WO2001043952A1 - A reinforcing structure for stiff composite articles - Google Patents

A reinforcing structure for stiff composite articles Download PDF

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Publication number
WO2001043952A1
WO2001043952A1 PCT/EP2000/012781 EP0012781W WO0143952A1 WO 2001043952 A1 WO2001043952 A1 WO 2001043952A1 EP 0012781 W EP0012781 W EP 0012781W WO 0143952 A1 WO0143952 A1 WO 0143952A1
Authority
WO
WIPO (PCT)
Prior art keywords
reinforcing structure
metallic
metallic element
reinforcing
stiff composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2000/012781
Other languages
English (en)
French (fr)
Inventor
Peter Boesman
Elsie De Clercq
Frans Van Giel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bekaert NV SA
Original Assignee
Bekaert NV SA
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 Bekaert NV SA filed Critical Bekaert NV SA
Priority to AU26739/01A priority Critical patent/AU2673901A/en
Priority to EP20000989982 priority patent/EP1237711B1/en
Priority to AT00989982T priority patent/ATE291530T1/de
Priority to JP2001545066A priority patent/JP4007537B2/ja
Priority to DE2000618969 priority patent/DE60018969T2/de
Priority to US10/149,595 priority patent/US6777081B2/en
Publication of WO2001043952A1 publication Critical patent/WO2001043952A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/10Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two-dimensional [2D] structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/26Non-fibrous reinforcements only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • B29C70/885Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding with incorporated metallic wires, nets, films or plates
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/242Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
    • D03D15/25Metal
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/44Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads with specific cross-section or surface shape
    • D03D15/46Flat yarns, e.g. tapes or films
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/60Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the warp or weft elements other than yarns or threads
    • D03D15/67Metal wires
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04BKNITTING
    • D04B1/00Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14Other fabrics or articles characterised primarily by the use of particular thread materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00Hoses, i.e. flexible pipes
    • F16L11/04Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • F16L11/085Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
    • F16L11/086Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers two layers
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00Hoses, i.e. flexible pipes
    • F16L11/04Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • F16L11/085Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
    • F16L11/087Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers three or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0809Fabrics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2305/00Use of metals, their alloys or their compounds, as reinforcement
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00Inorganic fibres
    • D10B2101/20Metallic fibres
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/022Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/04Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/041Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polyvinyl chloride or polyvinylidene chloride
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/12Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • D10B2321/121Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain polystyrene
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/04Heat-responsive characteristics
    • D10B2401/041Heat-responsive characteristics thermoplastic; thermosetting
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/061Load-responsive characteristics elastic
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/062Load-responsive characteristics stiff, shape retention
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00Industrial
    • D10B2505/02Reinforcing materials; Prepregs
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
    • Y10T428/24322Composite web or sheet
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24777Edge feature
    • Y10T428/24785Edge feature including layer embodying mechanically interengaged strands, strand portions or strand-like strips [e.g., weave, knit, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3033Including a strip or ribbon
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3049Including strand precoated with other than free metal or alloy
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3179Woven fabric is characterized by a particular or differential weave other than fabric in which the strand denier or warp/weft pick count is specified
    • Y10T442/322Warp differs from weft
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3179Woven fabric is characterized by a particular or differential weave other than fabric in which the strand denier or warp/weft pick count is specified
    • Y10T442/322Warp differs from weft
    • Y10T442/3228Materials differ
    • Y10T442/3236Including inorganic strand material
    • Y10T442/3252Including synthetic polymeric strand material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3179Woven fabric is characterized by a particular or differential weave other than fabric in which the strand denier or warp/weft pick count is specified
    • Y10T442/322Warp differs from weft
    • Y10T442/3228Materials differ
    • Y10T442/326Including synthetic polymeric strand material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3382Including a free metal or alloy constituent
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3382Including a free metal or alloy constituent
    • Y10T442/339Metal or metal-coated strand
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3707Woven fabric including a nonwoven fabric layer other than paper
    • Y10T442/3715Nonwoven fabric layer comprises parallel arrays of strand material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/40Knit fabric [i.e., knit strand or strip material]
    • Y10T442/475Including a free metal or alloy constituent

Definitions

  • a reinforcing structure for stiff composite articles is provided.
  • the invention relates to a reinforcing structure, comprising metallic elements, and the use of such reinforcing structure to reinforce stiff composite articles.
