WO2015133849A1 - Membrane nanocomposite d'oxyde de graphène présentant des caractéristiques de barrière contre les gaz améliorées et son procédé de fabrication - Google Patents

Membrane nanocomposite d'oxyde de graphène présentant des caractéristiques de barrière contre les gaz améliorées et son procédé de fabrication Download PDF

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WO2015133849A1
WO2015133849A1 PCT/KR2015/002156 KR2015002156W WO2015133849A1 WO 2015133849 A1 WO2015133849 A1 WO 2015133849A1 KR 2015002156 W KR2015002156 W KR 2015002156W WO 2015133849 A1 WO2015133849 A1 WO 2015133849A1
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graphene oxide
group
gas barrier
oxide nanocomposite
nanocomposite membrane
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PCT/KR2015/002156
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English (en)
Korean (ko)
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박호범
김효원
유병민
장승진
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한양대학교 산학협력단
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Priority claimed from KR1020150031035A external-priority patent/KR101972439B1/ko
Application filed by 한양대학교 산학협력단 filed Critical 한양대학교 산학협력단
Priority to US15/123,967 priority Critical patent/US20170015483A1/en
Priority to CN201580012597.4A priority patent/CN106061593B/zh
Publication of WO2015133849A1 publication Critical patent/WO2015133849A1/fr

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    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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Definitions

  • the present invention relates to a graphene oxide nanocomposite membrane having improved gas barrier properties and a method for manufacturing the same, and more particularly, graphene oxide coated with graphene oxide having a size of 3 ⁇ m to 50 ⁇ m on a variety of supports with a thickness of 10 nm or more.
  • the present invention relates to a technology capable of being applied to display devices, food and pharmaceutical packaging, etc. with excellent gas barrier properties.
  • Graphene is a material composed of a single layer of hexagonal honeycomb carbon atoms, which is very interesting and has excellent physicochemical properties due to its structural specificity of two-dimensional nanoplatelet structure. I became one. That is, it is the thinnest material in the world, but it has mechanical properties that are 200 times stronger than steel, 100 times more current transmission than copper, and 100 times faster electron transfer speed than silicon. In particular, despite being a single atom layer, it is known that gas and ion molecule blocking properties are excellent with high mechanical strength.
  • the excellent gas and ion molecule blocking characteristics of graphene are realized only in the defect-free graphene structure.
  • the gas and ion molecules easily penetrate into the graphene defects, thereby preventing the characteristic. Since the characteristics are lost, when graphene is formed into a thin film, it is difficult to maintain the blocking characteristics of gas and ion molecules.
  • gas diffusion barriers comprising a polymeric matrix and functionalized graphene having a surface density of 300-2,600 m 2 / g and a bulk density of 40-0.1 kg / m 3.
  • the surface area and bulk density of functionalized graphene are also known.
  • the technical features of the control are thick films in which the functionalized graphene is dispersed in the polymer matrix, and thus the gas barrier properties in the case of thin films are difficult to predict and the results are proved by quantitative data on the gas barrier properties. There is no mention in particular about the effect which becomes (patent document 3).
  • Non-Patent Document 1 graphene / polyurethane nanocomposites containing graphite oxide as a nanofiller in thermoplastic polyurethanes by melt mixing, solution blending, or co-polymerization have also been known. Although the barrier properties of nitrogen gas according to the amount of graphene contained are revealed, the barrier properties of various gases according to the size of the graphene oxide and the thickness of the graphene oxide film are not known (Non-Patent Document 1).
  • Patent Document 1 Korean Patent Publication No. 10-2014-0015926
  • Patent Document 2 Korea Patent Publication No. 10-2013-0001705
  • Patent Documents 3. US published patent US 2010/0096595
  • Non-Patent Document 1 Hyunwoo Kim et al., Chem. Mater. 22 , 3441-3450 (2010)
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a simple structure in which graphene oxide having a controlled size is coated with a nano-thick thin film, or graphene oxide is inserted into a polymer. It is to provide a graphene oxide nanocomposite membrane having excellent barrier properties of various gases and a method of manufacturing the same.
  • the present invention for achieving the above object is a support; And a coating layer having nanopores coated with a graphene oxide having a size of 3 ⁇ m to 50 ⁇ m on a thickness of 10 nm or more on the support.
