[go: up one dir, main page]

WO2016171486A1 - Matériau composite d'oxyde de graphène/polymère fonctionnalisé avec de la poly(éther-éther-cétone) sulfonée et film formant barrière aux gaz le comprenant - Google Patents

Matériau composite d'oxyde de graphène/polymère fonctionnalisé avec de la poly(éther-éther-cétone) sulfonée et film formant barrière aux gaz le comprenant Download PDF

Info

Publication number
WO2016171486A1
WO2016171486A1 PCT/KR2016/004152 KR2016004152W WO2016171486A1 WO 2016171486 A1 WO2016171486 A1 WO 2016171486A1 KR 2016004152 W KR2016004152 W KR 2016004152W WO 2016171486 A1 WO2016171486 A1 WO 2016171486A1
Authority
WO
WIPO (PCT)
Prior art keywords
ether
graphene oxide
functionalized
polymer
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2016/004152
Other languages
English (en)
Korean (ko)
Inventor
이중희
김남훈
라익라마칸타
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industry Academic Cooperation Foundation of Chonbuk National University
Original Assignee
Industry Academic Cooperation Foundation of Chonbuk National University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Industry Academic Cooperation Foundation of Chonbuk National University filed Critical Industry Academic Cooperation Foundation of Chonbuk National University
Publication of WO2016171486A1 publication Critical patent/WO2016171486A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride

