WO2002102500A1 - Membrane polymer compositions - Google Patents
Membrane polymer compositions Download PDFInfo
- Publication number
- WO2002102500A1 WO2002102500A1 PCT/AU2002/000784 AU0200784W WO02102500A1 WO 2002102500 A1 WO2002102500 A1 WO 2002102500A1 AU 0200784 W AU0200784 W AU 0200784W WO 02102500 A1 WO02102500 A1 WO 02102500A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- microfiltration
- monomer
- ultrafiltration
- membrane
- manufacturing
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 217
- 229920000642 polymer Polymers 0.000 title claims description 72
- 239000000203 mixture Substances 0.000 title claims description 19
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 238000001471 micro-filtration Methods 0.000 claims abstract description 70
- 239000011148 porous material Substances 0.000 claims abstract description 70
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 68
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 56
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 39
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 19
- 239000012633 leachable Substances 0.000 claims abstract description 12
- 229920001897 terpolymer Polymers 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 7
- 239000002033 PVDF binder Substances 0.000 claims abstract 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 238000004519 manufacturing process Methods 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 22
- 239000003518 caustics Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 230000004907 flux Effects 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 6
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 238000002145 thermally induced phase separation Methods 0.000 claims 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 26
- 239000000463 material Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 230000035699 permeability Effects 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- -1 poly(tetrafluoroethylene) Polymers 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004382 potting Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 208000037516 chromosome inversion disease Diseases 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- B01D67/0018—Thermally induced processes [TIPS]
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
-
- 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
- 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
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- 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
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/0231—Dense layers being placed on the outer side of the cross-section
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Definitions
- the invention relates to compositions suitable for use in forming membranes, in
- Synthetic membranes are used for a variety of applications including desalination, gas separation, filtration and dialysis.
- membranes can be used for specific separation processes, including
- Microfiltration, ultrafiltration and reverse osmosis are examples of microfiltration, ultrafiltration and reverse osmosis.
- Microfiltration can remove very
- microfiltration can filter particles down to 0.1 ⁇ m, whereas ultrafiltration can retain
- Modules of such fibres can be made with an extremely large
- Microporous synthetic membranes are particularly suitable for use in hollow fibres and are produced by phase inversion.
- at least one polymer is
- the polymer solution can be cast as a film or hollow fibre, and then immersed in
- porous structure containing a network of uniform pores.
- Production parameters that affect the membrane structure and properties include the polymer concentration, the
- microporous membranes with a large range of pore sizes (from less than 0.1 to 20 ⁇ m), and altering chemical, thermal
- Microporous phase inversion membranes are particularly well suited to the application of removal of viruses and bacteria.
- the hollow fibre contains the largest membrane area per unit volume.
- Flat sheet membranes are prepared by bringing a polymer solution consisting of at least one polymer and solvent into contact with a coagulation bath. The solvent diffuses outwards into the coagulation bath and the precipitating solution will diffuse into the cast film. After a given period of time, the exchange of the non-solvent and solvent has proceeded such that the solution becomes thermodynamically unstable and demixing occurs. Finally, a flat sheet is obtained with an asymmetric or symmetric structure.
- Hydrophobic surfaces are defined as “water hating” and hydrophilic surfaces as “water loving”. Many of the polymers that porous membranes are made of are hydrophobic polymers. Water can be forced through a hydrophobic membrane by use of sufficient pressure, but the pressure needed is very high (150-300 psi), and a membrane may be damaged at such pressures and generally does not become wetted evenly. Hydrophobic microporous membranes are characterised by their excellent chemical resistance, biocompatibility, low swelling and good separation performance. Thus, when used in water filtration applications, hydrophobic membranes need to be hydrophilised or "wet out” to allow water permeation.
- PVDF poly(vinylidene fluoride)
- PVDF exhibits a number of desirable characteristics for membrane applications, including thermal resistance, reasonable chemical resistance (to a range of corrosive chemicals, including sodium hypochlorite), and weather (UV) resistance. While PVDF has to date proven to be the most desirable material from a range of materials suitable for microporous membranes, the search continues for membrane materials which will provide better chemical stability and performance while retaining the desired physical properties required to allow the membranes to be formed and worked in an appropriate manner. In particular, a membrane is required which has a superior resistance (compared to
- PVDF to more aggressive chemical species, in particular, oxidising agents such as sodium hypochlorite and to conditions of high pH i.e. resistance to caustic solutions.
- the invention provides the use of polymer suitable for forming into an ultrafiltration or microfiltration membrane, said polymer being a terpolymer of tetrafluoroethylene (TFE), PVDF and hexafluoropropylene monomers.
- TFE tetrafluoroethylene
- the polymer includes from 20-65% PVDF monomer, from 10-20% hexafluoropropylene monomer and 30-70 % TFE. More preferably, the polymer includes from 30-50% PVDF monomer, from 15-
- the polymer includes from 35-40% PVDF and 17-20% HFP and 40-48% TFE.
