WO2009027376A1 - Filled polymeric membranes, use and method of manufacturing - Google Patents
Filled polymeric membranes, use and method of manufacturing Download PDFInfo
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- WO2009027376A1 WO2009027376A1 PCT/EP2008/061095 EP2008061095W WO2009027376A1 WO 2009027376 A1 WO2009027376 A1 WO 2009027376A1 EP 2008061095 W EP2008061095 W EP 2008061095W WO 2009027376 A1 WO2009027376 A1 WO 2009027376A1
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- Prior art keywords
- suspension
- filler
- aggregates
- filled polymeric
- mixing
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 128
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 105
- 239000000725 suspension Substances 0.000 claims abstract description 93
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000005373 pervaporation Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000001728 nano-filtration Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 78
- 238000002156 mixing Methods 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 35
- 238000009826 distribution Methods 0.000 claims description 34
- 238000003760 magnetic stirring Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000377 silicon dioxide Substances 0.000 description 20
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000035699 permeability Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000012466 permeate Substances 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000010633 broth Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- JSGITCLSCUKHFW-UHFFFAOYSA-N 2,2,4-trifluoro-5-(trifluoromethoxy)-1,3-dioxole Chemical compound FC1=C(OC(F)(F)F)OC(F)(F)O1 JSGITCLSCUKHFW-UHFFFAOYSA-N 0.000 description 1
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 1
- SLMFWJQZLPEDDU-UHFFFAOYSA-N 4-methylpent-2-yne Chemical compound CC#CC(C)C SLMFWJQZLPEDDU-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DCGLONGLPGISNX-UHFFFAOYSA-N trimethyl(prop-1-ynyl)silane Chemical compound CC#C[Si](C)(C)C DCGLONGLPGISNX-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01D61/362—Pervaporation
-
- 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
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix 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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
- B01D71/701—Polydimethylsiloxane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/21—Fillers
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- 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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- 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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249991—Synthetic resin or natural rubbers
Definitions
- the present invention is related to polymeric membranes comprising fillers, to methods of manufacturing them and to uses thereof.
- the fillers are nanometre-sized particles.
- the membrane polymers are glassy polymers having a glass transition temperature higher than or equal to 100 0 C. Filled polymeric membranes find application in processes for separating a mixture of (fluid) components. Examples of the latter are gas and vapour separation.
- the polymer is poly (1-trimethylsilyl-l- propyne) , also known as PTMSP and nanoparticles of silica are used as the filler material.
- the method of manufacturing the membrane is a three-step solvent casting procedure. First, silica is dispersed in toluene by 30 minutes ultrasonic and 3 hours magnetic stirring. Secondly, the PTMSP is dissolved in the silica/toluene dispersion and finally, the solution is cast on a glass plate and dried. [0003] By that method, membranes were obtained comprising aggregates of silica particles in the polymer matrix. It was observed that the silica aggregates in the polymer matrix comprised interstitial nanometre-sized cavities, the average size of which was found to increase with increasing filler content.
- interstitial cavities offer a faster, however non-selective, route of transportation to the penetrants. This results in a higher permeability of the filled membrane, but also in a decrease in selectivity.
- the present invention aims to provide a method of manufacturing a filled polymeric membrane, which method allows to tailor the membrane based on more than one parameter in order to obtain a membrane with predetermined properties .
- the present invention also aims to provide a method of manufacturing a filled polymeric membrane which allows a better control of the structure and/or the characteristics of the obtained membrane.
- the present invention also aims to provide a filled polymeric membrane having at least equal or improved properties compared to filled polymeric membranes of the prior art.
- the present invention also aims to provide membrane separation processes having an improved performance over processes of the prior art. Particularly, the present invention aims to provide an improved pervaporation process, in particular for concentrating ethanol out of ethanol/water mixtures. Furthermore, the invention aims to provide an improved nanofiltration process .
- Aims of the invention are achieved by providing a method of manufacturing a filled polymeric membrane as set out in the appended claims. [0015] Aims of the invention are achieved by providing a filled polymeric membrane as set out in the appended claims.
- Aims of the invention are achieved by providing, as set out in the appended claims, uses or applications of filled polymeric membranes of the invention in methods of pervaporation and/or uses or applications of said filled polymeric membranes in methods of nanofiltration .
- a method of manufacturing a filled polymeric membrane comprises a first step of preparing a filler suspension comprising (or consisting of) a solvent for a glassy polymer and nanometre-sized particles.