  • the support is characterized in that any one selected from the group consisting of polymers, ceramics, glass, paper, and metal layers.
  • the polymer may be polyester, polyolefin, polyvinyl chloride, polyurethane, polyacrylate, polycarbonate, polytetrafluoroethylene, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polyacrylonitrile, It is characterized by any one selected from the group consisting of cellulose acetate, cellulose triacetate, and polyvinylidene fluoride.
  • the ceramic is characterized in that any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride.
  • the metal layer is characterized in that the metal foil, a metal sheet or a metal film.
  • the material of the metal layer is characterized in that any one selected from the group consisting of copper, nickel, iron, aluminum, and titanium.
  • the graphene oxide is a functionalized graphene oxide characterized in that the hydroxyl group, carboxyl group, carbonyl group, or epoxy group present in the graphene oxide is converted to ester group, ether group, amide group, or amino group.
  • the nanopores are characterized in that the average diameter ranges from 0.5 nm to 1.0 nm.
  • the coating layer is characterized in that it comprises a single layer or a plurality of graphene oxide.
  • Graphene oxide of the single layer is characterized in that the thickness of 0.6 nm ⁇ 1 nm range.
  • the present invention also provides a gas barrier graphene oxide nanocomposite membrane having a structure in which graphene oxide is inserted into a polyethylene glycol diacrylate or polyethylene glycol dimethacrylate polymer.
  • the graphene oxide is characterized in that the size of 100 ⁇ 1000 nm.
  • the content of graphene oxide in the nanocomposite film is characterized in that less than 5% by weight.
  • the present invention provides a display device including the gas barrier graphene oxide nanocomposite membrane.
  • the present invention provides a food wrapper comprising the gas barrier graphene oxide nanocomposite membrane.
  • the present invention provides a pharmaceutical package containing the gas barrier graphene oxide nanocomposite membrane.
  • the present invention comprises the steps of i) dispersing the graphene oxide in distilled water and treating with an ultrasonic mill for 0.1 to 6 hours to obtain a graphene oxide dispersion solution; ii) centrifuging the dispersion solution to form graphene oxide having a size adjusted to 3 ⁇ m ⁇ 50 ⁇ m; iii) obtaining a solution in which the graphene oxide formed in step ii) is dispersed in distilled water again; And iv) coating the dispersion solution of step iii) on a support to form a coating layer having nanopores.
  • the method of manufacturing a gas barrier graphene oxide nanocomposite membrane comprising the same.
  • the graphene oxide is a functionalized graphene oxide characterized in that the hydroxyl group, carboxyl group, carbonyl group, or epoxy group present in the graphene oxide is converted to ester group, ether group, amide group, or amino group.
  • the support is characterized in that any one selected from the group consisting of polymers, ceramics, glass, paper, and metal layers.
  • the polymer may be polyester, polyolefin, polyvinyl chloride, polyurethane, polyacrylate, polycarbonate, polytetrafluoroethylene, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polyacrylonitrile, It is characterized by any one selected from the group consisting of cellulose acetate, cellulose triacetate, and polyvinylidene fluoride.
  • the ceramic is characterized in that any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride.
  • the metal layer is characterized in that the metal foil, a metal sheet or a metal film.
  • the material of the metal layer is characterized in that any one selected from the group consisting of copper, nickel, iron, aluminum, and titanium.
  • the coating is characterized in that it is carried out by any one method selected from the group consisting of a direct evaporation method, a transfer method, a spin coating method, and a spray coating method.
  • the spin coating is characterized in that it is performed 3 to 10 times.
  • the nanopores are characterized in that the average diameter ranges from 0.5 nm to 1.0 nm.
  • the coating layer is characterized in that it comprises a single layer or a plurality of graphene oxide.
  • Graphene oxide of the single layer is characterized in that the thickness of 0.6 nm ⁇ 1 nm range.
  • graphene oxide having a size of 3 ⁇ m to 50 ⁇ m is coated with a thin film of nano-thickness on various supports, or graphene oxide is inserted into a polymer. Even with a simple structure, it is excellent in blocking properties of various gases, and thus can be applied to display devices, food and pharmaceutical packaging.
