폴리비닐알코올 바인더 수지를 50 ~ 99: 1 ~ 50의 중량비로 포함하는 가스차단막을 제공한다. 상기 가스차단막은 수소 가스 및 산소가스 등을 차단할 수 있고, 상기 가스차단막의 두께가 증가함에 따라 가스차단능이 향상될 수 있어, 기판, 수소저장탱크 등에 적용되어 다양한 목적 및 용도로 사용될 수 있다. 이하, 본 발명을 구성요소별로 보다 상세하게 설명한다. Accordingly, the present invention provides a gas barrier membrane comprising a graphene oxide and a polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50. The gas barrier membrane may block hydrogen gas and oxygen gas, and the gas barrier membrane may be improved as the thickness of the gas barrier membrane increases, and thus the gas barrier membrane may be applied to a substrate, a hydrogen storage tank, and used for various purposes and uses. Hereinafter, the present invention will be described in more detail by component.
본 발명에 따른 가스차단막은 그래핀 옥사이드 및 폴리비닐알코올 바인더 수지를 50 ~ 99: 1 ~ 50의 중량비로 포함한다. 상기 그래핀 옥사이드는 서로 맞물린 층상구조로 형성됨으로써 기체 차단 특성이 향상될 수 있고, 폴리비닐알코올은 바인더 수지 역할을 하기 위하여 첨가된다. The gas barrier membrane according to the present invention includes graphene oxide and polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50. The graphene oxide may be formed in a layered structure interlocked with each other to improve gas barrier properties, and polyvinyl alcohol is added to serve as a binder resin.
이때, 그래핀 옥사이드와 폴리비닐알코올 용액은 50 ~ 99: 1 ~ 50의 중량비로 혼합될 수 있고, 보다 바람직하게는 80 ~ 99: 1 ~ 20의 중량비로 혼합되는 것이 좋다. 상기 그래핀 옥사이드와 폴리비닐알코올 용액이 50:50의 중량비 미만으로 혼합되는 경우 가스차단 특성이 충분히 향상되기 어려운 문제점이 있고, 99:1의 중량비를 초과하여 혼합되는 경우 코팅층을 형성하기 어려운 문제점이 있다. In this case, the graphene oxide and the polyvinyl alcohol solution may be mixed in a weight ratio of 50 to 99: 1 to 50, and more preferably in a weight ratio of 80 to 99: 1 to 20. When the graphene oxide and the polyvinyl alcohol solution are mixed at a weight ratio of less than 50:50, gas barrier properties are difficult to be sufficiently improved, and when mixed at a weight ratio of 99: 1, it is difficult to form a coating layer. have.
이때, 본 발명에 따른 가스차단막의 두께가 0.5 ㎛ ~ 500 ㎛일 때, 수소 가스 투과도가 0.01 ~ 100 cc/m2 atm day일 수 있다. 바람직하게는 코팅막의 두께가 0.5 ㎛ ~ 3 ㎛일 때 수소가스 투과도가 1 ~ 25 cc/m2 atm day일 수 있고, 가스차단막의 두께가 0.5 ㎛ ~ 2 ㎛일 때, 수소 가스투과도가 1 ~ 15 cc/m2 atm day일 수 있으며, 더욱 바람직하게는 코팅막의 두께가 0.5 ㎛ ~ 1 ㎛일 때, 수소 가스 투과도가 1 ~ 10 cc/m2 atm day일 수 있다. At this time, when the thickness of the gas barrier membrane according to the present invention is 0.5 ㎛ ~ 500 ㎛, hydrogen gas permeability may be 0.01 ~ 100 cc / m 2 atm day. Preferably, when the thickness of the coating film is 0.5 μm to 3 μm, the hydrogen gas permeability may be 1 to 25 cc / m 2 atm day, and when the thickness of the gas barrier film is 0.5 μm to 2 μm, the hydrogen gas permeability is 1 to It may be 15 cc / m 2 atm day, more preferably, when the thickness of the coating film is 0.5 ㎛ ~ 1 ㎛, hydrogen gas permeability may be 1 ~ 10 cc / m 2 atm day.
또한, 본 발명에 따른 가스차단막의 두께가 0.5 ㎛ ~ 3 ㎛ 일 때, 수소가스의 투과계수가 0.1 ~ 2.5 cc mm/m2 atm day일 수 있다. 바람직하게는 코팅막의 두께가 0.5 ㎛ ~ 2 ㎛ 일 때, 투과계수가 0.1 ~ 2 cc mm/m2 atm day일 수 있고, 더욱 바람직하게는 가스차단막의 두께가 0.5 ㎛ ~ 1 ㎛ 일 때, 투과계수가 0.1 ~ 1 cc mm/m2 atm day일 수 있다.In addition, when the thickness of the gas barrier membrane according to the present invention is 0.5 ㎛ ~ 3 ㎛, the transmission coefficient of hydrogen gas may be 0.1 ~ 2.5 cc mm / m 2 atm day. Preferably, when the thickness of the coating film is 0.5 ㎛ ~ 2 ㎛, the transmission coefficient may be 0.1 ~ 2 cc mm / m 2 atm day, more preferably, when the thickness of the gas barrier membrane is 0.5 ㎛ ~ 1 ㎛, The modulus may be between 0.1 and 1 cc mm / m 2 atm day.