- the nanometre-sized particles in said filler suspension are aggregated in aggregates having an average aggregate size in the range between 50 nm and up to but not including 200 nm.
- the glassy polymer has a glass transition temperature of at least 100 0 C.
- the glassy polymer is added to the filler suspension to obtain a polymer suspension.
- the glassy polymer is dissolved in the polymer suspension.
- the polymer suspension is cast on a substrate, followed by a step of removing the solvent.
- the step of preparing a filler suspension advantageously comprises a step of mixing said filler suspension so as to obtain the aggregates of nanometre- sized particles as indicated.
- the step of preparing a filler suspension comprises selecting (predetermining) a mixing method for mixing the filler suspension (so as to obtain the aggregates of nanometre-sized particles as indicated) .
- the mixing method can be magnetic stirring.
- the mixing method can also be mechanical stirring.
- the mixing method can be ultrasonic stirring as well.
- the mixing method can be rolling or shaking.
- the step of preparing a filler suspension comprises mixing the filler suspension by only one mixing method.
- the step of preparing a filler suspension comprises selecting (predetermining) a mixing time in which applying the mixing method to the filler suspension. More preferably, the step of preparing a filler suspension comprises selecting (predetermining) a mixing intensity for applying to the mixing method.
- the step of dissolving the glassy polymer comprises a step of mixing the polymer suspension. More preferably, said dissolving step further comprises selecting (predetermining) a mixing method for said mixing step.
- the mixing methods in the step of preparing the filler suspension and in the step of dissolving the glassy polymer are preferably the same.
- the size distribution of the aggregates of nanometre-sized particles has a standard deviation smaller than 100 nm, more preferably smaller than 50 nm. The standard deviation is calculated based on the size distribution of the aggregates.
- Average aggregate sizes and standard deviations are to be calculated based on number (size) distributions of the aggregate size.
- the size distribution of aggregates of nanometre-sized particles in filler suspensions according to the invention can be measured with dynamic light scattering.
- the suspension in the step of preparing a filler suspension, comprises between 0.01 wt% and 6 wt% nanometre-sized particles, more preferably between 0.01 wt% and 2.4 wt% .
- the suspension in the step of preparing a filler suspension, comprises between 0.001 vol% and 3 vo1% (volume%) nanometre-sized particles.
- the nanometre-sized particles are hydrophobic .
- the nanometre-sized particles are non-porous .
- a filled polymeric membrane for separating a mixture of fluids.
- the membrane comprises: a glassy polymer having a glass transition temperature of at least 100 0 C and nanometre-sized filler particles.
- the filler particles are arranged in aggregates, the aggregates having an average aggregate size of at least 50 nm and smaller than 200 nm.
- Filled polymeric membranes according to the invention can be obtained by application of methods of the invention .
- the size distribution of the aggregates of nanometre-sized particles in the filled polymeric membrane of the invention has a standard deviation smaller than or equal to 150 nm, more preferably smaller than 100 nm, even more preferably smaller than 50 nm. The standard deviation is calculated based on the size distribution of the aggregates.
- Average aggregate sizes and standard deviations are to be calculated based on number (size) distributions of the aggregate size.
- the size distribution of aggregates of nanometre-sized particles in polymeric membranes according to the invention can be measured with image analysis.
- the filled polymeric membrane of the invention comprises between 0.01 wt% and 90 wt% nanometre-sized filler particles, more preferably between 0.01 wt% and 60 wt%.
- the filled polymeric membrane of the invention comprises between 0.003 vol% and 75 vol% nanometre-sized filler particles.
- an apparatus for separating a mixture of components by pervaporation comprising the filled polymeric membrane of the invention.
- an apparatus for separating a mixture of components by nanofiltration comprising the filled polymeric membrane of the invention.
- a use or application of the abovementioned filled polymeric membrane in a process of separating a mixture of components is provided.
- the process of separating a mixture of components is preferably a pervaporation process. More preferably, said mixture of components consists
- the process of separating a mixture of components can be a nanofiltration process.
- Figure 1 represents the aggregate size distribution for a suspension of 0.2 g silica nanoparticles in 48 g toluene after 5 minutes magnetic stirring in a KMO 2B magnetic stirrer at 450 rpm (IKA Werke, Germany) .
- Figure 2 represents the aggregate size distribution for a suspension of 0.2 g silica nanoparticles in 48 g toluene after 20 minutes magnetic stirring (at 450 rpm) in the stirrer of figure 1.
