WO2003083985A3 - Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix - Google Patents

Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix Download PDF

Info

Publication number
WO2003083985A3
WO2003083985A3 PCT/CA2003/000435 CA0300435W WO03083985A3 WO 2003083985 A3 WO2003083985 A3 WO 2003083985A3 CA 0300435 W CA0300435 W CA 0300435W WO 03083985 A3 WO03083985 A3 WO 03083985A3
Authority
WO
WIPO (PCT)
Prior art keywords
composite material
silica particles
membrane
polymer matrix
gas
Prior art date
Application number
PCT/CA2003/000435
Other languages
French (fr)
Other versions
WO2003083985A2 (en
Inventor
Marc St-Arnaud
Philippe Bebin
Original Assignee
Sim Composites Inc
Marc St-Arnaud
Philippe Bebin
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sim Composites Inc, Marc St-Arnaud, Philippe Bebin filed Critical Sim Composites Inc
Priority to JP2003581295A priority Critical patent/JP2005521777A/en
Priority to CA002480345A priority patent/CA2480345A1/en
Priority to AU2003212171A priority patent/AU2003212171A1/en
Priority to KR1020047015543A priority patent/KR100759143B1/en
Priority to EP03707983A priority patent/EP1504486A2/en
Publication of WO2003083985A2 publication Critical patent/WO2003083985A2/en
Priority to US10/949,022 priority patent/US20050053818A1/en
Publication of WO2003083985A3 publication Critical patent/WO2003083985A3/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • 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
    • 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
    • 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
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • 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
    • B01D71/52—Polyethers
    • 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
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
    • 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
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C08J2365/02—Polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fuel Cell (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The composite material comprises acid functionalized silica dispersed in a polymer matrix that is based on poly(aromatic ether ketones), or poly(benzoyl phenylene), or derivatives thereof. The composite material is characterized by good water retention capabilities due to the acidic functions and the hydrophilicity of the silica particles. Moreover, a good impermeability to gas and liquid fuels commonly used in fuel cell technology, like hydrogen gas or methanol solution, is also obtained due to the presence of silica particles. Good mechanical properties of the composite material let the material to be formed easily in thin film or membrane form. In that form, the composite material is usable for proton exchange membrane for fuel cells, for drying or humidifying membrane for gas or solvent conditioning, or as acid catalytic membrane.
PCT/CA2003/000435 2002-03-28 2003-03-26 Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix WO2003083985A2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2003581295A JP2005521777A (en) 2002-03-28 2003-03-26 Ion exchange composites based on proton conducting silica particles dispersed in a polymer matrix
CA002480345A CA2480345A1 (en) 2002-03-28 2003-03-26 Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix
AU2003212171A AU2003212171A1 (en) 2002-03-28 2003-03-26 Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix
KR1020047015543A KR100759143B1 (en) 2002-03-28 2003-03-26 Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix
EP03707983A EP1504486A2 (en) 2002-03-28 2003-03-26 Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix
US10/949,022 US20050053818A1 (en) 2002-03-28 2004-09-24 Ion exchange composite material based on proton conductive functionalized inorganic support compounds in a polymer matrix

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36777102P 2002-03-28 2002-03-28
US60/367,771 2002-03-28

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/949,022 Continuation-In-Part US20050053818A1 (en) 2002-03-28 2004-09-24 Ion exchange composite material based on proton conductive functionalized inorganic support compounds in a polymer matrix

Publications (2)

Publication Number Publication Date
WO2003083985A2 WO2003083985A2 (en) 2003-10-09
WO2003083985A3 true WO2003083985A3 (en) 2004-12-16

Family

ID=28675398

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2003/000435 WO2003083985A2 (en) 2002-03-28 2003-03-26 Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix

Country Status (6)

Country Link
EP (1) EP1504486A2 (en)
JP (1) JP2005521777A (en)
KR (1) KR100759143B1 (en)
AU (1) AU2003212171A1 (en)
CA (1) CA2480345A1 (en)
WO (1) WO2003083985A2 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050053818A1 (en) * 2002-03-28 2005-03-10 Marc St-Arnaud Ion exchange composite material based on proton conductive functionalized inorganic support compounds in a polymer matrix
US6630265B1 (en) 2002-08-13 2003-10-07 Hoku Scientific, Inc. Composite electrolyte for fuel cells
EP1680831A2 (en) 2003-10-10 2006-07-19 Ballard Power Systems Inc. Water insoluble additive for improving conductivity of an ion exchange membrane
KR100684787B1 (en) * 2005-03-31 2007-02-20 삼성에스디아이 주식회사 Polymer membrane for fuel cell, method of preparing the same, and stack for fuel cell and full cell system comprising the same
CN101297377A (en) * 2005-08-19 2008-10-29 国立大学法人东京大学 Proton conductive hybrid material, and catalyst layer for fuel cell using the same
US7977392B2 (en) 2005-12-22 2011-07-12 Daimler Ag Water insoluble additive for improving conductivity of an ion exchange membrane
WO2008120379A1 (en) * 2007-03-29 2008-10-09 Fujitsu Limited Electrolyte membrane, process for producing the same, membrane electrode assembly and polymer electrolyte fuel cell
FR2917733B1 (en) * 2007-06-22 2011-05-06 Commissariat Energie Atomique ORGANOMODIFIED INORGANIC PARTICLES, PROCESS FOR PREPARING THE SAME, AND USE IN COMPOSITE MATERIAL FOR FUEL CELL MEMBRANE
KR100928718B1 (en) * 2007-10-09 2009-11-27 성균관대학교산학협력단 Process for producing PEEK electrolyte membrane with uniform sulfuric acid group by organic solvent drying method
DE102014208547A1 (en) * 2014-05-07 2015-11-12 Volkswagen Ag Membrane electrode unit with functionalized carrier material and fuel cell with such a

