EP1351818A2 - Corps moule multicouche a elements de renfort delimites localement - Google Patents

Corps moule multicouche a elements de renfort delimites localement

Info

Publication number
EP1351818A2
EP1351818A2 EP01989531A EP01989531A EP1351818A2 EP 1351818 A2 EP1351818 A2 EP 1351818A2 EP 01989531 A EP01989531 A EP 01989531A EP 01989531 A EP01989531 A EP 01989531A EP 1351818 A2 EP1351818 A2 EP 1351818A2
Authority
EP
European Patent Office
Prior art keywords
layer
molded body
reinforcing elements
binder
intermediate layer
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.)
Withdrawn
Application number
EP01989531A
Other languages
German (de)
English (en)
Inventor
Thomas Engels
Bernd Mayer
Werner Opitz
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1351818A2 publication Critical patent/EP1351818A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
    • E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
    • E04C2/292—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating composed of insulating material and sheet metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers

Definitions

  • Multi-layer molded body with locally limited reinforcement elements
  • the present invention relates to multi-layer molded articles composed of two outer metallic layers and at least one intermediate layer, processes for their production and use of these molded articles.
  • Multilayer moldings and methods for producing multilayer moldings are widely used wherever it is important to use specifically light structures with a high level of strength and / or rigidity.
  • the lightweight construction with increasingly thin sheet thicknesses reaches its limits especially where geometrically due to reduced cross-sections of the components, the rigidity of which no longer meets the requirements for usability.
  • the route via lighter or structurally stronger metals is also only pursued to a small extent for reasons of production technology and price, since the forming behavior is less favorable than normal steel sheets, and higher tool costs can also occur.
  • these materials have so far been used only to a limited extent, since these materials have less favorable properties than the conventional materials in terms of energy absorption and material failure in the event of a crash.
  • plastics have a low specific weight, they have so far not been able to achieve the performance level of metallic materials by far, and are therefore not used today in the area of structurally stable and load-bearing components.
  • a metal / thermoplastic / metal laminate which has a basis weight below 9.76 kg / m 2 and which is made of a thermoplastic core material based on partially crystalline polyamides or polyester with a crystalline melting point> 130 ° C consists of and a metal layer laminated on both sides of the core material, the metal layer having a melting point above the crystalline melting point of the thermoplastic core layer and the metal layer having a minimum thickness of 0.0127 mm.
  • the construction industry, appliance industry, automotive industry and aircraft construction are specified as use for these sandwich materials.
  • US-A-4759994 describes a sandwich-like structure consisting of two outer metal plates and an inner core between the two outer plates.
  • the core consists of a metallic network or grid.
  • This sandwich structure has an adhesive layer between the metal plates, which connects the two plates and the core to one another, which improves the punching behavior.
  • the adhesive should only be inside the latticework of the core material, while the contact zones between the core and metal plates should remain adhesive-free in order to enable the composite material to be weldable.
  • DE 19729566 C2 describes a metal composite panel with two outer sheets which are kept at a distance by elevations of a lightweight structural panel arranged therebetween, the lightweight structural panel and the outer panels being connected to one another at the elevations by soldering, welding or gluing.
  • An expanded metal is proposed as a lightweight structural panel.
  • EP-A-895852 describes a multi-layer steel sandwich structure consisting of two metal plates which are laminated to a core. This core is made of stainless steel wool. The sandwich structure is achieved by soldering, welding or gluing. Phenolic resins, epoxy resins or polyethylene or polypropylene-maleic anhydride copolymers are proposed as adhesives.
  • DE-A-3905871 discloses a composite material for thermal insulation and / or sound absorption that has a structurally stable covering layer made of a thermally stable metal foil on at least one side.
  • a thermally resistant, highly porous, inorganic material is proposed as the insulation layer, for example foamed glass with a sponge-like structure or gas concrete or foamed ceramic or clay mineral materials. Exhaust areas of an automobile are proposed as an application for this composite material in the automotive sector.
  • WO 00/13890 describes glued multilayer composite panels and methods for producing multilayer composite panels which consist of two outer metal plates which serve as upper and lower base plates and which are bonded to a deformable connecting intermediate layer.
  • the deformable web material lying in the intermediate layer is connected to the cover and base plate by means of a foaming adhesive which fills the cavities remaining in the composite.
  • the web material lying between the metal plates can consist of an expanded metal mesh, a wire mesh or a web plate and it can include a multi-layer sequence of expanded metal meshes, wire meshes, web plates with intermediate plates that are impermeable or permeable to the adhesive.
  • suitable compositions of the adhesive in this document.
  • EP 636517 B1 discloses a production method for a vehicle body part, at least in some areas, having a double sheet metal structure with an insulating layer in between.
  • the base plate and the cover plate of the double-sheet structure are first fixed to one another with the interposition of an insulation layer and then formed together, in particular deep-drawn.