나아가, 본 발명에 따른 가스차단막은 기판의 두께가 100 ㎛ ~ 120 ㎛이고, 가스차단막의 두께가 0.5 ㎛ ~ 1 ㎛일 때, 산소가스 투과도가 0.1 ~ 1 cc/m2 atm day 이고, 투과계수가 0.01 ~ 0.1 cc mm/m2 atm day 일 수 있다. Furthermore, the gas barrier membrane according to the present invention has an oxygen gas permeability of 0.1 to 1 cc / m 2 atm day and a transmission coefficient when the thickness of the substrate is 100 μm to 120 μm, and the thickness of the gas barrier membrane is 0.5 μm to 1 μm. May be 0.01 to 0.1 cc mm / m 2 atm day.
본 발명에 따른 가스차단막은 하기의 제조방법으로 제조될 수 있다. 본 발명은 그래핀 옥사이드를 물에 녹여 그래핀옥사이드 용액을 제조하는 1단계; 상기 그래핀 옥사이드 용액을 진공여과하여 농도를 증가시키는 2단계; 상기 농도가 증가된 그래핀 옥사이드에 폴리비닐알코올 용액을 혼합하여 혼합용액을 제조하는 3단계; 및 상기 3단계에서 제조된 혼합용액을 기판 상에 도포하여 가스차단막을 제조하는 4단계;를 포함하는 것을 특징으로 하는 가스차단막의 제조방법을 제공함으로써, 서로 맞물린 적층 구조를 갖는 그래핀 옥사이드를 형성하면 기체 차단 특성이 향상된 가스차단막 및 이의 제조방법을 제공한다. 이하, 본 발명을 단계별로 보다 상세하게 설명한다.Gas barrier membrane according to the invention can be prepared by the following manufacturing method. The present invention is a step of preparing a graphene oxide solution by dissolving the graphene oxide in water; Step 2 to increase the concentration by vacuum filtration of the graphene oxide solution; Preparing a mixed solution by mixing the polyvinyl alcohol solution with the graphene oxide having increased concentration; And forming a gas barrier layer by coating the mixed solution prepared in step 3 on the substrate to form a gas barrier layer, thereby forming graphene oxide having a laminated structure interlocked with each other. It provides a gas barrier membrane and a method for manufacturing the same improved gas barrier properties. Hereinafter, the present invention will be described in more detail step by step.
본 발명에 따른 가스차단막의 제조방법에 있어서, 상기 1단계는 그래핀 옥사이드를 물에 녹여 그래핀옥사이드 용액을 제조하는 단계로서, 상기 그래핀 옥사이드 용액은 이때, 상기 1단계의 그래핀 옥사이드 용액의 농도는 0.1 ~ 5 mg/ml일 수 있다. In the method of manufacturing a gas barrier membrane according to the present invention, the first step is to prepare a graphene oxide solution by dissolving the graphene oxide in water, wherein the graphene oxide solution is at this time, the graphene oxide solution of The concentration may be 0.1-5 mg / ml.
또한, 상기 그래핀 옥사이드는 공지된 방법으로서 휴머스 방법(Hummer's method) 또는 수정된 휴머스 방법(modified Hummer's method)을 이용하여 제조할 수 있으나, 이에 특별히 한정되는 것은 아니다. 상기와 같은 방법을 통해 그래핀 옥사이드를 제조하는 경우 산화-환원을 통해 적은 비용으로 대량의 그래핀을 얻을 수 있다. In addition, the graphene oxide may be prepared using a Hummer's method or a modified Hummer's method as a known method, but is not particularly limited thereto. When preparing the graphene oxide through the above method it is possible to obtain a large amount of graphene at a low cost through the oxidation-reduction.