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2292703A1 (en) * 1998-12-18 2000-06-18 Serge Kaliaguine Composite electrolyte membranes for fuel cells and methods of making same
JP2001155744A (en) * 1999-11-29 2001-06-08 Toyota Central Res & Dev Lab Inc Proton conductor
WO2002005370A1 (en) * 2000-07-07 2002-01-17 Fuma-Tech Gmbh Hybrid material, use of said hybrid material and method for making same
US6716548B1 (en) * 1998-12-18 2004-04-06 Universite Laval Composite electrolyte membranes for fuel cells and methods of making same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2292703A1 (en) * 1998-12-18 2000-06-18 Serge Kaliaguine Composite electrolyte membranes for fuel cells and methods of making same
US6716548B1 (en) * 1998-12-18 2004-04-06 Universite Laval Composite electrolyte membranes for fuel cells and methods of making same
JP2001155744A (en) * 1999-11-29 2001-06-08 Toyota Central Res & Dev Lab Inc Proton conductor
WO2002005370A1 (en) * 2000-07-07 2002-01-17 Fuma-Tech Gmbh Hybrid material, use of said hybrid material and method for making same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 23 10 February 2001 (2001-02-10) *

Also Published As

Publication number Publication date
CA2480345A1 (en) 2003-10-09
KR100759143B1 (en) 2007-09-14
JP2005521777A (en) 2005-07-21
EP1504486A2 (en) 2005-02-09
AU2003212171A8 (en) 2003-10-13
AU2003212171A1 (en) 2003-10-13
WO2003083985A2 (en) 2003-10-09
KR20040111458A (en) 2004-12-31

Similar Documents

Publication Publication Date Title
EP1646097A3 (en) Ion exchange composite material based on proton conductive functionalized inorganic support compounds in a polymer matrix
Ogungbemi et al. Fuel cell membranes–Pros and cons
Bébin et al. Nafion®/clay-SO3H membrane for proton exchange membrane fuel cell application
Chang et al. Proton-conducting composite membranes derived from sulfonated hydrocarbon and inorganic materials
Lin et al. Proton-conducting membranes with high selectivity from phosphotungstic acid-doped poly (vinyl alcohol) for DMFC applications
Fu et al. Synthesis and characterization of sulfonated polysulfone membranes for direct methanol fuel cells
Silva et al. Proton electrolyte membrane properties and direct methanol fuel cell performance: I. Characterization of hybrid sulfonated poly (ether ether ketone)/zirconium oxide membranes
Chen et al. Ion exchange resin/polystyrene sulfonate composite membranes for PEM fuel cells
Li et al. PBI‐based polymer membranes for high temperature fuel cells–preparation, characterization and fuel cell demonstration
US7183017B2 (en) Composite polymer electrolytes for proton exchange membrane fuel cells
US20100304272A1 (en) Proton conducting polymer electrolyte membrane useful in polymer electrolyte fuel cells
TWI423511B (en) Proton exchange membrane including organic-inorganic hybird
Hasani-Sadrabadi et al. Novel high-performance nanocomposite proton exchange membranes based on poly (ether sulfone)
US20080199753A1 (en) Fluorine Treatment of Polyelectrolyte Membranes
Yaguchi et al. Crosslinked membranes of sulfonated polyimides for polymer electrolyte fuel cell applications
KR100701473B1 (en) Proton conductive composite membrane comprising surfactant and inorganic filler, and fuel cell comprising the same
CN101087029A (en) Polymer electroyte membrane, membrane electrode assembly and fuel cell using the assembly
Wang et al. Sulfonated polyimide/PTFE reinforced membrane for PEMFCs
Sedesheva et al. Proton-exchange membranes based on sulfonated polymers
Okamoto et al. Sulfonated polyimide hybrid membranes for polymer electrolyte fuel cell applications
WO2009131294A1 (en) Highly proton conductive crosslinked vinylsulfonic acid polymer electrolyte composite membranes and its preparation method for polymer electrolyte fuel cells
WO2003083985A3 (en) Ion exchange composite material based on proton conductive silica particles dispersed in a polymer matrix
Üçtuğ et al. Characterization and fuel cell performance analysis of polyvinylalcohol–mordenite mixed-matrix membranes for direct methanol fuel cell use
JP2002298867A (en) Solid polymer fuel cell
Xie et al. Enhanced low-humidity performance of proton exchange membrane fuel cell by incorporating phosphoric acid-loaded covalent organic framework in anode catalyst layer

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 10949022

Country of ref document: US

Ref document number: 2872/DELNP/2004

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2480345

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2003581295

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 1020047015543

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2003707983

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020047015543

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2003707983

Country of ref document: EP