  • the invention further relates to stiff composite articles and a method to provide stiff composite articles.
  • Reinforcing structure are known to reinforce polymer articles. Often, glass fibers or C-fibers are used to reinforce polymer matrices, providing together a reinforced, eventually shaped article. During forming processes, the bending properties of the polymer matrix are influenced negatively, since the reinforcing structures are difficult to elongate.
  • metallic filaments or fibers are integrated into composite materials in order to obtain a material that is EMI shielded.
  • metallic filaments or fibers with fine diameters of 100 ⁇ m or less are used.
  • An example of this can be found in US5089326. It is known in the art that the addition of fine metallic fibers or filaments, usually less than 100 ⁇ m, does not increase the strength of the composite material.
  • Metal wires or metal wire textile fabrics are also known as reinforcing structures, e.g. from FR1290278, EP234463A1 , EP546962A1 or EP392904A1.
  • metal wires are preferably provided as knitted fabrics.
  • the present invention relates to a reinforcing structure comprising metallic elements.
  • the reinforcing structure can be used to manufacture stiff composite articles, which further comprises a polymer matrix. It is an object of the present invention to provide a reinforcing structure which comprises metallic elements, all metallic elements laying essentially parallel to each other, which has improved bending properties compared to the known wires or wire meshes, and which provide an alternative to the knitted wire structures.
  • a reinforcing structure as subject of the invention comprises metallic elements, which are all essentially parallel to each other in the reinforcing structure, each of the metallic elements is structurally deformed.
  • essentially parallel is meant that due to the nature of the metallic elements, the distance between adjacent metallic elements may vary only slightly.
  • metallic elements are to be understood as metallic wires, e.g. drawn metallic wires, a bundle of metallic wires, metallic strands or cords.
  • the bending properties of reinforcing structure are improved by integrating metallic elements in the reinforcing structure, which have an elongation at rupture of more than 3% compared to initial length.
  • This elongation can even be more than 5% or more than 7%, e.g. more than 10% and most preferentially more than 15% at rupture.
  • this elongation is obtained by the use of a metallic element having structural deformations.
  • Such structural deformation may have an irregular shape, e.g. undulated with a wavelength and/or amplitude, which varies over the length to the metallic element.
  • the metallic element are undulated or spirally shaped in a regular way, with constant parameters over the whole length of the metallic element.
  • a structural deformation can be e.g. an undulation.
  • the metallic element being a wire, strand or cord, is given a form, characterized by a wavelength and an amplitude.
  • This undulated metallic element is essentially comprehended in one plane, parallel to the axis of the metallic element.
  • Another structural deformation can be that e.g. a metallic element has obtained a spiral shape, characterized by a diameter of the spiral and the length of the metallic element, necessary to make a 360° revolution in the spiral shape.
  • the removal of the structural deformation of the metallic element will lead to an elastic elongation, a plastic elongation, or a combination of both of the metallic element during the forming process, mainly depending on the wavelength of the undulation.
  • the elongation of the metallic elements being undulated with a large wavelength can be more than 0.3%, e.g. more than 0.4%, or even more than 0.5%, preferably more than 1 % or more, applying a force of 10% of the force at rupture of the metallic element.
  • the metallic element has a spiral shape structural deformation
  • an identical behavior is obtainable.
  • the removal of the structural deformation of the metallic element will lead to an elastic elongation, a plastic elongation or a combination of both of the metallic element during the forming process.
  • the elongation due to a removing of the structural deformation can be either elastic, or plastic or a combination of a plastic and an elastic elongation, depending on the wavelength or the length to make a 360° revolution applied.
  • Metallic elements being part of a reinforcing structure as subject of the invention, may have more than one structural deformation, being e.g. undulations or spiral shape structural deformations, superposed one to another.
  • the forces F1 , F2 and F3, where the elongation change from elastic to plastic or vice versa, can be adjusted by the wavelength and amplitude of the undulations together with other parameters of the metallic element, such as diameter of wires, alloy and drawing history and eventually strand and cord construction.
  • the metallic element may either be undulated in one plane parallel to the axis of the metallic element, or the undulations may be provided in different planes, all parallel to the axis of the metallic element.
  • the reinforcing structure may comprise one or more layers, hereafter called reinforcing layers.