본 발명에 따른 가스차단막의 제조방법에 있어서, 상기 2단계는 상기 그래핀 옥사이드 용액을 진공여과하여 농도를 증가시키는 단계이다. 그래핀 옥사이드는 결함이 많기 때문에 환원된 그래핀 옥사이드에 비하여 기체 차단 특성이 적으나, 고분자 기판상에 코팅하기에 용이한 장점이 있다. 따라서, 상기와 같이 농도가 증가된 그래핀 옥사이드는 용액 내에서 서로 맞물린 층상구조로 형성됨으로써 기체 차단 특성이 향상되어 기체 차단 특성이 우수한 가스차단막을 제조할 수 있다.In the method of manufacturing a gas barrier film according to the present invention, the second step is to increase the concentration by vacuum filtration of the graphene oxide solution. Graphene oxide has fewer gas barrier properties than reduced graphene oxide because of many defects, but has an advantage of easy coating on a polymer substrate. Therefore, the graphene oxide with the increased concentration as described above is formed in a layered structure interlocked with each other in the solution to improve the gas barrier properties can be produced a gas barrier film excellent in gas barrier properties.
이때, 상기 2단계에서 그래핀 옥사이드를 진공여과하여 농도를 1.5 ~ 20 배 증가시키는 것이 좋고, 바람직하게는 5 ~ 10배 증가시키는 것이 좋고, 더욱 바람직하게는 8 ~ 10배 증가시키는 것이 좋다. 농도가 1.5배 미만으로 증가되는 경우, 층상구조를 형성하기 어려운 문제점이 있고, 농도가 20배를 초과하여 증가되는 경우 그래핀 옥사이드가 뭉쳐서 덩어리를 형성할 수 있고, 용액이 아닌 겔 상태가 되는 문제점이 있다. At this time, it is preferable to increase the concentration of 1.5 to 20 times by vacuum filtration of graphene oxide in the second step, preferably 5 to 10 times, and more preferably 8 to 10 times. When the concentration is increased to less than 1.5 times, there is a problem that it is difficult to form a layered structure, when the concentration is increased by more than 20 times, graphene oxide may aggregate to form agglomeration, and become a gel state rather than a solution. There is this.
본 발명에 따른 가스차단막의 제조방법에 있어서, 상기 3단계는 상기 농도가 증가된 그래핀 옥사이드에 폴리비닐알코올 용액을 혼합하여 혼합용액을 제조하는 단계로서, 상기 폴리비닐알코올 용액은 그래핀 옥사이드를 고정하기 위한 바인더의 역할을 할 수 있다. In the method of manufacturing a gas barrier membrane according to the present invention, the third step is to prepare a mixed solution by mixing the polyvinyl alcohol solution to the graphene oxide having increased concentration, the polyvinyl alcohol solution is a graphene oxide It can serve as a binder for fixing.
이때, 상기 3단계에서 그래핀 옥사이드와 폴리비닐알코올 용액은 50 ~ 99 : 1 ~ 50의 중량비로 혼합될 수 있고, 보다 바람직하게는 80 ~ 99 : 1 ~ 20의 중량비로 혼합되는 것이 좋다. 상기 그래핀 옥사이드와 폴리비닐알코올 용액이 50:50의 중량비 미만으로 혼합되는 경우 가스차단 특성이 충분히 향상되기 어려운 문제점이 있고, 99:1의 중량비를 초과하여 혼합되는 경우 코팅층을 형성하기 어려운 문제점이 있다. At this time, the graphene oxide and the polyvinyl alcohol solution in the third step may be mixed in a weight ratio of 50 to 99: 1 to 50, more preferably 80 to 99: 1 to 20 by weight ratio. When the graphene oxide and the polyvinyl alcohol solution are mixed at a weight ratio of less than 50:50, gas barrier properties are difficult to be sufficiently improved, and when mixed at a weight ratio of 99: 1, it is difficult to form a coating layer. have.
본 발명에 따른 가스차단막의 제조방법에 있어서, 상기 4단계는 상기 3단계에서 제조된 혼합용액을 도포하여 가스차단막을 제조하는 단계로서, 상기 3단계에서 제조된 혼합용액은 기판 또는 수소저장용 탱크 등의 표면에 도포되어 코팅막을 형성함으로써 가스 차단 특성을 향상시킬 수 있다. In the method of manufacturing a gas barrier membrane according to the present invention, the fourth step is to prepare a gas barrier membrane by applying the mixed solution prepared in step 3, wherein the mixed solution prepared in step 3 is a substrate or a tank for storing hydrogen It is possible to improve the gas barrier properties by applying to the surface, such as to form a coating film.