- Figure 3 represents the aggregate size distribution for a suspension of 0.2 g silica nanoparticles in 48 g toluene after 60 minutes magnetic stirring (at 450 rpm) in the stirrer of figure 1.
- Figure 4 represents the aggregate size distribution for a suspension of 1 g silica nanoparticles in 48 g toluene after 5 minutes magnetic stirring (at 450 rpm) in the stirrer of figure 1.
- Figure 5 represents the aggregate size distribution for a suspension of 1 g silica nanoparticles in 48 g toluene after 3 minutes ultrasonic stirring with a Vibracell CV 26 ultrasonic stirrer (Sonics & Materials, USA) .
- Figure 6 represents a flow chart of an embodiment of the method of the invention of manufacturing a filled polymeric membrane.
- the inventors have found a way of improving the performance of filled polymeric membranes, enabling to reconcile high permeabilities and high selectivities .
- the inventors found that, besides the filler content, also the aggregate size may play an important role in the performance of filled polymeric membranes. Indeed, a controlled size of the filler aggregates in the membrane, as identified in the present invention can allow to prevent a deterioration of the selectivity, and can possibly even increase it.
- the inventors have found a way of tailoring the size of aggregates of nanoparticle fillers during the manufacturing of a filled polymeric membrane. This can allow for tailoring the average interstitial cavity size not only based on the nanoparticle filler content, but also based on the size of the nanoparticle filler aggregates.
- the size of the nanoparticle (filler) aggregates can be an additional parameter for tailoring the membrane in order to achieve predetermined properties. For a given filler content, varying the filler aggregate size leads to differences in average interstitial cavity sizes. Moreover, as the interstitial cavities are believed to be responsible for the fast transportation of penetrants, the filler aggregates in the membrane matrix are tailored, such that their size fall in a predetermined range.
- Nanoparticle refers to a nanometre-sized particle. Nanoparticles can have a size smaller than 50 nm and preferably smaller than 25 nm. Nanoparticles preferably have a size larger than or equal to 1 nm.
- filler refers to a material in the form of nanoparticles which is suitable for use as filler material in a glassy polymeric membrane.
- Suitable filler materials can be silica and metal oxides, such as Ti ⁇ 2.
- the nanoparticles of the filler material are preferably non- porous.
- the nanoparticles preferably have a high specific surface area.
- the nanoparticles can be treated or coated, e.g. to make them hydrophobic.
- Glassy polymeric membranes comprise a glassy polymer as membrane material.
- a glassy polymer refers to a polymer having a glass transition temperature above the temperature at which the polymer will be used.
- the glassy polymers used for the present invention have a glass transition temperature of at least 100 0 C.
- the glassy polymers preferably have a high free volume, meaning a fractional free volume of at least 0.20.
- Possible glassy polymers envisaged by the invention are: substituted polyacetylene polymers, such as PTMSP and PMP: poly (4- methyl-2-pentyne) and amorphous perfluoropolymers, such as Teflon® (copolymer of tetrafluoroethylene and 2,2- bis (trifluoromethyl) -4, 5-difluoro-1, 3-dioxole) and Hyflon®
- the present invention presents a method of manufacturing a glassy polymeric membrane comprising nanoparticle fillers.
- the method of the invention comprises a first step SIl, as illustrated in the flow chart of figure 6, in which a suspension (filler suspension) is prepared of a solvent and a nanoparticle filler material.
- the solvent is a solvent for the glassy polymer of which the membrane is made.
- Toluene, cyclohexane, benzene, chloroform and tetrahydrofuran can be used as a solvent for dissolving PTMSP.
- Cyclohexane and carbon tetrachloride are preferably used as a solvent for dissolving PMP.
- the filler suspension preferably comprises between 0.01 and 6 weight% (wt%) nanoparticle fillers, more preferably between 0.01 and 2.4 wt%.
- the filler suspension can comprise between 0.001 and 3 volume% (vol%) nanoparticle fillers.
- the inventors have found that the nanoparticle fillers can be aggregated in aggregates of a predetermined average size during the step of preparing a suspension of a solvent and the filler (nanoparticles) .
- a suspension in which the nanoparticles form aggregates having a predetermined average aggregate size can be prepared by mixing the filler suspension with an appropriate mixing method.
- the mixing method can be applied to the suspension during a predetermined mixing time and preferably at a predetermined intensity.
- preparing the filler suspension comprises mixing the filler suspension with a mixing method during a mixing time.
- a predetermined average nanoparticle filler aggregate size can be obtained by applying a mixing method during a predetermined mixing time.
- the selection of a mixing intensity can additionally determine the aggregate size.