Definitions

  • the present invention relates to graphene oxide / polymer composites functionalized with sulfonated polyether-ether-ketone, more particularly sulfonated poly (ether-ether-ketone) Functionalized graphene oxide / functionalized graphene oxide / polymer composites characterized in that it comprises a polyvinylidene fluoride (PVDF) polymer, characterized by improved mechanical strength, thermal properties and gas barrier properties
  • PVDF polyvinylidene fluoride
  • Combination of the graphene and the polymer matrix can effectively strengthen the structure, and because of the improved features it can be applied to the graphene and various applications.
  • the graphene in order for the polymer matrix to be successfully strengthened using graphene, the graphene must be homogeneously dispersed in the matrix. Recently, various studies on a method for dispersing graphene in a polymer matrix have been performed. Examples include solution casting, melt mixing, and in situ polymerization.
  • Graphene oxide is difficult to mix with hydrophilic and hydrophobic polymers in nature.
  • the reduced graphene oxide is difficult to mix with both hydrophobic and hydrophilic polymers.
  • Graphene has a strong bonding force with the adjacent graphene layer, because the interfacial interaction between the polymer matrix and the graphene is very weak, there is a problem that the graphene clumps. Therefore, it is very difficult to disperse the graphene in the polymer matrix.
  • the inventors of the present invention functionalize the graphene oxide with a polyether-ether-ketone (Sulfonated poly (ether-ether-ketone)), and then introduced into the PVDF polymer mechanical strength, thermal properties and gas barrier ability, etc.
  • the present invention has been completed to realize that improved functionalized graphene oxide / polymer composites can be prepared.
  • An object of the present invention is to introduce a graphene oxide functionalized with sulfonated poly (ether-ether-ketone) into PVDF polymers, thereby improving the mechanical strength, thermal properties, and gas barrier properties.
  • sulfonated poly ether-ether-ketone
  • Functionalized graphene oxide characterized in that it comprises graphene oxide functionalized with sulfonated poly (ether-ether-ketone) and a polyvinylidene fluoride (PVDF) polymer matrix.
  • PVDF polyvinylidene fluoride
  • the graphene oxide functionalized with sulfonated poly is 0.1 to 40% by weight relative to the PVDF polymer matrix. May be included.
  • the dipole of the sulfonated group (-SO 3 H) contained in the graphene oxide functionalized with sulfonated poly (ether-ether-ketone) may bind through a dipole and dipole interaction of the difluoromethyl group (CF 2 ) included in the polyvinylidene fluoride (PVDF) polymer matrix.
  • the gas permeability may be 0.01 ⁇ 100 cc / m 2 atm day.
  • Another aspect of the present invention provides a gas barrier membrane comprising the functionalized graphene oxide / polymer composite material.
  • Functionalized graphene oxide characterized in that it comprises graphene oxide functionalized with sulfonated poly (ether-ether-ketone) and a polyvinylidene fluoride (PVDF) polymer matrix.
  • PVDF polyvinylidene fluoride
  • Example 3 is a field emission scanning electron microscope image showing a cross section of Example 1, Example 2 and Comparative Example 1.
  • FIG. 4 is an FTIR spectrum and a WAXS spectrum of Example 1, Example 2, and Comparative Example 1.
  • FIG. 4 is an FTIR spectrum and a WAXS spectrum of Example 1, Example 2, and Comparative Example 1.
  • Figure 5 (a) is a DSC result graph showing the melting point of Example 1, Example 2 and Comparative Example 1; (b) is a DSC result graph which shows the crystallization temperature of Example 1, Example 2, and Comparative Example 1.
  • FIG. 5 (a) is a DSC result graph showing the melting point of Example 1, Example 2 and Comparative Example 1; (b) is a DSC result graph which shows the crystallization temperature of Example 1, Example 2, and Comparative Example 1.
  • Example 6 is a graph showing the thermal stability of Example 1, Example 2 and Comparative Example 1.
  • Example 7 is a graph showing the mechanical strength of Example 1, Example 2 and Comparative Example 1.
  • Example 8 is a graph showing gas permeability and transmission coefficient of Example 1, Example 2 and Comparative Example 1.
  • Functionalized graphene oxide characterized in that it comprises graphene oxide functionalized with sulfonated poly (ether-ether-ketone) and a polyvinylidene fluoride (PVDF) polymer matrix.
  • PVDF polyvinylidene fluoride
  • the functionalized graphene oxide / polymer composite according to the present invention is characterized by functionalizing graphene oxide with sulfonated poly (ether-ether-ketone), and then dispersing it homogeneously in PVDF polymer. Mechanical and thermal properties and gas barrier properties can be improved.
  • the graphene oxide functionalized with sulfonated poly is 0.1 based on the total weight of the composite material. It is preferably included in the 40 to 40% by weight, preferably contained in 0.5 to 5% by weight, more preferably in the 1.5 to 3.5% by weight. According to the content of graphene oxide functionalized with sulfonated poly (ether-ether-ketone), beta crystals increase in the crystal structure of the manufactured composite material, and thus mechanical and thermal Characteristics and gas barrier performance can be improved.
  • the dipole of the sulfonated group (-SO 3 H) included in the graphene oxide functionalized with sulfonated poly (ether-ether-ketone) is PVDF (polyvinylidene fluoride). ) Can be bonded through dipole and dipole of the difluoromethyl group (CF 2 ) included in the polymer matrix. Through such a dipole interaction can have a more strong bonding force between the graphene oxide and the PVDF polymer matrix, the mechanical and thermal properties of the composite material according to the present invention can be improved.