이때, 상기 기판은 상용의 고분자 기판이라면 어느 것이든 사용 가능하고 특별히 한정되지 않으나, 바람직하게는 폴리에틸렌 기판, 폴리프로필렌, 폴리에틸렌 테레프탈레이트, 폴리에틸렌 테레프탈레이트 글리콜, 폴리카르보네이트, 폴리스티렌, 폴리아미드, 폴리부틸렌 테레프탈레이트, 폴리메틸 펜텐, 폴리비닐 클로라이드, 나일론 및 이들의 공중합체로 이루어진 군으로부터 선택되는 1종 이상의 기판을 포함할 수 있고, 더욱 바람직하게는 폴리에틸렌 기판, 폴리프로필렌, 폴리에틸렌 테레프탈레이트, 나일론 및 이들의 공중합체로 이루어진 군으로부터 선택되는 1종 이상의 기판을 포함할 수 있다. In this case, the substrate may be any commercially available polymer substrate, and is not particularly limited. Preferably, the substrate is a polyethylene substrate, polypropylene, polyethylene terephthalate, polyethylene terephthalate glycol, polycarbonate, polystyrene, polyamide, poly It may include at least one substrate selected from the group consisting of butylene terephthalate, polymethyl pentene, polyvinyl chloride, nylon and copolymers thereof, more preferably polyethylene substrate, polypropylene, polyethylene terephthalate, nylon And one or more substrates selected from the group consisting of copolymers thereof.
이때, 상기 코팅막은 도포할 혼합 용액의 용량을 조절하여 코팅막의 두께를 제어할 수 있고, 단위 면적당(cm2) 0.5 ~ 3 ml를 도포하는 것이 바람직하며, 더욱 바람직하게는 단위 면적당(cm2) 1.5~ 3 ml를 도포하는 것이 좋다. 상기와 같이 도포되는 경우 0.5 ㎛ ~ 3 ㎛ 두께의 코팅막이 제조될 수 있다. At this time, the coating film may control the thickness of the coating film by adjusting the volume of the mixed solution to be applied, it is preferable to apply 0.5 ~ 3 ml per unit area (cm 2 ), more preferably per unit area (cm 2 ) It is recommended to apply 1.5 to 3 ml. When applied as described above may be prepared a coating film of 0.5 ㎛ ~ 3 ㎛ thick.
또한, 상기 4단계에서 혼합용액은 기판에 도포하기 위한 상용의 방법이라면 어느 방법이든 사용 가능하고, 바람직하게는 스핀 코팅법, 스프레이 코팅법 및 딥 코팅법으로 이루어진 군으로부터 선택되는 1종의 방법을 이용하여 도포할 수 있고, 더욱 바람직하게는 스핀 코팅법을 사용하는 것이 좋다.In addition, the mixed solution in the step 4 may be used any method as long as it is a commercial method for applying to the substrate, preferably one method selected from the group consisting of spin coating method, spray coating method and dip coating method It can apply | coat and use, It is good to use a spin coating method more preferably.
이하, 본 발명을 하기 실시예들을 통해 보다 상세하게 설명한다. 이때, 하기 실시예들은 본 발명을 보다 상세하게 설명하기 위해 예시적으로 제시된 것일 뿐, 본 발명의 권리범위가 하기 실시예들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. At this time, the following examples are merely presented to illustrate the present invention in more detail, the scope of the present invention is not limited by the following examples.
[[ 실시예Example ]]
실시예Example 1.  One. 가스차단막의Gas barrier 제조 1 Manufacture 1
수정된 휴머스 방법을 이용하여 그래핀 옥사이드를 제조하였다. 1 mg/mL 농도의 그래핀 옥사이드 100 mL를 진공여과장치를 이용하여 8 mg/ml 농도로 농축하였다. 상기 농축된 그래핀 옥사이드 용액에 폴리비닐알코올(PVA, sigma aldrich) 용액을 8:2의 중량비로 혼합하여 GO/PVA 혼합 용액을 제조하였다. Graphene oxide was prepared using a modified human method. 100 mL of graphene oxide at a concentration of 1 mg / mL was concentrated to 8 mg / ml using a vacuum filter. A polyvinyl alcohol (PVA, sigma aldrich) solution was mixed with the concentrated graphene oxide solution at a weight ratio of 8: 2 to prepare a GO / PVA mixed solution.
110 ㎛ 두께의 폴리에틸렌테레프탈레이트(PET)기판의 상부 일면을 플라즈마 처리한 후, 상기 GO/PVA 혼합용액 3 ml를 스핀코팅법으로 도포하여 0.82 ㎛의 코팅막을 형성하여 가스차단막을 제조하였다. After plasma treatment of an upper surface of a polyethylene terephthalate (PET) substrate having a thickness of 110 μm, 3 ml of the GO / PVA mixed solution was applied by spin coating to form a coating film having a thickness of 0.82 μm to prepare a gas barrier film.
실시예Example 2.  2. 가스차단막의 Gas barrier 제조 2 Manufacture 2
GO/PVA 혼합용액 6 ml를 기판상에 도포하여 1.56 ㎛ 두께의 코팅막을 형성한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 가스차단막을 제조하였다. A gas barrier film was prepared in the same manner as in Example 1, except that 6 ml of the GO / PVA mixed solution was coated on a substrate to form a coating film having a thickness of 1.56 μm.