- a mixing time and preferably a mixing intensity are predetermined (selected) for the mixing method. Additional factors that influence the average aggregate size can be: the quantity to be prepared, the kind and size of nanoparticle fillers, the kind of glassy polymer and the kind of solvent.
- the mixing time and intensity can additionally depend on the mixing method.
- methods according to the invention preferably comprise a step of selecting a mixing method for mixing the filler suspension so as to obtain aggregate sizes as identified. More preferably, based on the mixing method, a mixing time and possibly a mixing intensity is selected.
- Magnetic stirring, mechanical stirring, ultrasonic stirring, rolling and shaking are preferred mixing methods, but the invention is not limited to these mixing methods. Magnetic stirring, mechanical stirring, rolling and shaking are more preferred mixing methods. Preferably, only one mixing method is used in the step SIl of preparing a filler suspension.
- the preferred average nanoparticle filler aggregate size in the filler suspension falls in the range between 50 nm and 250 nm, more preferably in the range between 50 nm and up to but not including 200 nm.
- the filler aggregate size distribution preferably has a standard deviation smaller than or equal to 100 nm, more preferably smaller than or equal to 50 nm. This means that the filler aggregate size is preferably distributed with standard deviations as indicated.
- Indicated filler aggregate sizes and distributions have found to be optimal in producing filled polymeric membranes. Smaller aggregates tend to combine into larger clusters at the time of casting and solvent evaporation and lead to an uncontrolled aggregate size and possibly to combined aggregates that are too large. Larger aggregates can feature larger deviations from the average, leading to varying product (membrane) characteristics. Larger aggregates offer increased non-selective permeation routes. [0071] When aggregates in the filler suspension occur with sizes (or in a distribution) as indicated, according to the invention the aggregates in the eventual filled polymeric membranes can occur with optimal aggregate size distributions.
- Aggregate size distributions in the filler suspension are preferably those falling in the range as indicated in table 1, more preferably those falling in the range as indicated in table 2.
- the amount of filler aggregates in the suspension, having a size smaller than 200 nm falls in the range between 51% and 90%.
- Table 1 Preferred size distribution of the filler aggregates in a filler suspension.
- Table 2 Preferred size distribution of the filler aggregates in a filler suspension.
- figures 1 to 3 plot the aggregate size distribution of nanoparticle-silica (Cabosil TS-530, Cabot Corp. Germany) in a toluene suspension.
- the diameter of the silica nanoparticles was measured based on the specific surface area and was found to be about 13 nm.
- the aggregate size in the suspension was measured with dynamic light scattering by a ZetaPlus Particle Sizing apparatus (Brookhaven Instruments Corp.).
- TS-530 is a fumed silica that has been made hydrophobic by a treatment with hexamethyldisilazane .
- the reported density is 2.2 g/cm 3
- the suspension was prepared by adding 0.2 g silica nanoparticles to 48 g of toluene.
- Five minutes of magnetic stirring with a KMO 2B magnetic stirrer (IKA Werke, Germany) at an intensity of 450 rpm lead to the aggregate size as shown in fig. 1.
- Twenty minutes magnetic stirring (with same device at the same intensity) lead to a different aggregate size as shown in fig. 2 and 60 minutes magnetic stirring lead to the aggregate size as in figure 3.
- Figures 1 to 3 show the distribution of the aggregate size, normalized with reference to the interval with highest occurrence (left scale, bar with highest occurrence is taken as reference of 100%) .
- the scale on the right refers to the curve indicating cumulative values.
- Figure 1 shows that after 5 minutes magnetic stirring, the majority of the aggregates had a size between 100 nm and 250 nm, while there were a smaller number of aggregates having a larger size (larger than 300 nm, between 500-800 nm) . After 20 minutes magnetic stirring, as illustrated by figure 2, all aggregates had sizes ranging between 100 and 300 nm (average aggregate size of 160 nm) .
- Figure 3 illustrates the effect of long stirring times on the aggregate size. The aggregates increased in size, having a range now between 900 and 1300 nm.
- figure 2 indicates a preferred distribution for the aggregate size. Hence, magnetic stirring for 20 minutes would be satisfactory for the given suspension. Magnetic stirring for 60 minutes leads to filler aggregate sizes which are too large. For the given suspension, magnetic stirring should be applied for less than 60 minutes.
- FIGS 4 and 5 plot the aggregate size distribution of suspensions of 1 g silica nanoparticles in 48 g toluene.
