WO2012069760A1 - Membranes de pvdf a surface superhydrophobe - Google Patents

Membranes de pvdf a surface superhydrophobe Download PDF

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Publication number
WO2012069760A1
WO2012069760A1 PCT/FR2011/052730 FR2011052730W WO2012069760A1 WO 2012069760 A1 WO2012069760 A1 WO 2012069760A1 FR 2011052730 W FR2011052730 W FR 2011052730W WO 2012069760 A1 WO2012069760 A1 WO 2012069760A1
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WO
WIPO (PCT)
Prior art keywords
pvdf
membrane
water
nodules
membranes
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/FR2011/052730
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English (en)
French (fr)
Inventor
André DERATANI
Damien Quemener
Denis Bouyer
Céline POCHAT-BOHATIER
Chia-Ling Li
Da-Ming Wang
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.)
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Universite de Montpellier
Original Assignee
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Universite de Montpellier
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 Centre National de la Recherche Scientifique CNRS, Arkema France SA, Universite de Montpellier filed Critical Centre National de la Recherche Scientifique CNRS
Priority to EP11802497.5A priority Critical patent/EP2643079A1/fr
Priority to US13/988,517 priority patent/US20130306560A1/en
Priority to CN201180065656.6A priority patent/CN103347597B/zh
Priority to KR1020137016007A priority patent/KR101796637B1/ko
Priority to JP2013539326A priority patent/JP5792823B2/ja
Priority to SG2013045836A priority patent/SG191730A1/en
Publication of WO2012069760A1 publication Critical patent/WO2012069760A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • B01D67/00165—Composition of the coagulation baths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/04—Hydrophobization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B01D2323/22—Specific non-solvents or non-solvent system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/38—Hydrophobic membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates generally to the field of hydrophobic solid surfaces, and more particularly to polyvinylidene fluoride (PVDF) membranes with superhydrophobic surface.
  • PVDF polyvinylidene fluoride
  • the invention also relates to the process for preparing these membranes as well as their industrial applications.
  • “superhydrophobic” is meant the characteristic of a surface on which a drop of water forms with said surface a contact angle greater than or equal to 150 °.
  • Superhydrophobia is a known physical property that responds to Cassie's law.
  • the contact angle is a dihedral angle formed by two interfaces contiguous to their apparent intersection.
  • the surface is described as “non-wetting” with respect to water. This property is commonly referred to as the Lotus effect.
  • Superhydrophobic surfaces have a high roughness. Indeed, it is the nanometric roughness of a surface that confers the property of superhydrophobia, as shown in the publication by Lafuma A. and Quowski D. (2003): “Superhydrophobie States", Nature Materials, 2 (457-460 ).
  • Polymeric membranes are generally produced by a phase inversion process. Entry of a non-solvent into a polymer solution causes separation between a polymer-rich phase constituting the continuous matrix of the material and a discontinuous polymer-poor phase at the origin of the pores.
  • VIPS vapor-induced phase inversion
  • the rapid entry of the non-solvent causes the mixture to be found very rapidly in the liquid-liquid demixing range; in this case the morphology is that of a conventional asymmetric membrane made of a dense surface skin supported on a spongy structure with more or less macrovoids; by precipitation from a PVDF / DMF solution in octanol, the slow entry of the non-solvent causes the mixture to remain a sufficiently long time in the solid-liquid demixing zone (crystallization domain), which gives a morphology in dense non-interconnected nodules.
  • the object of the present invention is to prepare superhydrophobic PVDF membranes. These membranes are porous and have a hierarchical surface morphology. The porosity of the membrane, associated with a double level of organization, at the micrometric scale and at the nanoscale, is capable of trapping air and makes it possible to generate superhydrophobic surface properties also known under the name lotus effect.
  • the subject of the invention is a PVDF membrane comprising a superhydrophobic surface comprising a porous structure at the nanometric scale and interconnected micron-sized crystalline nodules.
  • said superhydrophobic surface has a water contact angle greater than or equal to 150 °.
  • the contact angle is measured by deposition of a drop of water of 8 under ambient conditions of temperature (21 ⁇ 3 ° C) and pressure. The indicated value is an average of at least 4 independent measurements.