- the polymer is a terpolymer of 44.6% tetrafluoroethylene (TFE)
- the invention provides an ultrafiltration and/or microfiltration membrane formed from a terpolymer including TFE monomers, PVDF
- the monomer composition is
- TFE tetrafluoroethylene
- the membranes of the second aspect have an improved chemical stability to
- the invention provides a method of manufacturing a
- microfiltration or ultrafiltration membrane including the step of casting a membrane
- TFE tetrafluoroethylene
- the membrane is in the form of a hollow fibre, cast by the TIPS
- the polymer used is THV 220G, obtained from Dyneon ® (3M) as
- the polymer is a combination of approximately 44.6%
- the invention provides a method of forming a polymeric ultrafiltration or microfiltration membrane including the steps of: preparing a leachant resistant membrane dope; incorporating a leachable pore forming agent into the dope; casting a membrane; and leaching said leachable pore forming agent from said membrane with said leachant.
- the leachant resistant membrane polymer includes a terpolymer of TFE, PVDF and hexafluoropropylene. More preferably, the polymer includes 44.6% tetrafluoroethylene (TFE) monomers, 36.5% PVDF monomers, and 18.9% hexafluoropropylene monomers.
- TFE tetrafluoroethylene
- the leachable pore forming agent is silica, and the leachant is a caustic solution, but the pore forming agent may for preference be any inorganic solid with an average particle size less than 1 micron while the leachant may be any material/solution that leaches the said pore forming agent from the membrane.
- the invention provides a method of improving the structure of a polymeric ultrafiltration or microfiltration membrane by the addition of a nucleating agent to a membrane dope.
- a nucleating agent is added in catalytic amounts and most preferably it is TiO 2 , however, any insoluble/inert (unleachable) inorganic solid with an average particle size less than 1 micron may be used.
- the invention provides an elastic polymeric ultrafiltration or microfiltration membrane having an asymmetric cross section defining a large-pore face and a small-pore face; said membrane having a higher flux at a given pressure from said large-pore face to said small-pore face than from said small-pore face
- the elastic membrane is formed from the preferred membrane forming
- NMP methylpyrrolidone
- Non-solvent consisting of 20% NMP
- the hollow fibre was then spun into the quench bath and solidified, before being run out of the bath over driven rollers onto a winder situated in a secondary
- the membrane structure was reasonable although a skin was found on the surface
- the caustic resistance of the membrane was tested by placing a sample of the flat
- Table 1 shows the results of the caustic resistance tests. The results indicate that
- the PVDF membrane had lost a marked amount of flexibility and was
- hydrophilic membranes are simpler to operate than hydrophobic membranes as they do not require an additional wetting step.
- Lutonal A25 Polyvinylethylether
- GTA glycerine triacetate
- silica was added to the dope with the intention of leaching the silica
- hydrophilic silica Aerosil 200 and a hydrophobic silica Aerosil R972 were tested
- Table 2 demonstrates that the silica is required in reasonably high concentrations to make the membranes hydrophilic. It also shows the trend of increasing viscosity with increasing silica content. After the membranes were cast, and prior to leaching, the membranes were examined using scanning electron microscopy. The structures were generally extremely
- the cross-sectional appearance was more like a conglomerate of precipitated particles, rather than a true honeycomb like structure.
- silica appeared to be the hydrophobic Aerosil R972, although
- both forms of silica produced a hydrophilic membrane with a highly porous structure.
- the optimal dope for forming a DIPS polymer appears to be from a mixture of
- a number of hollow fibre membranes were prepared from the above dope.
- the leaching of the silica from the membranes has a positive effect upon permeability.
- the membrane had very few pores and extremely low flows.
- a long leaching time is not necessarily required and can be incorporated in the
- the silica particles have a size
- silica particle adheres to the polymer matrix by hydrophobic interaction and/or mechanical anchoring.
- the inside of the particle wall is
- hydrophilic because it consists of OH groups attached to silica. Because the silica is
- TiO 2 (titania) was also added to the membrane at a variety of concentrations. TiO 2 has been added to membrane forming mixtures previously as a filler to provide
- solidification sites at which precipitation occurs means that the pores formed near the
- membrane surface are smaller, fewer and further between.
- titania need be incorporated into the membrane, although as much as 3% can be used
- a dope formulation giving good results is 20 wt% THV 220G, 6 wt% Aerosil
- a dope having the above formulation was mixed and cast according to the DIPS
- Table 3 lists the properties of the membranes made which incorporate a small
- Table 4 lists the properties of the membrane made using 22% polymer (without
- PVDF membranes require a more flexible potting material such as polyurethane to prevent damage to the fibres. PVDF fibres can break with relative ease if the fibers are potted in a potting material which lacks any flexibility. If there is no flexibility in the potting material there can be breakage of the fiber at the point where the fiber enters the pot.