  • the metallic elements are present in at least one of the reinforcing layers, all metallic elements of this reinforcing layer are running essentially parallel to each other.
  • the reinforcing structure comprises more than one reinforcing layer, of which at least two reinforcing layers comprise metallic elements, the direction of the metallic elements of one layer may be different of the direction of the other layer.
  • the reinforcing structure is to be understood as all elements, which are used to provide the stiff composite article, next to the polymer matrix.
  • a person skilled in the art understands that also other materials can be used to provide elements of the reinforcing structure, e.g. glass fiber, C-fiber or mats or woven fabrics out of such materials, in addition to the metallic elements.
  • An object of the invention is to improve the bending properties and behavior of reinforcing structures comprising metallic elements during a forming process of a stiff composite article, comprising this reinforcing structure and a polymer matrix.
  • the reinforcing structure and the polymer matrix are subjected to heat and / or pressure in order to obtain a stiff composite article.
  • the forming can be done in one step or may require subsequent steps.
  • a reinforcing structure as subject of the invention may be subjected to a forming process, together with the polymer matrix. This process comprises a heating action to soften the polymer matrix, a forming action to form the softened matrix and the reinforcing structure in a desired form, and a cooling action to stiffen the matrix again.
  • a metallic element having more than one structural deformation is used as a part of the reinforcing structure of a stiff composite article
  • benefits are provided to the bending properties during the forming process on the one hand and to the stiff composite article on the other hand.
  • the force F, used to provide a stiff composite article comprising the reinforcing structure is approximately F2
  • the bending properties of the reinforcing structure are improved by the elastic and plastic elongation provided by the elongation zones below F2.
  • an impact force e.g. a force between F2 and F3
  • the stiff composite article will be able to absorb the impact energy in a reversible change of its shape. This because mainly the reinforcing structure will stretched under an essentially elastic elongation.
  • Such forming processes in which the reinforcing structure and the polymer matrix are subjected to heat and/or pressure in order to form a stiff composite article, may comprise one or subsequent steps.
  • polymer material to be used as polymer matrix in the stiff composite article, is added to the reinforcing structure.
  • metallic elements are laminated between two or more polymer layers.
  • other elements of the reinforcing structure are added before or during laminating.
  • An alternative is to extrude polymer material around the reinforcing structure, comprising the metallic elements, which are essentially parallel to each other. This combination of polymer material and reinforcing structure comprising metallic elements is subjected to a forming process.
  • Such a forming process could be e.g. press-forming, flow moulding, thermofolding or membrane forming.
  • a press-forming operation stamping
  • a reinforcing structure and the polymer matrix are heated to processing temperature and stamped to shape in a two-part-tool under pressure to provide a stiff composite article.
  • the reinforcing structure and the polymer matrix are placed in a two-part-tool and heated to the melting temperature of the polymer material. Eventually pressure is used.
  • the mould cavity is filled by polymer matrix, flowing into every recess of the mould, so providing a stiff composite article.
  • thermofolding operation the reinforcing structure and the polymer matrix are heated locally and folded to provide a stiff composite article.
  • an autoclave pressure is used to drape the preheated reinforcing structure and the polymer matrix over a tool, providing a stiff composite article.
  • metallic elements in the matrix during bending operations improves the heat distribution throughout the whole matrix. Since the metallic elements have a high thermal and electric conductivity. This leads to shorter cycle times compared to composite materials with other reinforcing structures, not comprising metallic elements such as glass fibers or carbon fibers.
  • the metallic elements can be woven or braided together with polymer filaments, yarns or polymer tapes into one and the same fabric.
  • the metallic elements run in only one direction of the fabric, either the warp or weft direction. This fabric itself forms part of the reinforcing structure.
  • the fabric may be laminated with one or more layers of polymer material.
  • the polymer filaments or yarns help to fill the spaces between the adjacent metallic elements. Especially when the filaments or yarns are of the same polymer nature as compared to the polymer matrix.
  • Another alternative is provided by providing a polymer coating around the metallic elements, preferably before they are given the structural deformation.
  • a polymer coating is extruded around the metallic element.
  • Such polymer coating helps to improve the adhesion between the metallic elements of the reinforcing structure and the polymer matrix.
  • thermoplastic material can be used as a polymer matrix.
  • a thermoplastic material has to be considered as any thermoplast and any thermoplastic elastomer.