실시예Example 3.  3. 가스차단막의 Gas barrier 제조 3 Manufacture 3
GO/PVA 혼합용액 9 ml를 기판상에 도포하여 2.56 ㎛ 두께의 코팅막을 형성한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 가스차단막을 제조하였다. A gas barrier film was prepared in the same manner as in Example 1 except that 9 ml of the GO / PVA mixed solution was coated on a substrate to form a coating film having a thickness of 2.56 μm.
비교예Comparative example 1.  One. 가스차단막의Gas barrier 제조  Produce
110 ㎛ 두께의 폴리에틸렌테레프탈레이트(PET)기판을 가스차단막으로 이용하였다. A polyethylene terephthalate (PET) substrate having a thickness of 110 μm was used as the gas barrier membrane.
비교예Comparative example 2.  2. 가스차단막의Gas barrier 제조  Produce
110 ㎛의 폴리에틸렌테레프탈레이트(PET)기판의 상부 일면을 플라즈마 처리한 후, 8 mg/ml 농도로 농축된 그래핀 옥사이드(GO)을 스핀코팅법으로 도포한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 가스차단막을 제조하였다. Plasma treatment of the upper surface of the polyethylene terephthalate (PET) substrate of 110 ㎛, the same as in Example 1 except that the coating of the graphene oxide (GO) concentrated at a concentration of 8 mg / ml by spin coating The gas barrier membrane was manufactured by the method.
비교예Comparative example 3.  3. 가스차단막의Gas barrier 제조  Produce
110 ㎛의 폴리에틸렌테레프탈레이트(PET)기판의 상부 일면을 플라즈마 처리한 후, PVA를 스핀코팅법으로 도포한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 가스차단막을 제조하였다. After the plasma treatment of the upper surface of the polyethylene terephthalate (PET) substrate of 110 ㎛, a gas barrier film was prepared in the same manner as in Example 1 except that the PVA was applied by a spin coating method.
실험예Experimental Example 1.  One. 그래핀Graphene 옥사이드Oxide 및  And PVAPVA 사이의 상호작용 관찰 The interaction between
본 발명에 따라 제조된 실시예 1 및 비교예 2 ~ 비교예 3을 FTIR(Fourier transform infrared spectroscopy)로 그래핀 사이드 및 폴리비닐알코올 간의 상호결합을 측정하였고, 그 결과를 도 2에 나타내었다. Example 1 and Comparative Examples 2 to 3 prepared according to the present invention was measured by Fourier transform infrared spectroscopy (FTIR) to measure the interaction between the graphene side and polyvinyl alcohol, the results are shown in FIG.
도 2에 나타낸 바와 같이, PVA는 3445 cm-1에서 넓은 피크를 가지고, 이는 H-기와 결합한 -OH 기의 분자간 상호작용에 의해 나타나며, 반면 동일한 결합에 대해서 그래핀 옥사이드에서는 3410 cm-1에서 피크가 나타난다. 또한, GO/PVA 나노복합체는 GO 및 PVA 각각의 피크에서와는 달리 3432 cm-1에서 피크를 가지고, 피크의 폭도 상대적으로 좁은 것을 확인할 수 있다. 또한, -C=O 결합에 대해서, PVA는 1730 cm-1에서 수화되지 않은 에스테르기에 대하여 피크를 가지고, GO는 COOH 기에 대해서 1718 cm-1에서 피크를 가진다. 한편, GO/PVA 나노복합체는 1724 cm-1에서 피크를 가지는 것을 확인할 수 있다. 이를 통해, GO/PVA 나노복합체의 경우, GO 시트 또는 PVA 체인 사이의 분자간 H-결합은 사라지고 GO 및 PVA 분자 내에 새로운 결합이 형성되는 것을 알 수 있다. As shown in FIG. 2, the PVA has a broad peak at 3445 cm −1 , which is manifested by the intermolecular interaction of the —OH group bound to the H-group, while the peak at 3410 cm −1 for graphene oxide for the same bond Appears. In addition, the GO / PVA nanocomposite has a peak at 3432 cm −1 , unlike the peaks of GO and PVA, respectively, and the width of the peak is also relatively narrow. Also, for -C = O bonds, PVA has a peak for unhydrated ester groups at 1730 cm -1 , and GO has a peak at 1718 cm -1 for COOH groups. On the other hand, GO / PVA nanocomposites can be seen that has a peak at 1724 cm -1 . Through this, in the case of the GO / PVA nanocomposite, it can be seen that the intermolecular H-bonds between the GO sheet or PVA chain disappears and new bonds are formed in the GO and PVA molecules.