  • the composite includes alpha crystals ( ⁇ -polymorph) and beta crystals ( ⁇ -polymorph), and alpha crystals and beta crystals of the PVDF polymer matrix are 100 : Included in a volume ratio of 0; Graphene oxide functionalized with sulfonated poly (ether-ether-ketone) is included in 3% by weight of the PVDF polymer matrix, alpha-crystal and beta-crystal of the composite material May be included in a volume ratio of 0: 100.
  • the PVDF polymer is a technically important semi-crystalline polymer, and includes alpha and beta crystal structures and functionalized with sulfonated poly (ether-ether-ketone) sulfonated to the PVDF polymer.
  • sulfonated poly ether-ether-ketone
  • the PVDF polymer includes alpha and beta crystal structures and functionalized with sulfonated poly (ether-ether-ketone) sulfonated to the PVDF polymer.
  • the functionalized graphene oxide / polymer composite material may have a melting point of 163 ° C. to 170 ° C., a crystallization temperature of 130 ° C. to 140 ° C., and a thermal decomposition temperature of 435 ° C. to 450 ° C. More preferably, it may be 164 ⁇ 170 °C, the crystallization temperature is 133 ⁇ 140 °C, pyrolysis temperature may be 440 °C ⁇ 450 °C.
  • the thermal properties are improved as the crystal structure is changed by adding and dispersing the functionalized graphene oxide to the polymer, and more specifically, the functionalized graphene oxide is contained in an amount of 0.5 to 5 wt% based on the PVDF polymer. If the thermal properties can be improved as described above.
  • the functionalized graphene oxide / polymer composite material may have a tensile strength of 10 to 30 MPa, a strain of 13% to 25%, and a Young's modulus of 1.5 to 3.5 GPa. More preferably, the tensile strength may be 15 to 30 MPa, the strain is 15% to 25%, and the Young's modulus may be 1.8 to 3.5 GPa.
  • the mechanical properties are improved as the crystal structure is changed by adding and dispersing the functionalized graphene oxide to the polymer, and more specifically, the functionalized graphene oxide is 0.5 to 5 wt% based on the total weight of the composite material. When included, the mechanical properties may be improved as described above.
  • oxygen gas permeability may be 0.01 ⁇ 100 cc / m 2 atm day.
  • the oxygen gas transmittance may be 1 to 16 cc / m 2 d.atm, and the transmission coefficient may be 0.1 to 1.2 cc.mm/m 2 d.atm.
  • oxygen gas barrier ability is improved as the crystal structure is changed by adding and dispersing functionalized graphene oxide to the polymer, and more specifically, sulfonated poly (ether-ether). -ketone)) functionalized graphene oxide can be improved oxygen gas barrier capacity as described above when included in 0.1 to 40% by weight based on the total weight of the composite material.
  • the present invention provides a gas barrier membrane comprising the functionalized graphene oxide / polymer composite material.
  • the functionalized graphene oxide / polymer composite material is excellent in mechanical and thermal properties, the oxygen blocking ability is improved can be used as a gas barrier film.
  • Graphene oxide was synthesized using Hummer's method. More specifically, 23 ml of concentrated sulfuric acid (Samchun Pure Chemical Co. Ltd) is placed in an Erlenmeyer flask, which is introduced into an ice bath and stirred at a uniform rate during the time at which the reaction is carried out at 0 to 5 ° C. It was. Next, 0.5 g of sodium nitrate and 1 g of graphite powder were added to the Erlenmeyer flask and stirred at a uniform speed.
  • Sulfonated poly (ether-ether-ketone) (SPEEK) by reacting polyetheretherketone (PEEK, poly (ether-ether-ketone), Victrex plc, UK) with concentrated sulfuric acid at 35 ° C ) was prepared.
  • SPG was prepared by liquid dispersion of GO with hydrazine in the presence of SPEEK. More specifically, 100 mg of GO was introduced into an Erlenmeyer flask containing 50 mL of water, followed by stirring by sonication. In another Erlenmeyer flask, 1 g of SPEEK was dissolved in 50 ml of water at 60 ° C.
  • the SPEEK aqueous solution was added to the GO dispersion solution, and then sonicated with a homogeneous solution for 30 minutes.
  • the reaction was reacted with hydrazine at 100 ° C. for 6 hours to reduce GO and permeate through a 0.2 um cellulose acetate membrane. This was dried under vacuum for 3 days to prepare SPG.
  • SPG-PVDF composite material was prepared by the solvent film method. More specifically, the SPG prepared in Preparation Example 2 was properly dispersed in 10 ml of DMF by sonication. Thereafter, an appropriate amount of PVDF was dissolved in the SPG dispersion so that SPG was included in an amount of 1 wt% based on the composite PVDF polymer matrix. Thereafter, the solution was sonicated for 30 minutes to prepare a homogeneous solution. The solution was poured into a Petri dish and evaporated in air at 60 ° C. to produce a composite membrane. The composite membrane was maintained at 6 ° C. in a vacuum for 3 days to remove the solvent to prepare a SPG-PVDF composite.
  • An SPG-PVDF composite material was manufactured in the same manner as in Example 1, except that 3 wt% of the PVDF polymer was included.
  • SPG liquid dispersion solution containing the SPG of Preparation Example 2 at 0.05% by weight was applied to a copper-coated copper grid, and evaporated at room temperature and observed with a transmission electron microscope (JEM2200FS Jeol, Japan). 1 is shown.
  • FTIR Fastier transform infrared, thermo scientific, USA
  • Figure 2 (b) the results are shown in Figure 2 (b).
  • the sample was introduced into the silicon wafer from the DMF solution. Prior to the FTIR measurement, the sample was held for 3 days in a vacuum at 60 ° C., and then the spectrum was recorded.
  • thermogravimetric analysis TGA, thermogravimetric analysis, TA Instruments, New castle, USA
  • TGA thermogravimetric analysis, TA Instruments, New castle, USA