- the distribution of figure 4 is obtained after 5 minutes magnetic stirring.
- the distribution of figure 5 is obtained after 3 minutes ultrasonic stirring.
- the membrane polymer is added to the filler suspension comprising the solvent and the aggregates of nanoparticles to form a polymer suspension.
- the membrane polymer is a glassy polymer, such as PTMSP or PMP.
- the amount of polymer added to the filler suspension can be such that the total dry matter of the polymer suspension falls in the range between 0.1 and 10 weight%, preferably between 0.1 wt% and 6 wt%.
- the total dry matter refers to the mass of the polymer and of the nanoparticle filler material in the polymer suspension.
- the glassy polymer is dissolved in the polymer suspension. This can be done by mixing the suspension in order to dissolve the polymer. As the suspension now has a higher viscosity, the mixing method in the present step is less critical for tailoring the size of the nanoparticle aggregates.
- the mixing method and the mixing time and preferably also the mixing intensity can be determined (selected) based on the same criteria as in the first step.
- the mixing method M2 of step S13 is preferably the same as mixing method Ml of the first step SIl.
- the mixing intensity 12 applied in step S13 is preferably not higher than the mixing intensity Il applied in step SIl.
- the mixing time T2 is typically longer than mixing time Tl due to the long times needed for dissolving the polymer.
- the suspension with dissolved polymer is cast on a substrate in a next step S14.
- the substrate can be porous or non-porous. Non-porous substrates, such as glass and polyacrylonitrile, are merely used to cast the membrane in a defined shape. Porous substrates can be membrane supports and can be used for reinforcing the membrane.
- the solvent is removed from the suspension, so as to obtain a membrane. Solvent removal can be performed by evaporation. After removal of the solvent, the membrane can be removed from the substrate (in case the substrate is not a reinforcing support) . Otherwise, a membrane with reinforcing support is obtained. Additional treatments can be performed on the membrane, as are known in the art.
- the invention is also related to nanoparticle-filled polymeric membranes comprising aggregates of nanoparticles .
- Such membranes can be obtained by methods of manufacturing of the invention.
- the polymer is a glassy polymer having a glass transition temperature of at least 100 0 C.
- the nanoparticles in the membrane are arranged in aggregates having an average aggregate size of at least 50 nm and smaller than 200 nm.
- the size distribution of the aggregates of filler particles in the filled polymeric membranes of the invention can have a standard deviation smaller than or equal to 150 nm, preferably smaller than 100 nm and more preferably smaller than 50 nm. This means that the aggregate size is preferably so distributed to have standard deviations as indicated.
- Average aggregate sizes and standard deviations are based on number distribution.
- Aggregate size distributions in filled membranes according to the invention are preferably those falling in the range as indicated in table 3, more preferably those falling in the range as indicated in table 4.
- the amount of filler aggregates in the filled membranes, having a size smaller than 200 nm falls in the range between 51% and 90%.
- a well-defined aggregate size distribution leads to a product with uniform and repeatable performance capabilities .
- aggregates that are too large in size can form interstitial cavities that are too large or too high in amount, which negatively affects the selectivity of a membrane. Therefore, in most cases the aggregate size is preferably selected such that an optimal balance is obtained between permeability and selectivity of the membrane .
- Table 3 Preferred size distribution of the filler aggregates in a filled polymeric membrane.
- Aggregate sizes in filled polymeric membranes according to the invention can be measured with image analysis. A possible procedure that can be followed is described by Mullens et al . in Cellular Ceramics, chapter “Characterization of structure and morphology” pp. 227-263, Wiley-VCH Verlag, 2005, edited by M. Scheffler and P. Colombo. Aggregate sizes as indicated refer to an equivalent circle diameter.
- the membranes of the invention preferably comprise between 0.01 wt% and 90 wt% nanoparticles, more preferably between 0.01 wt% and 60 wt% nanoparticles, even more preferably between 0.01 wt% and 40 wt% and particularly preferably between 0.01 wt% and 30 wt%.
- the membranes of the invention can comprise between 70 wt% and 90 wt% of nanoparticles.
- the membranes of the invention preferably comprise between 0.003 vol% and 75 vol% nanoparticles.
- the filled polymeric membranes of the invention can find application in apparatuses for separating a mixture of components by pervaporation . They can find application in nanofiltration apparatuses as well.
- Nanoparticle-filled glassy polymeric membranes can advantageously be used in processes for separating a mixture of (fluid) components. Examples of the latter are gas and vapour separation.
- the inventors found that such membranes can advantageously be used in pervaporation processes.