또한, GO는 산화되지 않은 그래파이트 또는 삽입된 물분자에 대해서 1622 cm-1에서 피크를 가지고, 이는 GO/PVA 복합체에서 1634 cm-1로 이동하였다. 이를 통해, GO/PVA 나노복합체의 경우, GO 시트 또는 PVA 체인 사이의 분자간 결합은 사라지고 GO 및 PVA 분자 내에 새로운 결합이 형성되는 것을 알 수 있다. In addition, GO had a peak at 1622 cm −1 for unoxidized graphite or inserted water molecules, which shifted to 1634 cm −1 in the GO / PVA complex. Through this, in the case of the GO / PVA nanocomposite, it can be seen that the intermolecular bonds between the GO sheet or the PVA chain disappears and new bonds are formed in the GO and PVA molecules.
실험예Experimental Example 2. GO/ 2. GO / PVAPVA 가스차단막의Gas barrier 결합구조 관찰 Binding structure observation
본 발명에 따른 GO/PVA 나노복합체의 결합구조를 조사하기 위하여, 실시예 1, 비교예 2 ~3의 시료를 WAXS(wide angle X-ray scattering)을 수행하였고, 그 결과를 도 3에 나타내었다. In order to investigate the binding structure of the GO / PVA nanocomposite according to the present invention, samples of Example 1 and Comparative Examples 2 to 3 were subjected to wide angle X-ray scattering (WAXS), and the results are shown in FIG. 3. .
GO 시트는 고인접한 두개의 층 간에 공간을 가지며, 고도로 정렬된 구조를 나타내는 것으로 알려진다. GO sheets are known to exhibit a highly ordered structure with a space between two layers that are highly adjacent.
GO 시트는 2θ=10°에서 뾰족한 피크를 가지는 것을 확인할 수 있고, 이를 통해 GO 시트가 서로 인접한 층상구조를 가지는 것을 알 수 있다. 또한, PVA는 피크를 가지지 않으며, GO/PVA 복합체는 2θ=8.58°에서 피크를 가지는 것을 확인할 수 있었다. It can be seen that the GO sheet has a sharp peak at 2θ = 10 °, and through this, it can be seen that the GO sheet has a layered structure adjacent to each other. In addition, PVA did not have a peak, it was confirmed that the GO / PVA complex has a peak at 2θ = 8.58 °.
GO/PVA 복합체는 GO 시트 단독으로 측정하였을 경우에 비해 회절 피크가 낮은 앵글로 이동하는 것을 확인할 수 있고, GO 시트 사이의 공간으로 PVA가 도입되어 GO 시트 사이의 공간이 확장되기 때문인 것으로 유추할 수 있다. The GO / PVA composite can be seen that the diffraction peak shifts to a lower angle than when measured by the GO sheet alone, and it can be inferred that the space between the GO sheets is expanded by introducing PVA into the space between the GO sheets. have.
실험예Experimental Example 3. GO/ 3. GO / PVAPVA 가스차단막의Gas barrier 미세구조 관찰 Microstructure Observation
본 발명에 따른 GO/PVA 나노복합체의 미세구조를 조사하기 위하여, 실시예 1 ~ 3의 시료를 전계방사주사전자현미경(FESEM, field emission scanning electron microscopy)을 이용하여 관찰하였고, 그 결과를 도 4 ~ 8에 나타내었다. In order to investigate the microstructure of the GO / PVA nanocomposite according to the present invention, the samples of Examples 1 to 3 were observed by using a field emission scanning electron microscopy (FESEM), and the results are shown in FIG. 4. ~ 8 is shown.
도 4(a) 및 4(b)에 나타낸 바와 같이, 실시예 1 및 실시예 2의 GO/PVA 코팅막 층이 균일한 두께로 형성된 것을 확인할 수 있고, 코팅막의 두께가 코팅 용액의 양에 따라 비례하여 증가하는 것을 확인할 수 있다. As shown in Figure 4 (a) and 4 (b), it can be seen that the GO / PVA coating film layer of Example 1 and Example 2 is formed in a uniform thickness, the thickness of the coating film is proportional to the amount of the coating solution You can see the increase.
또한, 도 5 ~ 7에 나타낸 바와 같이, 비교예 2 ~ 3은 실시예 1에 비해 얇은 두께로 코팅막이 형성되는 것을 확인할 수 있었다. 이는, PVA의 밀도는 GO에 비해 작기 때문에 PVA가 GO로 침투하게 되므로, GO만을 코팅한 비교예 2에 비해 PVA만을 코팅한 비교예3의 경우 상대적으로 얇은 두께로 코팅막이 형성되기 때문이다. In addition, as shown in Figures 5 to 7, Comparative Examples 2 to 3 it was confirmed that the coating film is formed in a thin thickness compared to Example 1. This is because the density of the PVA is smaller than the GO, so that the PVA penetrates into the GO, and therefore, in Comparative Example 3 in which only the PVA is coated, the coating film is formed in a relatively thin thickness compared to Comparative Example 2 in which only the GO is coated.