  • SPG shows that some wrinkles are formed on the graphene sheet completely peeled. This shows that the SPG sheet is dispersed completely in the DMF solution.
  • FIG. 1 (b) it can be observed for the cross section of the SPG, through which it is possible to determine the number of graphene layers formed in the SPG.
  • FIG. 1 (c) an electron diffraction pattern (SAED) in the selected area of the SPG can be confirmed, and the structure of the graphene sheet of the monolayer of the SPG can be confirmed. It can be seen that the relative strength of the inner and outer circles is ⁇ 1.
  • the SPG shows a weight loss of up to about 15% at temperatures between 200 ° C and 400 ° C, because the sulfonic acid groups in SPGdml SPEEK begin to decompose, and at a temperature above 400 ° C, the weight loss reaches about 28.5%. You can check it.
  • GO is 2933cm -1 and 2857cm - 1 has a CH bond of the sp3, which can be seen from the peak of 2933 and 2857cm -1, which means that the GO comprises a CH 2 and CH bond.
  • the spherical lamellar crystals have a structure in which they are unfolded from the center to the outside.
  • the spherical crystal and the fabric (fiber like structure) appears at the same time, it was confirmed that the crystal of the spherical phase was reduced compared to Comparative Example 1.
  • Example 2 it can be seen that the crystal of the spherical phase disappears completely, and is formed only in the form of a fabric. It can also be seen that the graphene sheet acts as a heterogeneous nucleating agent and provides a surface for crystallization of PVDF.
  • the peak at 876 cm -1 is due to the bending vibration of the CF2 functional group in PVDF.
  • the dipole of CF2 bonds through the strong dipole interaction with the dipole of SO3H of SPG, and therefore moves at a higher frequency.
  • Example 1 since the content of graphene is low and the beta crystals do not sufficiently nucleate, both alpha and beta crystals are included, but in Example 2, the beta crystals are nucleated at a sufficient surface area. You can see that.
  • the melting point of Comparative Example 1 is 160.5 °C
  • Example 1 is 163.6 °C
  • Example 2 is 165.5 °C.
  • Example 1 includes both alpha crystals and beta crystals
  • Example 2 includes only beta crystals, but the beta crystals have stronger binding. Therefore, alpha crystals decrease with increasing SPG content, beta crystals increase, and a higher temperature is required to melt the beta crystals. Therefore, the melting point increases as the SPG content increases.
  • thermogravimetric analyzer TGA
  • Comparative Example 1 may confirm that pyrolysis starts at 431 ° C.
  • Example 1 can be seen that pyrolysis starts at 440 ° C, and Example 2 starts pyrolysis at 445 ° C.
  • the thermal stability of the composite material according to the present invention is significantly improved compared to PVDF, it can be seen that the beta crystal layer shows a stronger bond than the alpha crystal layer.
  • the tensile strength increases and the strain decreases.
  • the strain and tensile strength simultaneously increase.
  • the tensile strength is increased by 138.7%
  • the strain is increased by 48.7% compared to the net PVDF.
  • the mechanical properties are affected by the microstructure, more particularly due to the relationship between dispersion and structural properties.
  • the net PVDF includes alpha crystals that represent spherical phase crystals, and in Example 1, it can be seen that spherical phase and alpha crystals and beta crystals are included.
  • Oxygen gas permeability OTR, pxygen gas transmittance rates
  • transmission coefficients were measured at 25 ° C. in order to confirm the oxygen barrier properties of Examples 1 to 2 and Comparative Example 1 according to the present invention. Indicated.
  • the electron density of the aromatic ring of graphene is very high, thereby preventing all molecules trying to pass through the surface thereof. Therefore, graphene is a very effective gas barrier material.
  • the impermeable nano-pillars dispersed in the proper direction significantly improves the gas barrier properties.
  • the oxygen gas permeability (OTR, pxygen gas transmittance rates) of Comparative Example 1 is 29.5 cc / m 2 d. Very high atm and significantly lowered to 16 cc / m 2 d.atm and 3.05 cc / m 2 d.atm for Example 1 and Example 2 with SPG added, respectively.
  • the permeability coefficient was derived by multiplying the oxygen gas permeability by the thicknesses of the membranes used in Examples 1 and 2 and Comparative Example 1, which is shown in FIG. 8 (b).
  • Comparative Example 1 that is, pure PVDF
  • the transmission coefficient is 2.36 cc.mm/m 2 d.atm
  • the transmission coefficients of Examples 1 and 2 according to the present invention are 1.12 cc.mm/m 2 d.atm and It can be seen that the value is significantly higher than 0.21 cc.mm / m 2 d.atm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un matériau composite d'oxyde de graphène/polymère fonctionnalisé avec de la poly(éther-éther-cétone) sulfonée. Plus spécifiquement, la présente invention peut produire un matériau composite d'oxyde de graphène/polymère présentant une résistance mécanique, des caractéristiques thermiques, et une capacité de barrière aux gaz améliorées, en fournissant un matériau composite d'oxyde de graphène/polymère fonctionnalisé caractérisé en ce qu'il comprend un oxyde de graphène fonctionnalisé avec de la poly(éther-éther-cétone) sulfonée et un polymère de poly(fluorure de vinylidène) (PVDF).
PCT/KR2016/004152 2015-04-23 2016-04-21 Matériau composite d'oxyde de graphène/polymère fonctionnalisé avec de la poly(éther-éther-cétone) sulfonée et film formant barrière aux gaz le comprenant Ceased WO2016171486A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020150057244A KR101698456B1 (ko) 2015-04-23 2015-04-23 술폰화된 폴리에테르-에테르-케톤으로 기능화된 그래핀 옥사이드/고분자 복합재료 및 이를 포함하는 가스차단막
KR10-2015-0057244 2015-04-23