  • a suitable insulation layer material should only be placed on selected surface sections of the flat base plate and a flat cover plate extending over a larger surface section is placed thereon, the insulation layer initially being sufficiently pressure-stable in the edge region to withstand the deformation.
  • the insulation layer material is to be glued to the base plate and the cover plate, the adhesive required for the gluing being applied by foil, sealing cord, rolling / rolling, spray film, adhesive beads or drops.
  • the object of the invention can be seen from the claims, it essentially consists in the provision of multilayered molded articles from two outer metallic layers and at least one intermediate layer, in which the entire surface of the laminated article has an anisotropic structure.
  • Another object of the present invention is a method for producing such multilayer molded articles and the use of multilayer laminates or molded articles for producing components in automobile construction.
  • the two outer metallic layers of the multi-layer molded body are usually metal sheets. These sheets can be normal steel sheets, but they can also be steel sheets refined by the various galvanizing processes, such as the electrolytically or hot-dip galvanized sheets and the corresponding thermally post-treated or galvanized or subsequently phosphated steel sheets and aluminum sheets.
  • the thickness of these outer sheets can be adapted to the structural conditions. It can be between 0.1 and 1.0 mm, preferably between 0.1 and 0.5 mm, preferably between 0.2 and 0.3 mm.
  • the intermediate layer consists of a polymeric binder composition and the reinforcing elements anisotropically distributed therein.
  • the binder of the intermediate layer can be selected from a variety of thermoplastic polymers or from reactive binders.
  • thermoplastic polymers are polyethylene, polypropylene, polyamide, polystyrene, styrene copolymers such as e.g. Acrylonitrile-butadiene-styrene (ABS) or thermoplastic elastomers based on block copolymers of styrene with butadiene or isoprene, optionally also in their hydrogenated form, both preferably as three-block copolymers.
  • ABS Acrylonitrile-butadiene-styrene
  • thermoplastic elastomers based on block copolymers of styrene with butadiene or isoprene optionally also in their hydrogenated form, both preferably as three-block copolymers.
  • thermoplastic polymers to be used according to the invention for the intermediate layer are vinyl chloride homo- and / or copolymers - e.g.
  • Vinyl chloride / vinyl acetate copolymers, ethylene-vinyl acetate copolymers (EVA), polyester or polycarbonate Particularly suitable as reactive binders are those based on epoxy resins, reactive rubbers or polyurethanes.
  • epoxy resin - binder composition are a variety of - preferably flexible - epoxy compositions.
  • the compositions mentioned in EP-A-354498, EP-A-591307, WO 00/20483, WO 00/37554 and the as yet unpublished applications DE 10017783.2 and DE 10017784.0 may be mentioned as examples.
  • the binder compositions to be used according to the invention contain at least one epoxy resin, a flexible epoxy compound, elastomer-modified Epoxy resin and possibly a reactive thinner and usually a latent hardener, which causes the crosslinking of the binder when the compositions are heated.
  • compositions of natural and / or synthetic rubbers i.e. elastomers containing olefinic double bonds
  • vulcanizing agents are suitable as the binder matrix based on reactive rubbers. These contain at least one of the following substances: one or more liquid rubbers and / or solid rubbers or elastomers, finely divided powders made of thermoplastic polymers, vulcanizing agents, vulcanization accelerators, catalysts, fillers, tackifiers and / or adhesion promoters, blowing agents, extender oils, anti-aging agents, rheology aids.
  • Suitable binders are e.g. described in WO 96/23040.
  • thermosetting binders In addition to the aforementioned one-component thermosetting binders, two-component epoxy, rubber or even polyurethane binders which cure at room temperature can also be used.
  • the anisotropically distributed reinforcing elements of the intermediate layer can be constructed from conventional metal sheets, hardened metal alloys, multi-phase steels, aluminum, expanded metals, organic foams based on epoxides or polyurethanes, which may be fiber-reinforced, or other plastics. These reinforcing elements are preferably arranged at those locations to which the molded body is exposed to high structural loads or forces. These reinforcement elements are already installed during the production of the multilayered molded article as a semi-finished product ("multilayer laminate") in such a way that they are later present exactly at the points of the construction or component where the particularly high structural loads or forces act on the component , These reinforcement elements are preferably tailored in their geometric shape specifically to the load case.
  • the multilayer molded articles according to the invention can additionally contain functional built-in elements such as Cable channels included. This procedure is particularly useful when these moldings are to be used as roof structures or underbody groups in vehicle construction.
  • Figure 1 shows the general structure of an anisotropic multilayer laminate
  • FIG. 2 shows the additional installation of functional elements
  • Figure 3 shows the exemplary structure of a hood
  • Figure 4 shows an embodiment of a weldable component.
  • the two outer metal layers (M1) and (M2) are metal sheets with a thickness of 0.1 to 1.0 mm.
  • the intermediate polymer layer (P) usually has a layer thickness of 0.3 to 5.0 mm, its thickness depends on the intended use of the component made from the multilayer laminate. All of the aforementioned types of polymers can be used as polymers.
  • the thicker reinforcing element (V1) is arranged at a point where the greatest force (F1) is expected later in the component.