또한, 도 8에 나타낸 바와 같이, 코팅막의 질량도 코팅용액의 양에 따라 비례하여 증가하는 것을 확인할 수 있다. In addition, as shown in Figure 8, it can be seen that the mass of the coating film also increases in proportion to the amount of the coating solution.
실험예Experimental Example 4.  4. 가스차단막의Gas barrier 가스차단능Gas barrier ability 측정 Measure
본 발명에 따른 GO/PVA 나노복합체의 가스차단능에 대하여 알아보기 위하여, 본 발명에 따른 실시예 1 ~ 3 및 비교예 1 ~ 3의 수소투과율 및 투과계수를 25℃, 100 kPa에서 측정하였고, 그 결과를 하기 표 1 및 도 9에 나타내었다. 또한, 본 발명에 따른 실시예 1 및 비교예 1의 산소투과율 및 투과계수를 측정하였고, 그 결과를 하기 표 2에 나타내었다. In order to investigate the gas barrier ability of the GO / PVA nanocomposite according to the present invention, the hydrogen permeability and the coefficient of permeability of Examples 1 to 3 and Comparative Examples 1 to 3 were measured at 25 ° C. and 100 kPa. The results are shown in Table 1 and FIG. 9. In addition, the oxygen transmission rate and transmission coefficient of Example 1 and Comparative Example 1 according to the present invention were measured, and the results are shown in Table 2 below.
구분division 코팅막 두께(㎛)Coating film thickness (㎛) 가스차단막 두께(㎛)Gas barrier film thickness (㎛) 수소투과율(cc/m2 atm day)Hydrogen transmittance (cc / m 2 atm day) 투과계수(cc.mm./m2 atm day)Transmission coefficient (cc.mm./m 2 atm day)
실시예 1Example 1 0.820.82 110.82110.82 2121 2.322.32
실시예 2Example 2 1.561.56 111.56111.56 1414 1.561.56
실시예 3Example 3 2.562.56 112.56112.56 55 0.560.56
비교예 1Comparative Example 1 -- 110110 122122 13.4213.42
비교예 2Comparative Example 2 0.520.52 110.52110.52 6969 7.627.62
비교예 3Comparative Example 3 0.2800.280 110.28110.28 110110 12.4012.40
구분division 코팅막 두께(㎛)Coating film thickness (㎛) 가스차단막 두께(㎛)Gas barrier film thickness (㎛) 산소투과율(cc/m2 atm day)Oxygen transmittance (cc / m 2 atm day) 투과계수(cc.mm./m2 atm day)Transmission coefficient (cc.mm./m 2 atm day)
실시예 1Example 1 0.820.82 110.82110.82 0.780.78 0.0860.086
비교예 1Comparative Example 1 -- 110110 21.221.2 2.232.23
표 1 및 도 4에 따르면, 기판의 두께가 100 ㎛ ~ 120 ㎛이고, 가스차단막의 두께가 0.5 ㎛ ~ 3 ㎛일 때, 수소가스투과도가 1 ~ 25 cc/m2 atm day 이고, 투과계수가 0.1 ~ 2.5 cc mm/m2 atm day인 것을 확인할 수 있다. According to Table 1 and FIG. 4, when the substrate thickness is 100 μm to 120 μm, the gas barrier film is 0.5 μm to 3 μm, the hydrogen gas permeability is 1 to 25 cc / m 2 atm day, and the transmission coefficient is It can be seen that 0.1 ~ 2.5 cc mm / m 2 atm day.
이때, 상기 가스차단막의 두께는 0.5 ~ 3 ㎛일 수 있고, 바람직하게는 1 ~ 3 ㎛ 일 수 있고, 더욱 바람직하게는 2 ~ 3 ㎛인 것이 좋다. 상기 코팅막의 두께에 따라 수소투과율 및 투과계수가 감소하는 것을 확인할 수 있다. 상기 코팅막의 두께가 2.56 ㎛인 경우, 코팅막이 없는 비교예 1에 비해 96%까지 수소투과율이 감소하는 것을 확인할 수 있었고, 투과계수도 95%까지 감소하는 것을 확인할 수 있었다. In this case, the thickness of the gas barrier membrane may be 0.5 to 3 ㎛, preferably 1 to 3 ㎛, more preferably 2 to 3 ㎛. It can be seen that the hydrogen permeability and the coefficient of permeability decrease according to the thickness of the coating film. When the thickness of the coating film is 2.56 ㎛, it was confirmed that the hydrogen transmittance is reduced by 96% compared to Comparative Example 1 without the coating film, it was confirmed that the transmission coefficient is also reduced to 95%.