  • 1 is a structure of graphene oxide and functionalized graphene oxide.
  • FIG. 2 is a transmission electron microscope (TEM) photograph of graphene oxide scaled according to Example 1.
  • FIG. 2 is a transmission electron microscope (TEM) photograph of graphene oxide scaled according to Example 1.
  • Figure 3 is a photograph taken of the graphene oxide nanocomposite membrane prepared from Example 1.
  • Figure 4 is a transmission electron microscope (TEM) photograph taken a cross section of the graphene oxide film coated on a polymer support (PES) according to Example 1.
  • TEM transmission electron microscope
  • Figure 5 is a photograph of the graphene oxide nanocomposite according to the content of the graphene oxide prepared from Example 2 (graphene oxide size: 270 nm)
  • FIG. 6 is a scanning electron microscope (SEM) photograph (graphene oxide size: 270 nm) of graphene oxide nanocomposites according to the amount of graphene oxide prepared from Example 2.
  • SEM scanning electron microscope
  • Figure 7 is a photograph of the graphene oxide nanocomposite film according to the size of the graphene oxide prepared from Example 2 (graphene oxide content: 4% by weight)
  • Figure 9 is a graph showing the gas barrier properties and gas permeable pressure of the ultra-thin graphene oxide film according to the size of graphene oxide.
  • SEM 10 is a scanning electron microscope (SEM) photograph of a graphene oxide film having a thickness of about 5 ⁇ m prepared using a conventional vacuum filtration method.
  • FIG. 11 is a graph showing various gas barrier properties according to graphene oxide size of a graphene oxide film prepared using a conventional vacuum filtration method.
  • FIG. 13 is a graph of oxygen permeability of graphene oxide nanocomposites according to the amount of graphene oxide prepared from Example 2 (graphene oxide size: 270 nm).
  • the support may perform a function of a reinforcing material for supporting the coating layer, and various materials contacting the coating layer are possible, and the support may be any one selected from the group consisting of polymer, ceramic, glass, paper, and metal layers. have.
  • the polymer polyester, polyolefin, polyvinyl chloride, polyurethane, polyacrylate, polycarbonate, polytetrafluoroethylene, polysulfone, polyether sulfone, polyimide, polyetherimide, polyamide, polyacrylonitrile
  • Any one selected from the group consisting of cellulose acetate, cellulose triacetate, and polyvinylidene fluoride can be used without limitation, and among these, polyether sulfone may be more preferably used, but is not limited thereto.
  • any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride is used, and alumina or silicon carbide is preferably used.
  • the support is composed of a metal layer
  • various forms such as a metal foil, a metal sheet, or a metal film are possible
  • the material of the metal layer may be any one selected from the group consisting of copper, nickel, iron, aluminum, and titanium. Can be.
  • the coating layer having a nano-pores coated with a graphene oxide of 3 ⁇ m ⁇ 50 ⁇ m size in a thickness of 10 nm or more on the various supports.
  • Graphene oxide used in the present invention can be produced in large quantities by oxidizing graphite using an oxidizing agent, and includes a hydrophilic functional group such as a hydroxyl group, a carboxyl group, a carbonyl group, or an epoxy group.
  • a hydrophilic functional group such as a hydroxyl group, a carboxyl group, a carbonyl group, or an epoxy group.
  • graphene oxide is mostly Hummers method [Hummers, WS & Offeman, RE Preparation of graphite oxide. J. Am. Chem. Soc. 80 . 1339 (1958) or by the Hummers method modified in part, bar graphene oxide was also obtained in accordance with the Hummers method in the present invention.
  • the graphene oxide of the present invention is a hydroxyl group, a carboxyl group, a carbonyl group, or a hydrophilic functional group such as an epoxy group present in the graphene oxide chemically reacts with other compounds to ester group, ether group, amide group, or amino group
  • converted functionalized graphene oxide For example, the carboxyl group of graphene oxide is converted into an ester group by reaction with an alcohol, the hydroxyl group of graphene oxide is converted to an ether group by reaction with an alkyl halide, and the carboxyl group of graphene oxide is reacted with an alkyl amine. Converted to an amide group, or an epoxy group of graphene oxide is converted to an amino group by an alkyl amine ring-opening reaction.