  • the reinforcing element (V2) is located at a point where a lower force (F2) will act. No reinforcement element is provided in places with even less force (F3).
  • FIG. 2 also shows the installation of a functional element, for example a channel (K) for receiving electrical cables.
  • a functional element for example a channel (K) for receiving electrical cables.
  • the remaining structural components of this laminate correspond to the elements shown in FIG. 1.
  • FIG. 3 shows an exemplary schematic structure of a bonnet in a top view.
  • the geometrical dimensions of the reinforcement elements (V1) to (V5) are adapted to the requirements for the forces acting on the bonnet or the vibration behavior of the bonnet itself. This is important for the mechanical rigidity and / or to minimize the acoustic radiation of the hood. For the sake of completeness it should be mentioned that the reinforcing elements are not visible from the outside.
  • FIG. 4 shows an exemplary embodiment of a multi-layer molded body which is to be used as a weldable component.
  • the anisotropically distributed reinforcing elements (V1) and (V2) are arranged in the polymeric binder matrix (P), but the metal sheet (M1) does not reach into the edge area.
  • the edge areas of the lower metal layer (M2) are provided with welding points (S1) and (S2), so that this component can be installed using conventional welding methods, in particular electrical welding methods.
  • These welds are preferably separated from the metal sheet (M1) by areas of the polymeric binder matrix (P1) and (P2).
  • multilayered molded articles according to FIG. 4 can also be inserted into the body using structural adhesives instead of welding them together.
  • the multilayer molded articles according to the invention can in principle be produced by continuous or discontinuous production.
  • a lower cover plate runs horizontally into the production system, then a first binder layer made of the aforementioned polymeric binders is applied from above to the lower cover plate running below using a slot die or a roller.
  • the reinforcing elements and / or functional built-in elements are then applied to the binder layer at the predetermined locations, preferably using a robot.
  • a second binder layer is also applied from above onto the semi-finished product, consisting of a lower cover plate, binder layer and reinforcing elements, using a slot die or a roller.
  • An upper cover sheet is joined to a complete laminate on the semifinished product formed in this way and the entire laminate is pressed onto the final layer thickness using rollers, if necessary with heating.
  • the heating during the joining and / or pressing can be designed in such a way that the crosslinking of the binder system is carried out at an intermediate stage, ie to a pre-hardening step, so that the binder - and thus the multilayer laminate - is still highly deformable and the multilayer laminate produced in this way can be easily deformed in conventional forming processes.
  • a final curing can then take place after the installation of the component thus produced, for example in a motor vehicle body, in the oven for the electrocoating.
  • a molded part is punched from a lower cover plate, a first binder layer made of the aforementioned polymeric binders is applied to the stamped lower cover plate with the aid of a slot die or a roller or a doctor blade, the reinforcing elements and / or functional built-in elements are attached to the predetermined ones Place, if necessary with the help of a robot, on the binder layer.
  • a second binder layer using the abovementioned application methods, the upper cover plate is joined to the layer body thus formed and the entire layer body is pressed, if necessary with heating, to the final layer thickness using rollers or presses.
  • the laminate produced in this way can then be pressed or deep-drawn by shaping into a three-dimensional shaped body.
  • reactive binders can be cured in two stages, so that forming is facilitated, and the final hardness only takes place after the molded part has been installed in the complete assembly.
  • the multilayer molded articles produced according to the invention can be used for a large number of applications in which specifically light materials are required which have high structural strength.
  • the areas of application mentioned at the beginning in mechanical engineering, in device construction and in vehicle construction, here in particular in automobile construction, may be mentioned as examples.
  • Specific examples from the automotive industry are the manufacture of roof structures, bonnets, door side panels, walls to the engine compartment ("firewall"), underbody assemblies and walls to the trunk.
  • firewall roof structures, bonnets, door side panels, walls to the engine compartment
  • underbody assemblies and walls to the trunk.
  • the multilayer according to the invention have
  • Molded parts have the following advantages: low specific weight, low overall weight, the structural reinforcement performance can be significantly improved locally in flat areas of a body at the highly stressed points, through the laminate structure - e.g. For roof constructions, bonnets or door side parts, improved acoustic properties can be achieved, in addition, the structural depth of such components can be reduced and thus additional usable space can be obtained.
  • suitable polymeric binders improved heat and heat resistance up to 300 ° can be achieved C, this is important for use in the underbody area or as a wall to the engine compartment (“firewall”) the installation of functional elements such as Cable ducts in the organic intermediate layer are possible, e.g. for use in the roof or underbody area, thanks to a staggered production method in which the components are created separately from the production line ("preformed laminate"), individual high-performance modules or high-performance components can be created very quickly and flexibly.