Publications (1)

Publication Number Publication Date
WO2016171486A1 true WO2016171486A1 (fr) 2016-10-27

Family

ID=57143204

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/004152 Ceased WO2016171486A1 (fr) 2015-04-23 2016-04-21 Matériau composite d'oxyde de graphène/polymère fonctionnalisé avec de la poly(éther-éther-cétone) sulfonée et film formant barrière aux gaz le comprenant

Country Status (2)

Country Link
KR (1) KR101698456B1 (fr)
WO (1) WO2016171486A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107266833A (zh) * 2017-07-24 2017-10-20 轩福君 一种热塑膜回收利用改性剂及回收工艺
CN112480576A (zh) * 2020-11-20 2021-03-12 扬州大学 一种高压电性能pvdf薄膜的制备方法
US11183700B2 (en) 2019-09-16 2021-11-23 Saudi Arabian Oil Company Ion exchange membrane for a redox flow battery
CN119838574A (zh) * 2024-12-30 2025-04-18 佛山西陇化工有限公司 降低电子级硫酸中Ag/Au/Pt含量的纳米多孔膜材及制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150026088A (ko) * 2013-08-30 2015-03-11 전남대학교산학협력단 고분자 전해질 복합막 및 상기 고분자 전해질 복합막 제조방법 및 그 복합막을 포함하는 에너지저장장치

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150026088A (ko) * 2013-08-30 2015-03-11 전남대학교산학협력단 고분자 전해질 복합막 및 상기 고분자 전해질 복합막 제조방법 및 그 복합막을 포함하는 에너지저장장치

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ANSARI, S. ET AL.: "Functionalized Graphene Sheet-Poly(Vinylidene Fluoride) Conductive Nanocomposites", JOURNAL OF POLYMER SCIENCE : PART B: POLYMER PHYSICS, vol. 47, 25 March 2009 (2009-03-25), pages 888 - 897, XP055307269 *
DAI, W. ET AL.: "SPEEK/Graphene Oxide Nanocomposite Membranes with Superior Cyclability for Highly Efficient Vanadium Redox Flow Battery", JOURNAL OF MATERIALS CHEMISTRY A, vol. 2, 2014, pages 12423 - 12432, XP055324103 *
HOE, Y. ET AL.: "The Effect of Sulfonated Graphene Oxide on Sulfonated Poly(Ether Ether Ketone) Membrane for Direct Methanol Fuel Cells", JOURNAL OF MEMBRANE SCIENCE, vol. 425-426, 26 September 2012 (2012-09-26), pages 11 - 22, XP055324159 *
LAYEK, R. K. ET AL.: "Enhancement of Physical, Mechanical, and Gas Barrier Properties in Noncovalently Functionalized Graphene Oxide/Poly(Vinylidene Fluoride) Composites", CARBON, vol. 81, January 2015 (2015-01-01), pages 329 - 338, XP029093005 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107266833A (zh) * 2017-07-24 2017-10-20 轩福君 一种热塑膜回收利用改性剂及回收工艺
US11183700B2 (en) 2019-09-16 2021-11-23 Saudi Arabian Oil Company Ion exchange membrane for a redox flow battery
CN112480576A (zh) * 2020-11-20 2021-03-12 扬州大学 一种高压电性能pvdf薄膜的制备方法
CN119838574A (zh) * 2024-12-30 2025-04-18 佛山西陇化工有限公司 降低电子级硫酸中Ag/Au/Pt含量的纳米多孔膜材及制备方法