  • the invention relates to a process for preparing the superhydrophobic PVDF membrane according to the invention, comprising a precipitation operation from a dual alcohol-water bath system.
  • FIG 1 illustrates the membranes prepared in Example 1
  • FIG. 2 illustrates the membranes prepared in example 2
  • FIG. 3 illustrates the membranes prepared in Example 3
  • FIG. 4 illustrates the membranes prepared in Example 4.
  • FIG. 5 illustrates the membranes prepared in Example 5.
  • FIG. 6 is the image obtained by scanning electron microscopy (SEM) of a superhydrophobic membrane according to the invention obtained by precipitation of PVDF in a double iso-propanol-water bath;
  • FIG. 7 illustrates the structure of several membranes observed with SEM, prepared by the VIPS method and by precipitation of PVDF in a double bath: methanol-water; ethanol-water; n-propanol-water; iso-propanol-water; 1-butanol-water; 1-octanol-water and 1-decanol-water, respectively.
  • PVDF polystyrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-sulfate, polystyrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styren
  • the present invention therefore proposes to provide superhydrophobic PVDF membranes, as well as a method of manufacturing these membranes.
  • the PVDF membranes according to the invention comprise a superhydrophobic surface comprising a hierarchical structure with two levels of organization, namely inter-nodule porosity at the micrometric scale and intranodular porosity at the nanoscale, and nodules. interconnected crystalline Said superhydrophobic surface has a water contact angle greater than or equal to 150 ° C.
  • Scanning electron microscopy images show that said nodules have a size of between 5 and 12 microns, preferably between 6 and 8 microns. These nodules have an inter-nodular porosity of less than 5 microns, whereas the intra-nodular pores have a submicron size (of a few hundred nanometers), giving a sponge-like morphology.
  • the images also show that the nodules are connected to each other, which gives mechanical strength to the whole.
  • the PVDF membranes according to the invention have a pore volume greater than 70%, preferably greater than 75% and advantageously equal to or greater than
  • the structure of the PVDF membranes according to the invention is of the interconnected type.
  • phase can be defined as a portion of "uniform" material that has stable properties and reproducible. In other words, the properties of a phase are exclusively a function of the thermodynamic variables and are independent of time.
  • This type of structure traps the air and prevents a close contact of water with the surface resulting in very high contact angles.
  • the membrane has a resistance to a pressure of up to at least 5 bar, testifying to its good mechanical strength.
  • the reinforced membrane especially textile
  • the reinforced membrane is subjected to water under pressure and it is verified that it remains intact.
  • the invention relates to a process for preparing the superhydrophobic PVDF membrane according to the invention, comprising a precipitation operation from a dual alcohol-water bath system.
  • the method according to the invention comprises the following steps:
  • the PVDF is dissolved in a solvent, chosen for example from the list: HMPA, DMAc, NMP, DMF, DMSO, TMP, TMU.
  • a solvent chosen for example from the list: HMPA, DMAc, NMP, DMF, DMSO, TMP, TMU.
  • the homogeneous solution obtained is deposited on a glass plate and then spread with a knife.
  • the glass plate is then immersed in a first coagulant bath containing either a low molecular weight alcohol such as methanol, ethanol, n-propanol or isopropanol, or an alcohol of higher molecular weight such as n butanol, n-octanol or n-decanol.
  • Said plate is then immersed in a second water bath, and then it is dried.
  • Membranes comprising a superhydrophobic surface, comprising a nanoscale rough structure, and interconnected crystalline nodules were obtained when the alcohol was methanol, ethanol, n-propanol, iso-propanol or n-propanol. butanol.
  • the nodules are interconnected and have a "sponge" morphology as shown in the appended FIG. 6, which illustrates the precipitation of the PVDF when the non-solvent is isopropanol.
  • the membranes obtained after a first bath in 1-octanol or 1-decanol have dense nodules. The denser the nodules, the less they can trap the air and the lower the hydrophobicity of the surface.
  • Pore size, porosity and morphology of nodules from porous nodules to dense nodules in a bi-continuous structure through "sponge" nodules of all shapes can be obtained by varying the concentration of polymer, the temperature and the alcohol considered ( Figure 7).
  • the invention also relates to the application of the membranes described herein for the distillation of water, filtration and Li-ion batteries.