또한, 표 2에 따르면, 기판의 두께가 100 ㎛ ~ 120 ㎛이고, 코팅막의 두께가 0.5 ㎛ ~ 1 ㎛일 때, 산소가스투과도가 0.1 ~ 1 cc/m2 atm day 이고, 투과계수가 0.01 ~ 0.1 cc mm/m2 atm day인 것을 확인할 수 있어, 코팅막이 형성되지 않은 비교예 1보다 산소차단능이 현저히 우수한 것을 확인할 수 있다.In addition, according to Table 2, when the thickness of the substrate is 100 ㎛ ~ 120 ㎛, the thickness of the coating film is 0.5 ㎛ ~ 1 ㎛, the oxygen gas permeability is 0.1 ~ 1 cc / m 2 atm day, the transmission coefficient is 0.01 ~ 0.1 cc mm / m 2 atm day can be confirmed, it can be seen that the oxygen blocking ability is significantly superior to Comparative Example 1, the coating film is not formed.
따라서, 본 발명에 따른 가스차단막은 수소가스 및 산소가스 차단능이 현저히 우수한 것을 확인할 수 있었다. Therefore, the gas barrier membrane according to the present invention was confirmed that the hydrogen gas and oxygen gas blocking ability is remarkably excellent.

Claims (6)

  1. 그래핀 옥사이드(Graphene oxide) 및 폴리비닐알코올 바인더 수지를 50 ~ 99: 1 ~ 50의 중량비로 포함하는 가스차단막.Graphene oxide (Graphene oxide) and a polyvinyl alcohol binder resin 50 to 99: a gas barrier film comprising a weight ratio of 1 to 50.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 가스차단막의 두께가 0.5 ㎛ ~ 500 ㎛일 때, 수소가스 투과도가 0.01 ~ 100 cc/m2 atm day인 것을 특징으로 하는 가스차단막.When the thickness of the gas barrier membrane is 0.5 ㎛ ~ 500 ㎛, the gas barrier membrane, characterized in that the hydrogen gas permeability is 0.01 ~ 100 cc / m 2 atm day.
  3. 그래핀 옥사이드를 물에 녹여 그래핀옥사이드 용액을 제조하는 1단계;Dissolving graphene oxide in water to prepare a graphene oxide solution;
    상기 그래핀 옥사이드 용액을 진공여과하여 농도를 증가시키는 2단계;Step 2 to increase the concentration by vacuum filtration of the graphene oxide solution;
    상기 농도가 증가된 그래핀 옥사이드에 폴리비닐알코올 용액을 혼합하여 혼합용액을 제조하는 3단계; 및Preparing a mixed solution by mixing the polyvinyl alcohol solution with the graphene oxide having increased concentration; And
    상기 3단계에서 제조된 혼합용액을 도포하여 가스차단막을 제조하는 4단계;를 포함하는 것을 특징으로 하는 가스차단막의 제조방법.And applying a mixed solution prepared in step 3 to produce a gas barrier membrane. 4.
  4. 제3항에 있어서,The method of claim 3,
    상기 1단계의 그래핀 옥사이드 용액의 농도는 0.1 ~ 5 mg/ml이고, 상기 2단계에서 그래핀 옥사이드를 진공여과하여 농도를 1.5 ~ 20 배 증가시키는 것을 특징으로 하는 가스차단막의 제조방법.The concentration of the graphene oxide solution of the first step is 0.1 ~ 5 mg / ml, the method of producing a gas barrier membrane, characterized in that to increase the concentration by 1.5 to 20 times by vacuum filtration of graphene oxide in the second step.
  5. 제3항에 있어서,The method of claim 3,
    상기 3단계에서 그래핀 옥사이드와 폴리비닐알코올 용액은 50 ~ 99: 1 ~ 50의 중량비로 혼합되는 것을 특징으로 하는 가스차단막의 제조방법.Graphene oxide and the polyvinyl alcohol solution in the third step is a method of producing a gas barrier membrane, characterized in that mixed in a weight ratio of 50 ~ 99: 1 ~ 50.
  6. 제3항에 있어서,The method of claim 3,
    상기 4단계에서 혼합용액을 스핀 코팅법, 스프레이 코팅법 및 딥 코팅법으로 이루어진 군으로부터 선택되는 1종의 방법을 이용하여 도포하는 것을 특징으로 하는 가스차단막의 제조방법.Method for producing a gas barrier membrane, characterized in that for applying the mixed solution in one of the four steps selected from the group consisting of spin coating method, spray coating method and dip coating method.
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