- the membranes can also be used in nanofiltration processes.
- Pervaporation is a fractionation process, in which a liquid mixture is maintained at atmospheric pressure on the feed side of the membrane and the permeate is removed as a vapour. Transport through the membrane is induced by the vapour pressure difference between the feed and the permeate vapour. The pressure difference can be achieved by using a vacuum pump at the permeate side, or by cooling the permeate vapour to create a partial vacuum.
- the properties of a gas separation membrane for a given gas mixture can be predicted by measuring the pure gas properties, this is not the case for pervaporation, because the separation of a liquid mixture is influenced by the interaction of each feed component with the polymer and possibly the filler material and the interaction between the different feed components.
- the affinity of liquids for polymers is much larger than the affinity of gasses for the same polymers, which leads to higher sorption coefficients.
- the separation capacity of a pervaporation membrane is primarily a function of the membrane material and the feed species . Secondary influences are feed temperature, feed composition and permeate pressure. Hence, finding a performing membrane for concentrating a given liquid mixture by pervaporation is not a straightforward task.
- Pervaporation is used on an industrial scale to separate ethanol from its dilute aqueous solutions.
- One of the applications wherein ethanol/water separation is the key factor is the production of bio-ethanol.
- Bio-ethanol can be produced from the fermentation of sugar by enzymes produced from specific varieties of yeast.
- the fermentation product comprises large quantities of water, hence requiring bio-ethanol to be extracted from an ethanol/water mixture. This can be performed by conventional techniques, such as distillation and solvent extraction, but these processes are very energy consuming.
- Pervaporation with ethanol-selective membranes allows to concentrate low-concentration bio-ethanol from fermentation broths in an economically effective way.
- PDMS polydimethylsiloxane
- Table 5 compares the performance of prior art membranes and of membranes obtained by the invention in pervaporation of ethanol/water mixtures.
- the latter membranes offer a higher selectivity and high permeabilities compared with the membranes used in the art for ethanol/water pervaporation.
- Table 5 Comparison of filled PDMS and PTMSP (with 50 wt% filler content) membranes for pervaporation.
- the feed consisted of ethanol and water.
- the separation factor is the ratio of the permeate-to-feed weight fraction of ethanol to the permeate-to-feed weight fraction of water.
- the filled PDMS membrane is a PERVAP 1070 from Sulzer, Switzerland (hydrophobic zeolite silicalite-1 filled membrane) .
- 1.002 g of silica nanoparticles were added tot 50 g toluene and magnetically stirred during 5 minutes.
- the aggregates of the silica nanoparticles in the suspension had an average aggregate size of 110 nm.
- 1 g PTMSP was added and the suspension was magnetically stirred during 4 days, until the polymer was completely dissolved in the suspension.
- the suspension was cast on a glass plate and the solvent was allowed to evaporate under ambient conditions, leaving a filled polymer film (i.e. the membrane) of 125 ⁇ m thickness. After evaporation, the polymer film was removed from the glass plate by immersion in demi-water.
- the nanoparticle fillers constituted 50 wt% of the membrane.
- the membrane was heated for 2 hours at 80 0 C and tested for the pervaporation of ethanol/water mixtures.
- a feed of 10 wt% ethanol in water mixture was circulated at one side of the membrane and a vacuum of 0.2 mbar was maintained on the other side of the membrane.
- a permeate of 63 wt% ethanol/water mixture was collected at said other side.
- the flux through the membrane was 0.4 kg/m 2 .h.
- the PTMSP/silica/toluene suspension of example 1 was diluted to a dry matter content of 3 wt% and cast on a porous polyacrylonitrile (PAN) layer with a casting thickness of 1 mm. After evaporation of the solvent, a filled polymer film (i.e. the membrane) of 30 ⁇ m was formed on top of the porous PAN layer. The weight fraction of the nanoparticle fillers in the membrane was 50 wt% . [0102] The obtained membrane was heated for 2 hours at 80°C in order to completely remove the solvent and tested for the pervaporation of ethanol/water mixtures.
- PAN polyacrylonitrile
- a 5 wt% ethanol in water mixture was circulated at one side of the membrane and a vacuum of 0.2 mbar was maintained on the other side of the membrane.
- a permeate of 40 wt% ethanol/water mixture was collected on said other side.