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Body Structure For Vehicles (AREA)

Abstract

L'invention concerne des corps moulés multicouches pourvus d'éléments de renfort délimités localement. Le corps moulé multicouche selon l'invention comprend deux couches métalliques externes et au moins une couche intermédiaire constituée d'un liant organique et dans laquelle sont inclus des éléments de renfort à répartition anisotrope. Ces éléments de renfort anisotropes sont placés aux endroits de la couche intermédiaire de l'élément qui sont soumis à des effets de force ou à des sollicitations structurelles particulièrement importantes ou au niveau desquels le rayonnement acoustique est élevé. Ces corps moulés multicouches permettent de fournir des stratifiés particulièrement légers qui présentent toutefois une grande résistance structurelle et qui sont utilisés de préférence dans la construction mécanique, la construction automobile ou la construction d'appareils.
EP01989531A 2000-12-07 2001-11-28 Corps moule multicouche a elements de renfort delimites localement Withdrawn EP1351818A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10060816 2000-12-07
DE10060816A DE10060816A1 (de) 2000-12-07 2000-12-07 Mehrschichtiger Formkörper mit lokal begrenzten Verstärkungselementen
PCT/EP2001/013893 WO2002045954A2 (fr) 2000-12-07 2001-11-28 Corps moule multicouche a elements de renfort delimites localement