Also Published As

Publication number Publication date
KR101698456B1 (ko) 2017-01-20
KR20160126320A (ko) 2016-11-02

Similar Documents

Publication Publication Date Title
Huang et al. Silane grafted graphene oxide papers for improved flame resistance and fast fire alarm response
Layek et al. Enhancement of physical, mechanical, and gas barrier properties in noncovalently functionalized graphene oxide/poly (vinylidene fluoride) composites
US8709213B2 (en) Composite graphene oxide-polymer laminate and method
Hwang et al. Poly (vinyl alcohol) reinforced and toughened with poly (dopamine)-treated graphene oxide, and its use for humidity sensing
Putz et al. High‐nanofiller‐content graphene oxide–polymer nanocomposites via vacuum‐assisted self‐assembly
US9147881B2 (en) Graphene paper which reduced graphene oxide layers and coating layers are stacked in sequence and preparation method thereof
US9318231B2 (en) Method of preparing reduced graphene oxide and reduced graphene oxide-polymer composites
Cheng et al. Glycera‐inspired synergistic interfacial interactions for constructing ultrastrong graphene‐based nanocomposites
Fan et al. Constructing fibrillated skeleton with highly aligned boron nitride nanosheets confined in alumina fiber via electrospinning and sintering for thermally conductive composite
WO2015163595A1 (fr) Procédé de production d'une nanofibre de carbone à base de graphène par auto-assemblage intercouche
WO2016171486A1 (fr) Matériau composite d'oxyde de graphène/polymère fonctionnalisé avec de la poly(éther-éther-cétone) sulfonée et film formant barrière aux gaz le comprenant
WO2015099415A1 (fr) Composite nanométrique en graphite de type plaque-métal et son procédé de fabrication
Pan et al. Large‐Scale Production of Rectorite Nanosheets and Their Co‐Assembly with Aramid Nanofibers for High‐Performance Electrical Insulating Nanopapers
Liu et al. Ice-templated anisotropic flame-resistant boron nitride aerogels enhanced through surface modification and cellulose nanofibrils
WO2017188564A1 (fr) Procédé de fabrication de fibre d'oxyde de graphène, de fibre de graphène, et ou de fibre composite de graphène ou (d'oxyde) de graphène à l'aide d'un procédé de filage humide induit par champ électrique
US11613464B2 (en) Modified boron nitride nanotubes and solutions thereof
Zhu et al. Nacre-like composite films with a conductive interconnected network consisting of graphene oxide, polyvinyl alcohol and single-walled carbon nanotubes
US8349219B2 (en) Carbon nanotube bulk material and method of fabricating the same
WO2014148705A1 (fr) Procédé permettant de produire un composite nanotube de carbone
KR101701238B1 (ko) 금속산화물 나노입자가 코팅된 그래핀 옥사이드/고분자 복합체 및 그 제조방법
WO2020032684A1 (fr) Bain de coagulation de filage de graphène par voie humide et procédé de fabrication d'une fibre d'oxyde de graphène l'utilisant
Durso et al. Versatile fabrication of carbon nanotube yarn composites by in-situ interfacial polymerization of polyetherimide
Yi et al. Enhanced mechanical strength and electrical conductivity of carbon-nanotube/TiC hybrid fibers
Yin et al. Enhancing the reinforcing efficiency in CNT nanocomposites via the development of pyrene-based active dispersants
KR102382709B1 (ko) 단분자가 결합된 질화붕소 나노튜브와 이를 이용한 콜로이드 용액의 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16783419

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16783419

Country of ref document: EP

Kind code of ref document: A1