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.
• FIG 1 illustrates the membranes prepared in Example 1
• FIG. 2 illustrates the membranes prepared in example 2
• 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;
• the structure of the PVDF membranes according to the invention is of the interconnected type.
• 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 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 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)
• Laminated Bodies (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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• 2010
  • 2010-11-22 FR FR1059604A patent/FR2967591B1/fr not_active Expired - Fee Related
• 2011
  • 2011-11-22 WO PCT/FR2011/052730 patent/WO2012069760A1/fr not_active Ceased
  • 2011-11-22 SG SG2013045836A patent/SG191730A1/en unknown
  • 2011-11-22 US US13/988,517 patent/US20130306560A1/en not_active Abandoned
  • 2011-11-22 EP EP11802497.5A patent/EP2643079A1/fr not_active Ceased
  • 2011-11-22 JP JP2013539326A patent/JP5792823B2/ja not_active Expired - Fee Related
  • 2011-11-22 KR KR1020137016007A patent/KR101796637B1/ko not_active Expired - Fee Related
  • 2011-11-22 CN CN201180065656.6A patent/CN103347597B/zh not_active Expired - Fee Related

Non-Patent Citations (4)

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