- the membranes of the invention can be potted into epoxy potting material and the fibers will not be significantly damaged during use. In fact, the membranes of the present invention can be stretched to the normal break extension of the fibre when pulled parallel to the pot
- Table 6 gives a comparison between THV membranes manufactured using the
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/738,628 US7226541B2 (en) | 2001-06-20 | 2003-12-16 | Membrane polymer compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPR5843A AUPR584301A0 (en) | 2001-06-20 | 2001-06-20 | Membrane polymer compositions |
AUPR5843 | 2001-06-20 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/738,628 Continuation US7226541B2 (en) | 2001-06-20 | 2003-12-16 | Membrane polymer compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002102500A1 true WO2002102500A1 (en) | 2002-12-27 |
Family
ID=3829814
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2002/000784 WO2002102500A1 (en) | 2001-06-20 | 2002-06-14 | Membrane polymer compositions |
Country Status (3)
Country | Link |
---|---|
US (1) | US7226541B2 (en) |
AU (1) | AUPR584301A0 (en) |
WO (1) | WO2002102500A1 (en) |
Cited By (8)
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WO2003086595A1 (en) * | 2002-04-12 | 2003-10-23 | Pall Corporation | Hydrophobic membrane materials for filter venting applications |
US7140496B2 (en) | 2001-08-01 | 2006-11-28 | Asahi Kasei Medical Co., Ltd. | Multilayer microporous membrane |
US7459085B2 (en) | 2002-10-18 | 2008-12-02 | Asahi Kasei Medical Co., Ltd. | Microporous hydrophilic membrane |
US7635513B1 (en) | 1999-10-22 | 2009-12-22 | Asahi Kasei Medical Co., Ltd. | Heat resistant microporous film |
WO2012027970A1 (en) * | 2010-09-02 | 2012-03-08 | The University Of Hong Kong | Doping of inorganic minerals to hydrophobic membrane surface |
CN104437123A (en) * | 2014-11-14 | 2015-03-25 | 陈泉学 | Production method of polyvinylidene fluoride microporous film |
CN104857866A (en) * | 2015-05-18 | 2015-08-26 | 上海交通大学 | Method for preparing hydrophilic modified polyvinylidene fluoride membrane |
CN106362602A (en) * | 2016-11-21 | 2017-02-01 | 天津华清健坤膜科技有限公司 | Hollow fiber hydrophobic membrane and preparation method thereof |
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AUPR143400A0 (en) * | 2000-11-13 | 2000-12-07 | Usf Filtration And Separations Group Inc. | Modified membranes |
AUPR421501A0 (en) | 2001-04-04 | 2001-05-03 | U.S. Filter Wastewater Group, Inc. | Potting method |
AUPR692401A0 (en) | 2001-08-09 | 2001-08-30 | U.S. Filter Wastewater Group, Inc. | Method of cleaning membrane modules |
AUPS300602A0 (en) | 2002-06-18 | 2002-07-11 | U.S. Filter Wastewater Group, Inc. | Methods of minimising the effect of integrity loss in hollow fibre membrane modules |
JP4282598B2 (en) | 2002-10-10 | 2009-06-24 | シーメンス・ウォーター・テクノロジーズ・コーポレーション | Filtration device and method for cleaning the filtration device |
AU2002953111A0 (en) | 2002-12-05 | 2002-12-19 | U. S. Filter Wastewater Group, Inc. | Mixing chamber |
AU2003903507A0 (en) | 2003-07-08 | 2003-07-24 | U. S. Filter Wastewater Group, Inc. | Membrane post-treatment |
WO2005014151A1 (en) * | 2003-08-06 | 2005-02-17 | Zhejiang Omex Environmental Engineering Ltd. | The preparation method of exo-pressure type poly(vinylidene fluoride) hollow fiber membrane spinned utilizing a immersion-coagulation method and the product thereof |
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WO2005037917A1 (en) * | 2003-10-20 | 2005-04-28 | Zenon Environmental Inc. | System and method for synthesizing a polymer membrane |
KR20070003783A (en) | 2003-11-14 | 2007-01-05 | 유.에스. 필터 웨이스트워터 그룹, 인크. | Improved module cleaning method |
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WO2012027970A1 (en) * | 2010-09-02 | 2012-03-08 | The University Of Hong Kong | Doping of inorganic minerals to hydrophobic membrane surface |
US20160129399A1 (en) * | 2010-09-02 | 2016-05-12 | The University Of Hong Kong | Doping of inorganic minerals to hydrophobic membrane surface |
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US10940445B2 (en) | 2010-09-02 | 2021-03-09 | The University Of Hong Kong | Doping of inorganic minerals to hydrophobic membrane surface |
CN104437123A (en) * | 2014-11-14 | 2015-03-25 | 陈泉学 | Production method of polyvinylidene fluoride microporous film |
CN104857866A (en) * | 2015-05-18 | 2015-08-26 | 上海交通大学 | Method for preparing hydrophilic modified polyvinylidene fluoride membrane |
CN106362602A (en) * | 2016-11-21 | 2017-02-01 | 天津华清健坤膜科技有限公司 | Hollow fiber hydrophobic membrane and preparation method thereof |
Also Published As
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US7226541B2 (en) | 2007-06-05 |
US20040191894A1 (en) | 2004-09-30 |
AUPR584301A0 (en) | 2001-07-12 |
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