EP1347869A1 - Formwerkzeuge zur verarbeitung von kunststoff- und verbundmaterialien und verwandte verarbeitungsverfahren - Google Patents

Formwerkzeuge zur verarbeitung von kunststoff- und verbundmaterialien und verwandte verarbeitungsverfahren

Info

Publication number
EP1347869A1
EP1347869A1 EP01993535A EP01993535A EP1347869A1 EP 1347869 A1 EP1347869 A1 EP 1347869A1 EP 01993535 A EP01993535 A EP 01993535A EP 01993535 A EP01993535 A EP 01993535A EP 1347869 A1 EP1347869 A1 EP 1347869A1
Authority
EP
European Patent Office
Prior art keywords
mold
imprint
composites
plastics
transformation
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
EP01993535A
Other languages
English (en)
French (fr)
Inventor
Alexandre Guichard
Gérard Legerot
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.)
RocTool SA
Original Assignee
RocTool 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 RocTool SA filed Critical RocTool SA
Publication of EP1347869A1 publication Critical patent/EP1347869A1/de
Ceased legal-status Critical Current

Links

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
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/02Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
    • B29C33/04Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means using liquids, gas or steam
    • 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
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/02Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
    • B29C33/06Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means using radiation, e.g. electro-magnetic waves, induction heating
    • 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
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/10Isostatic pressing, i.e. using non-rigid pressure-exerting members against rigid parts or dies
    • B29C43/12Isostatic pressing, i.e. using non-rigid pressure-exerting members against rigid parts or dies using bags surrounding the moulding material or using membranes contacting the moulding material
    • 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
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32Component parts, details or accessories; Auxiliary operations
    • B29C43/52Heating or cooling
    • 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
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0811Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using induction
    • 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
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32Component parts, details or accessories; Auxiliary operations
    • B29C43/36Moulds for making articles of definite length, i.e. discrete articles
    • B29C43/3642Bags, bleeder sheets or cauls for isostatic pressing
    • B29C2043/3649Inflatable bladders using gas or fluid and related details