  • graphene oxide thin film according to the present invention in order for the graphene oxide thin film according to the present invention to exhibit excellent barrier properties for gases having various molecular sizes, it is preferable to control the size of graphene oxide in the range of 3 ⁇ m to 50 ⁇ m, in particular, 3 ⁇ m to 10 ⁇ m. The range is more preferable because graphene oxide exhibits excellent gas barrier properties even when formed into an ultra-thin film.
  • Figure 1 shows the structure of the graphene oxide obtained by the Hummers method from graphite, the functionalized graphene oxide produced by the reaction of the graphene oxide with other compounds.
  • the graphene oxide coating layer formed on various supports includes a single layer or a plurality of layers of graphene oxide, and the graphene oxide of the single layer has a thickness in the range of 0.6 nm to 1 nm.
  • a single layer of graphene oxide may be stacked to form a plurality of layers of graphene oxide, wherein the interlayer distance of the graphene oxide is about 0.34 nm to 0.5 nm, so that an additional path of movement between grain boundaries is generated.
  • the graphene oxide coating layer more preferably comprises a plurality of laminated graphene oxide. desirable.
  • the graphene oxide coating layer When the graphene oxide coating layer is thick, it is a natural result that the gas barrier property is improved, but in the present invention, as described above, when the size of the graphene oxide is controlled in the range of 3 ⁇ m to 50 ⁇ m, the graphene oxide Even if the thickness of the coating layer is formed as an ultra-thin film of at least 10 nm, since the gas barrier properties can exhibit an excellent effect, the thickness of the graphene oxide coating layer is preferably 10 nm or more. In addition, the graphene oxide coating layer forms nanopores with an average diameter in the range of 0.5 nm to 1.0 nm.
  • the present invention in addition to the gas barrier graphene oxide nanocomposite membrane coated with graphene oxide on a variety of supports, including the support of the polymer material as described above, in the polyethylene glycol diacrylate or polyethylene glycol dimethacrylate polymer Provided is a gas barrier graphene oxide nanocomposite membrane having a pin oxide-inserted structure.
  • the number average molecular weight (Mn) of the polyethylene glycol diacrylate or polyethylene glycol dimethacrylate macromer is in the range of 250 to 1000 in the polymerization reaction, in particular in the ultraviolet (UV) polymerization reaction using a photoinitiator and the formation of a crosslinked structure. Suitable.
  • the graphene oxide is preferably in the size range of 100 ⁇ 1000 nm, if the size of the graphene oxide is less than 100 nm gas barrier properties may fall, if the size exceeds 1000 nm cross-linked polyethylene glycol It may be difficult to uniformly disperse and insert into the diacrylate or polyethyleneglycol dimethacrylate polymer.
  • the content of graphene oxide in the gas barrier graphene oxide nanocomposite membrane having a structure in which graphene oxide is inserted in the polyethylene glycol diacrylate or polyethylene glycol dimethacrylate polymer is 5% by weight or less, the gas permeability is reduced. It is desirable to maximize the.
  • the present invention comprises the steps of i) dispersing the graphene oxide in distilled water and treating with an ultrasonic mill for 0.1 to 6 hours to obtain a graphene oxide dispersion solution; ii) centrifuging the dispersion solution to form graphene oxide having a size adjusted to 3 ⁇ m ⁇ 50 ⁇ m; iii) obtaining a solution in which the graphene oxide formed in step ii) is dispersed in distilled water again; And iv) coating the dispersion solution of step iii) on a support to form a coating layer having nanopores.
  • the method of manufacturing a gas barrier graphene oxide nanocomposite membrane comprising the same.
  • the graphene oxide of step i) may be a functionalized graphene oxide in which a hydroxyl group, a carboxyl group, a carbonyl group, or an epoxy group present in the graphene oxide is converted to an ester group, an ether group, an amide group, or an amino group.
  • the graphene oxide may be dispersed in distilled water and treated with an ultrasonic grinder for 0.1 to 6 hours to improve dispersibility of graphene oxide in the dispersion solution.