  • a homogeneous solution of PVDF at 20% by weight is prepared by dissolving it in NMP or DMAc at 60 ° C.
  • the solution obtained is deposited on a glass plate and then spread with a knife whose air gap is set at 250 ⁇ .
  • the glass plate is then either subjected to moist air (VIPS process) to generate the phase separation (Comparative Example), or immersed in a first coagulant bath containing a low molecular weight alcohol such as methanol (Example 1b). ), Ethanol, n-propanol, isopropanol (Example 1c), 1-octanol (Comparative Example) and water (Comparative Example 1) for 10 min at 25 ° C.
  • Said plate is then immersed in a second bath consisting of water (except in the case of VIPS where it is immersed in water or in ethanol), then it is dried at room temperature.
  • the membranes thus obtained were observed under a scanning electron microscope. Their resistance to a pressure of 5 Bar was also measured, when the membranes are reinforced, especially on textile. Finally, the angle of contact with water is measured by depositing a drop of water of 8 under ambient conditions of temperature (21 ⁇ 3 ° C) and pressure. The indicated value is an average of at least 4 independent measurements. Table 1 summarizes the characteristics of the membranes formed. The images corresponding to these membrane samples, obtained by scanning electron microscopy, are shown in FIG.
  • a homogeneous solution of PVDF at 20% by weight is prepared by dissolving it in NMP at 60 ° C.
  • the solution obtained is deposited on a glass plate and then spread with a knife whose air gap is set at 250 ⁇ .
  • the glass plate is then immersed in a first coagulant bath containing methanol for varying times at 25 ° C.
  • the said plate is then immersed in a second bath made of water, then it is dried at room temperature.
  • Table 2 shows the water contact angles of the membranes formed.
  • a homogeneous solution of PVDF at 20% by weight is prepared by dissolving it at 80 ° C in wet NMP with varying amounts of water (up to 6% by weight).
  • the solution obtained is deposited on a glass plate and then spread with a knife whose air gap is set at 250 ⁇ .
  • the glass plate is then immersed in a first coagulant bath containing a low molecular weight alcohol such as iso-propanol for 10 minutes at 25 ° C.
  • the said plate is then immersed in a second bath consisting of water, and then it is dried at room temperature.
  • Table 3 shows the water contact angles of the membranes formed. The images corresponding to these membrane samples, obtained by scanning electron microscopy, are shown in FIG. 3. These results show that the addition of a few percent of water in the polymer solution makes it possible to adjust the contact angle. membranes prepared according to Example 3 without modifying the morphology obtained in porous nodules. Table 3 shows that superhydrophobic membranes are obtained for water addition values in the casting solution of between 3 and 5% (Ex. 3c, 3d and 3e).
  • a homogeneous solution of PVDF at 20% by weight is prepared by dissolving it in NMP at temperatures between 32 and 110 ° C.
  • the solution obtained is deposited on a glass plate and then spread with a knife whose air gap is set at 250 ⁇ .
  • the glass plate is then immersed in a first coagulant bath containing a low molecular weight alcohol such as methanol, ethanol or iso-propanol for 10 min at 25 ° C.
  • the said plate is then immersed in a second bath consisting of water, and then it is dried at room temperature.
  • Table 4 shows the water contact angles of the membranes formed. The images corresponding to these membrane samples, obtained by scanning electron microscopy, are shown in FIG. 4.
  • Table 4 The results in Table 4 show that the dissolution temperature of the PVDF influences the morphology of the membrane obtained. Thus, bi-continuous morphologies are obtained below 50 ° C in either ethanol or iso-propanol. A temperature higher than this value is necessary to obtain the morphology in connected nodules with a porous structure essential for obtaining superhydrophobic membranes as seen in the preceding examples.
  • a homogeneous solution of PVDF at different concentrations is prepared by dissolving it in NMP or in wet DMAc with 4% water at temperatures between 60 and 120 ° C.
  • the solution obtained is deposited on a glass plate and then spread with a knife whose air gap is set at 250 ⁇ .
  • the glass plate is then immersed in a first coagulant bath containing a low molecular weight alcohol such as iso-propanol for 10 minutes.
  • Said plate is then immersed in a second bath consisting of water and then dried at room temperature.
  • Table 5 shows the water contact angles of the membranes prepared according to Example 5. The images corresponding to these membrane samples, obtained by scanning electron microscopy, are shown in FIG. 5.
  • PVDF polyvinylidene fluoride