  • thermoplastic materials are : polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyethylene napthalate (PEN), polybuteen terephthalate (PBT) polyvi ⁇ ylchloride (PVC), polyamide (PA) , polyester (PES), polyimide (PI), polycarbonate (PC) , styrene acrilonitryl (SAN), acrylonitril- butadiene-styrene (ABS), thermoplastic polyurethane (TPU), thermoplastic polyolefins (TPO), thermoplastic copolyetheresters , copolymers of these polymers or similar materials.
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PET polyethylene terephthalate
  • PEN polyethylene napthalate
  • PBT polybuteen terephthalate
  • PVC polyvi ⁇ ylchloride
  • PA polyamide
  • PET polyester
  • These polymer matrices could be defined by a Young's modulus of more than 10 7 Pa, preferably between 10 8 Pa and 5 * 10 9 Pa. The Young's modulus is measured at the origin of the stress-strain curve of the polymer at ambient temperatures.
  • thermoset polymers by forming the reinforcing structure without polymer matrix, and adding the thermoset matrix, being the polymer matrix, to the formed reinforcing structure by e.g. injection molding.
  • the metallic elements can be coated with a metallic coating layer such as zinc or a zinc alloy such as brass.
  • a metallic coating layer such as zinc or a zinc alloy such as brass.
  • a suitable zinc alloy is an alloy comprising 2 to 10 % Al and 0.1 to 0.4 % of a rare earth element such as La and/or Ce.
  • an adhesion promoter can be applied on the metallic element.
  • Possible adhesion promoters are bifunctional coupling agents such as silane compounds.
  • One functional group of these coupling agents is responsible for the binding with the metal or metal oxides; the other functional group reacts with the polymer.
  • Wires used as metallic elements as such or comprised in a strand or cord may have various cross-sections and geometries, e.g. circular, oval or flat.
  • Wires used as such or comprised in a strand or cord can have a diameter of 0.04mm to 1.0 mm, preferably between 0.1 mm and 0.4mm, e.g. 0.15mm, 0.175mm or 0.3mm.
  • Wires having structural deformations may also be used to provide a strand or cord. These strands or cords may form part of the reinforcing structure.
  • Any metal can be used to provide the metallic elements.
  • alloys such as high carbon steel alloys or stainless steel alloys are used.
  • the tensile strength of the steel wires ranges from 1500 N/mm 2 to 3000 N/mm 2 and even more, and is mainly dependent upon the composition of the steel and the diameter.
  • a strand or cord such as the construction of the strand or cord, the number of wires and the diameters of each wire comprised in a strand or cord, the force at rupture of each wire comprised in the strand or cord, can be chosen to provide the required mechanical properties such as strength and elongation at rupture.
  • FIGURE 1 A and B shows a schematic view of a stiff planar composite structure as subject of the invention.
  • FIGURE 2 shows a side view of an undulated wire.
  • FIGURE 3 shows stress strain curves of undulated wires.
  • FIGURE 4 shows a metallic element, having two undulations superposed to each other.
  • FIGURE 5 shows a stress-strain curve of an undulated wire as shown in FIGURE 4.
  • FIGURE 6, 7 and 8 shows a schematic view of another stiff planar composite structure as subject of the invention.
  • FIGURE 9 shows a reinforcing structure comprising a textile woven fabric. Description of the preferred embodiments of the invention.
  • the stiff planar composite material 11 comprises a polymer matrix 12, e.g. a PES matrix, and a reinforcing structure 13, comprising only one reinforcing layer 14.
  • the reinforcing layer 14 consists of a number of undulated wires 15, laying essentially parallel to each other in one reinforcing layer (as shown in FIGURE 1A) or a number of undulated wires 16, laying essentially parallel to each other in one reinforcing layer (as shown in FIGURE 1 B).
  • FIGURE 2 shows a side view of an undulated wire 21.
  • the wire has its original axis 22, to which it is undulated in one plane with a wavelength
  • a wire diameter of 0.3mm is chosen.
  • Different embodiments of an undulated wire were provided, having characteristics as shown in the table underneath.
  • Sample A, B and C were provided using the wire of sample D.
  • FIGURE 3 shows the stress strain curves of sample A, B, C and D.
  • abscissa the elongation compared to the length at start is shown.