  • the dispersion solution obtained in step iii) is a 0.01 to 0.5% by weight aqueous solution of graphene oxide adjusted to pH 10.0 using 1M aqueous sodium hydroxide solution, it is uniform if the concentration of the aqueous solution of graphene oxide is less than 0.01% by weight It is difficult to obtain a coating layer, and if the concentration is more than 0.5% by weight, the viscosity is too high, so a problem that a smooth coating can not be performed, the concentration of the graphene oxide aqueous solution is preferably 0.01 to 0.5% by weight.
  • the support of step iv) is capable of performing the function of the reinforcing material for supporting the coating layer is possible various materials in contact with the coating layer, the support is selected from the group consisting of polymer, ceramic, glass, paper, and metal layer It may be either one.
  • polyether sulfone may be more preferably used, but is not limited thereto.
  • any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride is used, and alumina or silicon carbide is preferably used.
  • the support is composed of a metal layer
  • various forms such as a metal foil, a metal sheet, or a metal film are possible
  • the material of the metal layer may be any one selected from the group consisting of copper, nickel, iron, aluminum, and titanium. Can be.
  • any known coating method may be used without limitation, but may be performed by any one method selected from the group consisting of a direct evaporation method, a transfer method, a spin coating method, and a spray coating method. It is preferable that a uniform coating layer can be obtained simply, and spin coating method is especially preferable.
  • the spin coating is preferably performed 3 to 10 times. If the spin coating is performed less than 3 times, it is difficult to expect a function as a gas barrier layer. If the spin coating is performed 10 times or more, the thickness of the coating layer becomes too thick. There is a disadvantage that it is difficult to obtain one coating layer.
  • the coating layer may include a single layer or a plurality of layers of graphene oxide, and the graphene oxide of the single layer has a thickness in the range of 0.6 nm to 1 nm, and the graphene oxide coating layer has an average diameter.
  • the nanopores in the range of 0.5 nm to 1.0 nm are formed.
  • Graphene oxide prepared by the Hummers method was dispersed in distilled water and treated with an ultrasonic mill for 3 hours to obtain a graphene oxide dispersion solution. Centrifuge the dispersion solution After forming the graphene oxide adjusted to 3 ⁇ m and dispersed in distilled water again to obtain a 0.1 wt% aqueous solution of graphene oxide adjusted to pH 10.0 using 1M aqueous sodium hydroxide solution. 1 mL of the graphene oxide aqueous solution was spin-coated five times on a porous polyether sulfone (PES) support to prepare a graphene oxide nanocomposite membrane having a graphene oxide coating layer having a thickness of 10 nm.
  • PES polyether sulfone
  • Polyethylene glycol diacrylate (PEGDA) macromer (number average molecular weight 250) and deionized water were mixed at a ratio of 7: 3 (weight ratio), followed by stirring for 12 hours to obtain a uniform solution.
  • the graphene oxide prepared by the Hummers method was added to the solution by 1% by weight of PEGDA macromer and 0.1% by weight of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator, sonicated for 2 hours, and then stirred for 24 hours. A precursor solution was obtained.
  • a graphene oxide nanocomposite film was prepared by irradiating 312 nm UV for 5 minutes under a nitrogen atmosphere (in this case, graphene oxide was used having a size of 270 nm and 800 nm, The content was also changed to 1, 2, 3, 4% by weight based on PEGDA macromer).
  • the gas barrier properties of the graphene oxide nanocomposite membranes prepared in Examples 1 and 2 were measured by a constant pressure / transformation volume measurement device equipped with gas chromatography.
  • Figure 2 shows a transmission electron microscope (TEM) of the graphene oxide obtained after centrifugation of the graphene oxide dispersion solution according to an embodiment of the present invention, it can be seen that the size is adjusted to about 3 ⁇ m.
  • TEM transmission electron microscope
  • the graphene oxide nanocomposite film prepared according to the embodiment forms a graphene oxide coating layer on the polyether sulfone support.
  • TEM 4 is a transmission electron microscope (TEM) image of a cross-section of a graphene oxide film coated with a 10 nm thickness on a porous polyether sulfone (PES) support according to an embodiment of the present invention, graphene oxide uniformly without defects It can be seen that it is laminated.