- the flux through the membrane was 1,25 kg/m 2 .h.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08787450A EP2180939A1 (en) | 2007-08-24 | 2008-08-25 | Filled polymeric membranes, use and method of manufacturing |
CN2008801042127A CN101820986B (en) | 2007-08-24 | 2008-08-25 | Filled polymeric membranes, use and method of manufacturing |
CA 2695730 CA2695730A1 (en) | 2007-08-24 | 2008-08-25 | Filled polymeric membranes, use and method of manufacturing |
US12/675,056 US8557022B2 (en) | 2007-08-24 | 2008-08-25 | Filled polymeric membranes, use and method of manufacturing |
BRPI0814905 BRPI0814905A2 (en) | 2007-08-24 | 2008-08-25 | METHOD OF MANUFACTURING A POLYMERIC FILLED MEMBRANE, POLYMERIC FILLED MEMBRANE, APPLIANCE FOR SEPARATING A MIX OF COMPONENTS, APPLIANCE FOR SEPARATING A MIXTURE OF COMPONENTS FOR NANOFILTRATION MEMBRANE |
RU2010105765/05A RU2470701C2 (en) | 2007-08-24 | 2008-08-25 | Polymer membranes with filler, application and method of production |
AU2008292221A AU2008292221B2 (en) | 2007-08-24 | 2008-08-25 | Filled polymeric membranes, use and method of manufacturing |
JP2010522337A JP5097826B2 (en) | 2007-08-24 | 2008-08-25 | Filled polymer membrane, use and manufacturing method |
ZA2010/00680A ZA201000680B (en) | 2007-08-24 | 2010-01-28 | Filled polymeric membranes,use and method of manufacturing |
Applications Claiming Priority (2)
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EP07114971 | 2007-08-24 | ||
EP07114971.0 | 2007-08-24 |
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WO2009027376A1 true WO2009027376A1 (en) | 2009-03-05 |
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PCT/EP2008/061095 WO2009027376A1 (en) | 2007-08-24 | 2008-08-25 | Filled polymeric membranes, use and method of manufacturing |
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US (1) | US8557022B2 (en) |
EP (1) | EP2180939A1 (en) |
JP (1) | JP5097826B2 (en) |
CN (1) | CN101820986B (en) |
AU (1) | AU2008292221B2 (en) |
BR (1) | BRPI0814905A2 (en) |
CA (1) | CA2695730A1 (en) |
RU (1) | RU2470701C2 (en) |
WO (1) | WO2009027376A1 (en) |
ZA (1) | ZA201000680B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US20110089110A1 (en) * | 2007-08-24 | 2011-04-21 | Vlaamse Instelling Voor Technologisch Onderzoek N.V. (Vito) | Filled polymeric membranes, use and method of manufacturing |
CN102427873A (en) * | 2009-05-18 | 2012-04-25 | 威拓股份有限公司 | Thin film pervaporation membranes |
WO2012112118A1 (en) * | 2011-02-20 | 2012-08-23 | Franciscus Hubertus Jacobus Maurer | Expanded polymeric membranes |
US8889766B2 (en) | 2011-03-01 | 2014-11-18 | The Trustees Of Columbia University In The City Of New York | Thin glassy polymer films including spherical nanoparticles |
US9133314B2 (en) | 2007-12-17 | 2015-09-15 | The Trustees Of Columbia University In The City Of New York | Anisotropic self-assembly of nanoparticles in composites |
EP2432578B1 (en) * | 2009-05-18 | 2018-09-12 | Vito NV | Thin film pervaporation membranes |
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JP5981140B2 (en) * | 2008-11-07 | 2016-08-31 | エフ.ホフマン−ラ ロシュ アーゲーF. Hoffmann−La Roche Aktiengesellschaft | Fine particle packing material for photoreactive film |
CN104936684B (en) * | 2012-11-26 | 2018-07-03 | 联邦科学与工业研究组织 | Mixed-matrix polymer composition |
US20150114906A1 (en) * | 2013-10-24 | 2015-04-30 | Phillips 66 Company | Silylated mesoporous silica membranes on polymeric hollow fiber supports |
US20170015433A1 (en) * | 2015-07-14 | 2017-01-19 | Hamilton Sundstrand Corporation | Protection system for polymeric air separation membrane |
US10016720B2 (en) * | 2015-07-14 | 2018-07-10 | Hamilton Sundstrand Corporation | Oxygen sensing for fuel tank inerting system |
US10052582B1 (en) * | 2017-03-29 | 2018-08-21 | Uop Llc | Super high permeance and high selectivity rubbery polymeric membranes for separations |