Publications (1)

Publication Number Publication Date
EP1351818A2 true EP1351818A2 (fr) 2003-10-15

Family

ID=7666138

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01989531A Withdrawn EP1351818A2 (fr) 2000-12-07 2001-11-28 Corps moule multicouche a elements de renfort delimites localement

Country Status (5)

Country Link
US (1) US20040091723A1 (fr)
EP (1) EP1351818A2 (fr)
AU (1) AU2002227955A1 (fr)
DE (1) DE10060816A1 (fr)
WO (1) WO2002045954A2 (fr)

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Publication number Priority date Publication date Assignee Title
DE10062009A1 (de) * 2000-12-13 2002-07-04 Henkel Teroson Gmbh Mehrschichtige Sandwich-Materialien mit organischen Zwischenschichten auf Epoxidbasis
DE10062859A1 (de) * 2000-12-16 2002-06-27 Henkel Teroson Gmbh Mehrschichtige Verbundmaterialien mit organischen Zwischenschichten auf Kautschukbasis
DE102004023058B4 (de) * 2004-05-11 2006-11-02 Bayerische Motoren Werke Ag Verfahren zur Herstellung eines Karosserieteils für ein Fahrzeug und ein nach diesem Verfahren hergestelltes Karosserieteil
US7973106B2 (en) * 2005-04-26 2011-07-05 Shiloh Industries, Inc. Acrylate-based sound damping material and method of preparing same
DE102016004446A1 (de) 2016-04-12 2017-10-12 Audi Ag 3D-Druck mit Verstärkungselementen
DE102017201834A1 (de) * 2017-02-06 2018-08-09 Thyssenkrupp Ag Halbzeug mit unterschiedlichen Eigenschaften
DE102018204407A1 (de) * 2018-03-22 2019-09-26 Thyssenkrupp Ag Funktionsintegrierte Temperierung in Stahl-Kunststoff-Hybriden durch wärmeleitfähige Füllstoffe

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JPS4865168A (fr) * 1971-12-06 1973-09-08
EP0145577B1 (fr) * 1983-12-12 1989-01-25 Hugues Lesourd Structure métallique emboutissable, de type sandwich, son procédé de fabrication et une installation pour la mise en oeuvre de ce procédé
DE3935120C2 (de) * 1989-10-21 1997-03-13 Reiner Prof Dr Ing Kopp Verfahren zur Herstellung von Metallverbundplatten
US5360647A (en) * 1990-09-28 1994-11-01 Daicel Chemical Industries, Ltd. Composite metal sheets
US5401564A (en) * 1993-03-23 1995-03-28 Hexcel Corporation Materials and processes for fabricating formed composite articles and use in shoe arch
DE19736839A1 (de) * 1997-08-23 1999-02-25 Volkswagen Ag Deformationsstruktur für den Insassenschutz in Fahrzeugen
DE19839931A1 (de) * 1998-09-02 2000-03-09 Daimler Chrysler Ag Geklebte Mehrschichtverbundplatten und Verfahren zur Herstellung von Mehrschichtverbundplatten
DE10062009A1 (de) * 2000-12-13 2002-07-04 Henkel Teroson Gmbh Mehrschichtige Sandwich-Materialien mit organischen Zwischenschichten auf Epoxidbasis
DE10062859A1 (de) * 2000-12-16 2002-06-27 Henkel Teroson Gmbh Mehrschichtige Verbundmaterialien mit organischen Zwischenschichten auf Kautschukbasis

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Title
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Also Published As

Publication number Publication date
WO2002045954A3 (fr) 2002-10-03
DE10060816A1 (de) 2002-06-20
WO2002045954A2 (fr) 2002-06-13
US20040091723A1 (en) 2004-05-13
AU2002227955A1 (en) 2002-06-18

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