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
PCT/FR2011/052730 2010-11-22 2011-11-22 Membranes de pvdf a surface superhydrophobe Ceased WO2012069760A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP11802497.5A EP2643079A1 (fr) 2010-11-22 2011-11-22 Membranes de pvdf a surface superhydrophobe
US13/988,517 US20130306560A1 (en) 2010-11-22 2011-11-22 Pvdf membranes having a superhydrophobic surface
CN201180065656.6A CN103347597B (zh) 2010-11-22 2011-11-22 具有超疏水性表面的pvdf膜
KR1020137016007A KR101796637B1 (ko) 2010-11-22 2011-11-22 초소수성 표면을 갖는 pvdf 멤브레인
JP2013539326A JP5792823B2 (ja) 2010-11-22 2011-11-22 超疎水性表面を有するｐｖｄｆ膜
SG2013045836A SG191730A1 (en) 2010-11-22 2011-11-22 Pvdf membranes having a superhydrophobic surface

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1059604 2010-11-22
FR1059604A FR2967591B1 (fr) 2010-11-22 2010-11-22 Membranes de pvdf a surface superhydrophobe

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US (1) US20130306560A1 (enExample)
EP (1) EP2643079A1 (enExample)
JP (1) JP5792823B2 (enExample)
KR (1) KR101796637B1 (enExample)
CN (1) CN103347597B (enExample)
FR (1) FR2967591B1 (enExample)
SG (1) SG191730A1 (enExample)
WO (1) WO2012069760A1 (enExample)

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CN103570251A (zh) * 2012-08-01 2014-02-12 青岛大学 一种绝缘超疏水涂层的制备方法
JP2015505725A (ja) * 2011-12-13 2015-02-26 ザルトリウス ステディム ビオテック ゲーエムベーハー 構造的に誘導されるビーディング効果を有する疎水性又は疎油性の微孔性高分子膜
CN106334461A (zh) * 2016-09-26 2017-01-18 天津华清健坤膜科技有限公司 一种pvdf和psf二元共混的超滤膜及其制备方法
EP3702019A1 (en) * 2012-10-02 2020-09-02 JNC Corporation Microporous membrane and manufacturing process therefor

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CN104923085B (zh) * 2015-06-04 2017-01-18 宁波聿丰新材料科技有限公司 一种高疏水性聚偏氟乙烯复合多孔膜的制备方法
WO2017015140A1 (en) * 2015-07-17 2017-01-26 Massachusetts Institute Of Technology Multi-effect membrane distillation
CN107326670B (zh) * 2017-07-26 2020-04-07 陕西科技大学 一种耐磨超疏水纺织品涂层及制备方法
CN109486482B (zh) * 2017-09-11 2021-11-23 天津大学 氟化碳量子点、发光超疏水膜及其制备方法和应用
JP7545958B2 (ja) * 2018-10-04 2024-09-05 ユニバーシティ オブ サウス アフリカ 膜蒸留脱塩技術のための膜
US20230191335A1 (en) * 2020-05-13 2023-06-22 National University Of Singapore A semi-crystalline polymer membrane
CN111992060B (zh) * 2020-09-09 2022-05-27 天津工业大学 基于巯基烯烃点击反应改性pvdf超疏水复合膜的制备方法
CN112724437A (zh) * 2020-12-29 2021-04-30 陕西科技大学 一种超疏水辐射降温薄膜及其制备方法
CN115869778B (zh) * 2023-03-02 2023-05-16 广东省科学院生态环境与土壤研究所 一种pvdf纳米颗粒阵列多孔膜及其制备方法与应用
CN116808851B (zh) * 2023-03-08 2024-11-08 杭州师范大学 一种基于体积排斥效应的聚偏氟乙烯阶层式多孔薄膜及其制备方法和应用

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JP2015505725A (ja) * 2011-12-13 2015-02-26 ザルトリウス ステディム ビオテック ゲーエムベーハー 構造的に誘導されるビーディング効果を有する疎水性又は疎油性の微孔性高分子膜
CN103570251A (zh) * 2012-08-01 2014-02-12 青岛大学 一种绝缘超疏水涂层的制备方法
EP3702019A1 (en) * 2012-10-02 2020-09-02 JNC Corporation Microporous membrane and manufacturing process therefor
CN106334461A (zh) * 2016-09-26 2017-01-18 天津华清健坤膜科技有限公司 一种pvdf和psf二元共混的超滤膜及其制备方法

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CN103347597B (zh) 2016-07-20
SG191730A1 (en) 2013-08-30
US20130306560A1 (en) 2013-11-21
CN103347597A (zh) 2013-10-09
KR20140037018A (ko) 2014-03-26
KR101796637B1 (ko) 2017-11-10
EP2643079A1 (fr) 2013-10-02

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