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JPH078926B2 (en) * | 1989-12-07 | 1995-02-01 | ダイキン工業株式会社 | Method for producing polytetrafluoroethylene multilayer porous membrane |
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US6316684B1 (en) * | 1999-09-01 | 2001-11-13 | Membrane Technology And Research, Inc. | Filled superglassy membrane |
KR100353867B1 (en) | 1999-11-30 | 2002-09-26 | 한국전자통신연구원 | Polymer Electrolyte for Rechargeable Lithium Batteries |
ITMI20010384A1 (en) * | 2001-02-26 | 2002-08-26 | Ausimont Spa | POROUS HYDROPHILIC MEMBRANES |
US6626980B2 (en) * | 2001-09-21 | 2003-09-30 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Mixed matrix membranes incorporating chabazite type molecular sieves |
US7479227B2 (en) * | 2003-03-07 | 2009-01-20 | Membrane Technology And Research, Inc. | Liquid-phase separation of low molecular weight organic compounds |
EP1698656B2 (en) * | 2003-12-24 | 2017-04-26 | Asahi Kasei Kabushiki Kaisha | Microporous membrane made from polyolefin |
KR100611682B1 (en) * | 2005-07-12 | 2006-08-14 | 한국과학기술연구원 | Silver nanoparticles/polymer nanocomposites for olefin/paraffin separation membranes and preparation method thereof |
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- 2008-08-25 RU RU2010105765/05A patent/RU2470701C2/en not_active IP Right Cessation
- 2008-08-25 CA CA 2695730 patent/CA2695730A1/en not_active Abandoned
- 2008-08-25 CN CN2008801042127A patent/CN101820986B/en not_active Expired - Fee Related
- 2008-08-25 JP JP2010522337A patent/JP5097826B2/en not_active Expired - Fee Related
- 2008-08-25 US US12/675,056 patent/US8557022B2/en not_active Expired - Fee Related
- 2008-08-25 EP EP08787450A patent/EP2180939A1/en not_active Withdrawn
- 2008-08-25 BR BRPI0814905 patent/BRPI0814905A2/en not_active IP Right Cessation
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US20110089110A1 (en) * | 2007-08-24 | 2011-04-21 | Vlaamse Instelling Voor Technologisch Onderzoek N.V. (Vito) | Filled polymeric membranes, use and method of manufacturing |
US8557022B2 (en) * | 2007-08-24 | 2013-10-15 | Vlaamse Instelling Voor Technologisch Onderzoek N.V. (Vito) | Filled polymeric membranes, use and method of manufacturing |
US9133314B2 (en) | 2007-12-17 | 2015-09-15 | The Trustees Of Columbia University In The City Of New York | Anisotropic self-assembly of nanoparticles in composites |
CN102427873A (en) * | 2009-05-18 | 2012-04-25 | 威拓股份有限公司 | Thin film pervaporation membranes |
JP2012527340A (en) * | 2009-05-18 | 2012-11-08 | ヴィト ナームロゼ ベンノートチャップ | Thin film-containing pervaporation film |
RU2492918C2 (en) * | 2009-05-18 | 2013-09-20 | Вито Н.В. | Thin pervaporation membranes |
US9339771B2 (en) | 2009-05-18 | 2016-05-17 | Vito N.V. | Thin film pervaporation membranes |
EP2432578B1 (en) * | 2009-05-18 | 2018-09-12 | Vito NV | Thin film pervaporation membranes |
WO2012112118A1 (en) * | 2011-02-20 | 2012-08-23 | Franciscus Hubertus Jacobus Maurer | Expanded polymeric membranes |
US8889766B2 (en) | 2011-03-01 | 2014-11-18 | The Trustees Of Columbia University In The City Of New York | Thin glassy polymer films including spherical nanoparticles |
Also Published As
Publication number | Publication date |
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AU2008292221B2 (en) | 2012-03-29 |
CN101820986B (en) | 2013-06-19 |
BRPI0814905A2 (en) | 2015-02-03 |
ZA201000680B (en) | 2011-07-27 |
CN101820986A (en) | 2010-09-01 |
US8557022B2 (en) | 2013-10-15 |
CA2695730A1 (en) | 2009-03-05 |
AU2008292221A1 (en) | 2009-03-05 |
RU2470701C2 (en) | 2012-12-27 |
EP2180939A1 (en) | 2010-05-05 |
RU2010105765A (en) | 2011-09-27 |
JP2010537032A (en) | 2010-12-02 |
JP5097826B2 (en) | 2012-12-12 |
US20110089110A1 (en) | 2011-04-21 |
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