  • the ordinate shows the force applied compared to the total force at rupture.
  • the stress strain curve 31 shows that the major part of the elongation is found in the essentially elastic deformation zone 32 of the curve, whereas only a smaller part of the elongation is found in the plastic deformation zone 33.
  • the stress-strain curve 37 shows that only a small elastic elongation can be found in the elastic deformation zone 38, compared to the large elongation in the plastic deformation zone 39.
  • the removing of the structural deformation for these rather short wavelengths is essentially obtained by a plastic elongation.
  • FIGURE 4 Another embodiment is obtainable using metallic element with more than one structural deformation superposed to each other.
  • a wire 41 is shown, having 2 undulations superposed to each other. The two undulations are provided in the same plane.
  • a first undulation characterized with a large wavelength 42 and amplitude 43, compared to the axis 44 of the wire as if there was no such undulation, is superposed to an undulation with short wavelength 45 and amplitude 46 compared to the axis 47 of the wire as if there was no such undulation.
  • An embodiment was provided with characteristics as in the table underneath :
  • FIGURE 5 shows the stress strain curves of sample E.
  • abscissa the elongation compared to the length at start is shown.
  • the ordinate shows the force applied compared to the total force at rupture.
  • curve 51 shows 4 zones.
  • zone 52 the elongation obtained is essentially elastic.
  • Zone 53 provided an additional elongation which is mainly plastic, whereas zone 54 provides an elongation which is again more elastic.
  • Zone 55 provides a plastic elongation until rupture occurs.
  • FIGURE 6 A reinforcing structure having 2 reinforcing layers is shown in FIGURE 6.
  • undulated wires 61 are laying essentially parallel to each other in one direction.
  • undulated wires 62 are laying essentially parallel to each other in a direction, which is different from the direction of the wires 61 of the first reinforcing layer.
  • a stiff composite article may be obtained when a polymer matrix 63 is provided to the reinforcing structure, e.g. by laminating polymer sheets under increased temperature to both sides of the reinforcing structure. By applying heat and/or pressure, the polymer matrix 63 adheres to the reinforcing structure. Possibly, the stiff composite article is given its final form at the same time. Alternatively, a planar stiff composite article is provided, which may be deformed to a final shape later in a separate operation applying heat and/or pressure to the planar stiff composite article.
  • FIGURE 7 Another reinforcing structure is shown in FIGURE 7.
  • Wires 71 and 72 each having two undulations superposed to each other, are arranged in two reinforcing layers. In each reinforcing layer, the wires 71 , respectively 72 are laying essentially parallel to each other. The directions of wires 71 and 72 may be different.
  • a polymer matrix 73 is additionally provided and adheres via heat and/or pressure tot he reinforcing structure, so providing a planar stiff composite article.
  • FIGURE 8 Another reinforcing structure having 2 reinforcing layers is shown in FIGURE 8.
  • spirally shaped wires 81 are laying essentially parallel to each other in one direction.
  • spirally shaped wires 82 are laying essentially parallel to each other in a direction, which is different from the direction of the wires
  • a polymer matrix 83 is additionally provided and adheres via heat and/or pressure to the reinforcing structure, so providing a planar stiff composite article.
  • Another reinforcing structure being a textile woven fabric 91 is shown in
  • FIGURE 9 comprising undulated wires as metallic element 92.
  • Metallic elements 92 are present in warp or weft direction on the woven fabric, whereas the other direction of the woven fabric, being the weft respectively the warp, is provided using polymer filaments 93.
  • These filaments may be made from the same or a different polymer as the polymer matrix of the stiff composite article.
  • the polymer filament may be replaced by polymer tapes, having a width preferably in the range of 1 to 10 mm, and a thickness preferably between 20 and 300 ⁇ m.
  • some polymer material can be present as coating on the metallic elements or on a number of metallic elements to form strips.
  • the total volume of the thermoplastic material present as filament and/or as coating may even be more than 40 % of the total volume of the woven fabric.
  • a reinforcing structure may comprise one or more reinforcing layers, each layer being such a textile fabric as described above.
  • the adhesion between metallic element and polymer matrix could be influenced by a coating of the metallic element.
  • a brass, zinc or zinc alloy coating on the metallic element can improve the adhesion between polymer matrix and metallic element.