  • TEM transmission electron microscope
  • the graphene oxide nanocomposite according to the content of the graphene oxide prepared from Example 2 of Figure 5 increases as the graphene oxide content increases to confirm that the darker color It can be seen that the graphene oxide is uniformly dispersed and inserted in the crosslinked PEGDA polymer while increasing the graphene oxide content.
  • Figure 6 shows a scanning electron microscope (SEM) picture (graphene oxide size: 270 nm) of the graphene oxide nanocomposite according to the content of the graphene oxide prepared from Example 2, containing graphene oxide
  • SEM scanning electron microscope
  • Fig. 7 shows a photograph (graphene oxide content: 4% by weight) of the graphene oxide nanocomposite according to the size of the graphene oxide prepared from Example 2, the size of the graphene oxide 800 at 270 nm Even with increasing nm, it can be seen that graphene oxide is uniformly dispersed and inserted in the crosslinked PEGDA polymer.
  • a graphene oxide film without a support using a conventional vacuum filtration method Prepared. 10 is a scanning electron micrograph of a graphene oxide film having a thickness of about 5 ⁇ m manufactured by a conventional vacuum filtration method, and it can be seen that graphene oxide having a two-dimensional structure is stacked without gaps.
  • FIG. 11 shows a gas barrier property of a graphene oxide film prepared by preparing a graphene oxide film without a support by a conventional vacuum filtration method, and controlling the graphene oxide to have a specific size (0.5, 1.0, and 5.0 ⁇ m).
  • a specific size 0.5, 1.0, and 5.0 ⁇ m.
  • FIG. 12 is a graph of theoretically calculating the gas permeation channel length at the same thickness of the film of graphene oxide of various sizes, confirming that the gas permeation channel length gradually increases as the size of the graphene oxide increases at the same thickness.
  • the film is manufactured using graphene oxide having a specific size (3.0 ⁇ m), it can be seen that the gas permeation channel length increases to show excellent blocking characteristics. It shows a match.
  • FIG. 13 shows a graph of oxygen permeability (graphene oxide size: 270 nm) of graphene oxide nanocomposites according to the content of graphene oxide prepared from Example 2, and as the content of graphene oxide increases, oxygen It can be seen that the permeability gradually decreases, and in particular, when the content of graphene oxide in the graphene oxide nanocomposite film is 4% by weight, the oxygen permeability is 83 compared to that of the PEGDA polymer containing no graphene oxide. It can be seen that the percentage decreases.
  • FIG. 14 shows a graph of oxygen permeability (graphene oxide content: 4 wt%) of graphene oxide nanocomposite membrane according to the size of graphene oxide prepared from Example 2, as graphene oxide increases in size. It can be seen that the gas barrier property is improved, and in particular, when the size of the graphene oxide inserted into the graphene oxide nanocomposite membrane is 800 nm, the oxygen permeability is higher than that of the PEGDA polymer containing no graphene oxide. It can be seen that the reduction by 90%.
  • the graphene oxide nanocomposite membrane prepared according to the present invention the graphene oxide adjusted to a size of 3 ⁇ m ⁇ 50 ⁇ m is coated with a thin film of nano-thickness on various supports, or the graphene oxide is inserted into the polymer Its simple structure makes it suitable for display devices, food and pharmaceutical packaging because of its excellent barrier properties.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne une technique de fabrication d'une membrane nanocomposite d'oxyde de graphène dans laquelle un oxyde de graphène de 3 µm à 5 µm de taille est déposée avec une épaisseur de 10 nm ou plus sur divers supports, ou une membrane nanocomposite d'oxyde de graphène ayant une structure dans laquelle l'oxyde de graphène est inséré dans un polymère. La membrane nanocomposite d'oxyde de graphène fabriquée selon la présente invention présente d'excellentes caractéristiques de barrière contre divers gaz même lorsque de l'oxyde de graphène, dont la taille est régulée entre 3 µm et 5 µm, est déposé sous la forme d'un film mince d'épaisseur nanométrique sur divers supports ou la membrane nanocomposite d'oxyde de graphène a une structure simple dans laquelle l'oxyde de graphène est inséré dans un polymère, et la membrane nanocomposite d'oxyde de graphène peut donc être appliquée à l'emballage de dispositifs d'affichage, d'aliments et de produits médicaux.