  • a possible zinc alloy is an alloy comprising 2 to 10% Al and 0.1 to 0.4% of a rare earth element such as La and/or Ce.
  • adhesion promoters such as silane compounds, aluminates, zirconates or titanates.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Woven Fabrics (AREA)
  • Laminated Bodies (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Reinforced Plastic Materials (AREA)
  • Knitting Of Fabric (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Moulding By Coating Moulds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Ceramic Products (AREA)
  • Prostheses (AREA)
  • Materials For Medical Uses (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
PCT/EP2000/012781 1999-12-15 2000-12-13 A reinforcing structure for stiff composite articles Ceased WO2001043952A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU26739/01A AU2673901A (en) 1999-12-15 2000-12-13 A reinforcing structure for stiff composite articles
EP20000989982 EP1237711B1 (en) 1999-12-15 2000-12-13 A reinforcing structure for composite articles
AT00989982T ATE291530T1 (de) 1999-12-15 2000-12-13 Stützstruktur für verbundbauteile
JP2001545066A JP4007537B2 (ja) 1999-12-15 2000-12-13 剛性複合物品用補強構造体
DE2000618969 DE60018969T2 (de) 1999-12-15 2000-12-13 Stützstruktur für verbundbauteile
US10/149,595 US6777081B2 (en) 1999-12-15 2000-12-13 Reinforcing structure for stiff composite articles

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EP99204339 1999-12-15
EP99204339.8 1999-12-15
EP99204338.0 1999-12-15
EP99204340.6 1999-12-15
EP99204338 1999-12-15
EP99204340 1999-12-15

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PCT/EP2000/012781 Ceased WO2001043952A1 (en) 1999-12-15 2000-12-13 A reinforcing structure for stiff composite articles
PCT/EP2000/012765 Ceased WO2001044548A1 (en) 1999-12-15 2000-12-13 Reinforced fabric
PCT/EP2000/012760 Ceased WO2001044549A1 (en) 1999-12-15 2000-12-13 Woven composite fabric
PCT/EP2000/012779 Ceased WO2001043951A1 (en) 1999-12-15 2000-12-13 A reinforcing structure for stiff composite articles

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PCT/EP2000/012760 Ceased WO2001044549A1 (en) 1999-12-15 2000-12-13 Woven composite fabric
PCT/EP2000/012779 Ceased WO2001043951A1 (en) 1999-12-15 2000-12-13 A reinforcing structure for stiff composite articles

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AU (4) AU2673901A (https=)
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ATE264185T1 (de) 2004-04-15
EP1238129A1 (en) 2002-09-11
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DK1238128T3 (da) 2006-03-13
EP1237711B1 (en) 2005-03-23
ES2218274T3 (es) 2004-11-16
AU3012201A (en) 2001-06-25
DK1238129T3 (da) 2004-04-05
JP2003517106A (ja) 2003-05-20
ATE311490T1 (de) 2005-12-15
US20020182961A1 (en) 2002-12-05
US7304007B2 (en) 2007-12-04
ES2252082T3 (es) 2006-05-16
US20030022579A1 (en) 2003-01-30
ATE291530T1 (de) 2005-04-15
JP4323127B2 (ja) 2009-09-02
DE60007662T2 (de) 2004-11-11
AU2673901A (en) 2001-06-25
WO2001044548A1 (en) 2001-06-21
US6787491B2 (en) 2004-09-07
ATE257524T1 (de) 2004-01-15
EP1238128B1 (en) 2005-11-30
JP4880157B2 (ja) 2012-02-22
US20040176007A1 (en) 2004-09-09
EP1237710B1 (en) 2004-04-14
AU2673801A (en) 2001-06-25
JP4184664B2 (ja) 2008-11-19
JP2003517110A (ja) 2003-05-20
EP1238128A1 (en) 2002-09-11
DE60018969D1 (de) 2005-04-28
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EP1238129B1 (en) 2004-01-07
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DE60007662D1 (de) 2004-02-12
DE60024485D1 (de) 2006-01-05
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DE60009951D1 (de) 2004-05-19
US20030082336A1 (en) 2003-05-01
EP1237711A1 (en) 2002-09-11
ES2214343T3 (es) 2004-09-16
WO2001044549A1 (en) 2001-06-21
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DE60024485T2 (de) 2006-08-03
DE60018969T2 (de) 2006-03-23

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