PCT/KR2015/002156 2014-03-07 2015-03-06 Membrane nanocomposite d'oxyde de graphène présentant des caractéristiques de barrière contre les gaz améliorées et son procédé de fabrication WO2015133849A1 (fr)

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CN201580012597.4A CN106061593B (zh) 2014-03-07 2015-03-06 具有改善的气体阻隔特性的氧化石墨烯纳米复合膜及其制备方法

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CN109092087A (zh) * 2018-09-28 2018-12-28 南京科技职业学院 一种氧化石墨烯改性聚酰胺复合纳滤膜及其制备方法
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CN111547716A (zh) * 2020-06-19 2020-08-18 天津单从新材料科技有限公司 一种独立自支撑人工纳米石墨膜的制备方法
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EP3665009B1 (fr) * 2017-05-26 2022-03-23 Graphitene Ltd. Film multicouche pour emballage et son procédé de fabrication
CN115534368A (zh) * 2022-09-21 2022-12-30 湖北航天化学技术研究所 石墨烯基防迁移层制备方法
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CN117067737B (zh) * 2023-08-14 2024-02-09 青岛中海环境工程有限公司 一种堆肥发酵用聚四氟乙烯复合膜及其加工工艺

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US10751519B2 (en) 2010-11-22 2020-08-25 Aria Cv, Inc. System and method for reducing pulsatile pressure
US11406803B2 (en) 2010-11-22 2022-08-09 Aria Cv, Inc. System and method for reducing pulsatile pressure
US11938291B2 (en) 2010-11-22 2024-03-26 Aria Cv, Inc. System and method for reducing pulsatile pressure
US10702682B2 (en) 2010-11-22 2020-07-07 Aria Cv, Inc. System and method for reducing pulsatile pressure
US10682448B2 (en) 2014-06-19 2020-06-16 Aria Cv, Inc. Systems and methods for treating pulmonary hypertension
US11992636B2 (en) 2014-06-19 2024-05-28 Aria Cv, Inc. Systems and methods for treating pulmonary hypertension
US11511089B2 (en) 2014-06-19 2022-11-29 Aria Cv, Inc. Systems and methods for treating pulmonary hypertension
US11331105B2 (en) 2016-10-19 2022-05-17 Aria Cv, Inc. Diffusion resistant implantable devices for reducing pulsatile pressure
WO2018075552A1 (fr) * 2016-10-19 2018-04-26 Aria Cv, Inc. Dispositifs implantables résistant à la diffusion pour réduire la pression pulsatile
EP3665009B1 (fr) * 2017-05-26 2022-03-23 Graphitene Ltd. Film multicouche pour emballage et son procédé de fabrication
EP4177397A1 (fr) * 2018-02-16 2023-05-10 Ahlstrom-Munksjö Oyj Procédé de fabrication d'une couche de graphène/oxyde de graphène et support revêtu de graphène/oxyde de graphène
WO2019158707A1 (fr) * 2018-02-16 2019-08-22 Ahlstrom-Munksjö Oyj Procédé de fabrication d'une couche d'oxyde de graphène/graphène et support revêtu d'oxyde de graphène/graphène
CN109092087A (zh) * 2018-09-28 2018-12-28 南京科技职业学院 一种氧化石墨烯改性聚酰胺复合纳滤膜及其制备方法
US11833343B2 (en) 2019-09-06 2023-12-05 Aria Cv, Inc. Diffusion and infusion resistant implantable devices for reducing pulsatile pressure
US11141581B2 (en) 2019-09-06 2021-10-12 Aria Cv, Inc. Diffusion and infusion resistant implantable devices for reducing pulsatile pressure
CN111547716A (zh) * 2020-06-19 2020-08-18 天津单从新材料科技有限公司 一种独立自支撑人工纳米石墨膜的制备方法
CN115534368A (zh) * 2022-09-21 2022-12-30 湖北航天化学技术研究所 石墨烯基防迁移层制备方法
CN115534368B (zh) * 2022-09-21 2024-04-05 湖北航天化学技术研究所 石墨烯基防迁移层制备方法
CN117067737B (zh) * 2023-08-14 2024-02-09 青岛中海环境工程有限公司 一种堆肥发酵用聚四氟乙烯复合膜及其加工工艺

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