Definitions

  • the present invention relates to molds for processing plastics and composites and the associated processing methods.
  • thermoplastic or thermosetting polymers as well as vulcanizable compounds
  • vulcanizable compounds there are numerous processes which consist in heating the material inside a mold while at the same time pressurizing so that it polymerizes taking the shape of the mold imprint.
  • These transformation processes generally use the thermal conduction of the molds to bring the material to the temperature desired for its polymerization.
  • the molds used are made of materials which conduct heat, on the one hand, and which withstand the temperature at which one wishes to heat the material, on the other hand.
  • the molds used in the prior art are therefore of two types: metal molds which conduct heat well and which easily withstand high temperatures and composite molds which only allow working at relatively low temperatures and with which can therefore only work with certain plastics or composites which have low processing temperatures.
  • metal molds which conduct heat well and which easily withstand high temperatures
  • composite molds which only allow working at relatively low temperatures and with which can therefore only work with certain plastics or composites which have low processing temperatures.
  • Metal molds are very expensive and require heavy investment. In addition, they rise in temperature and therefore pose problems in handling the molded parts, problems in cooling and heating the parts and molds and therefore problems related to cycle times. In addition, the need to bring the entire mold to temperature requires a very high energy consumption, especially in the case of large parts dimension.
  • Composite molds are less expensive but they are made of materials which do not withstand high temperatures; they can therefore only transform plastic and composite materials whose transformation temperature is low. In addition, they degrade easily when the temperature rises and they allow only a very limited number of cycles compared to metal molds.
  • the present invention aims to solve the aforementioned drawbacks using simple means, easy to implement and inexpensive. It offers a new generation of molds of composite types for the transformation of plastics and composites which make it possible to transform the material at high temperatures without damaging the molds and which allow a large number of cycles, while improving the duration of cycle times. whose length is linked to the problems of raising the temperature of the molds and of the material. They also allow significant energy savings compared to traditional metal molds.
  • these new molds allow in some cases to take advantage of a possibility of rapid maintenance without requiring the change of the entire mold when the imprint thereof is damaged.
  • the mold for the transformation of plastics and / or composites such as thermoplastic polymers, thermosetting polymers and vulcanizable compounds
  • the mold body provided with an imprint
  • the mold body includes heating means which directly heat the material to be transformed or an intermediate surface imprint contiguous to said material, without using the thermal conductivity of the mold body and / or of the imprint to heat the material to be transformed .
  • the imprint is made of a material which prevents the transfer of heat energy from the material to the mold body and vice versa.
  • the material forming the imprint is a mineral resin formed by the association of non-organic constituents.
  • the mold for the transformation of plastics and / or composites of the invention comprises complementary insulation means formed by at least one reflective sheet disposed in the material forming the imprint or between said material and that forming the mold body.
  • the heating means are of electrokinetic or magnetodynamic type and pass an electric current directly or by induction into the material or into the surface imprint.
  • the mold for the transformation of plastics and / or composites of the invention comprises a surface imprint made of electrically conductive material and disposed between the material and the imprint, to cover at least partially said imprint.
  • the surface imprint is produced by electrodeposition of a metal or of several layers of different metals, by machining of a metal or an alloy or by the shaping of an eri alloy strip malleable metal, by plasma spraying of metals or ceramics or by deposition of metals or ceramics in vapor phase under vacuum or chemical.
  • the mold for the transformation of plastics and / or composites of the invention comprises a mold body produced in two parts, a lower part or base which has an indentation and an upper part or punch which has a raised imprint.
  • the mold of the invention is characterized in that it comprises a device for pressurizing of the material to be transformed which has a flexible membrane.
  • the membrane is arranged around the raised impression to be pressurized by means of air circulation.
  • the membrane is made of silicone, of fluorinated elastomer or any other extensible material resistant to high temperatures.
  • the mold of the invention is characterized in that it has means for cooling the material.
  • the cooling means are at least partly formed by the pressurizing device which allows the circulation of fresh air between the imprint and the membrane .
  • the mold for processing plastics and / or composites can include additional cooling means which separate the surface imprint and / or the material from the mold imprint to allow the circulation of fresh air between them.
  • the mold body is made of cast resin.
  • the invention also relates to a process for transforming plastics or composites which is characterized in that it comprises a main step which consists in heating in a mold the material or a surface imprint which is directly contiguous thereto. without using the thermal conductivity of the mold body.
  • Figure 1 shows a perspective mold
  • Figures 2a to 2d schematically illustrate a complete cycle of transformation of a material in a mold of the invention.
  • Figure 2a illustrates the heating step
  • Figure 2b illustrates the pressurization step
  • Figure 2c shows the cooling step
  • Figure 2d illustrates the release of the part obtained.
  • Figures 3a to 3d and 4a to 4d illustrate in similar views the transformation cycle with two other variants of molds of the invention.
  • Figure 5 illustrates in perspective a second embodiment of a mold of the invention
  • Figures 6a to 6d respectively illustrate in cross section the different steps of a molding process of the invention, the establishment, heating, temperature control and cooling.
  • Figures 7a to 7 ⁇ respectively illustrate in cross section the heating, the temperature control, the cooling and the additional cooling and demolding step of the process of the invention.
  • FIG. 8 illustrates in perspective a variant construction of the mold of the invention
  • the present invention relates to a new generation of molds intended for the transformation of plastics and composites.
  • thermoplastic polymers such as polypropylene, polyethylene, polyamides, and all thermosetting polymers such as Epoxy and polyester for example.
  • these polymers may or may not be loaded with short, long or continuous fibers of carbon, glass, aramids, metallic, mineral or vegetable.
  • vulcanizable compounds such as rubber for example. All of these plastics and composites which can be transformed can be in several forms such as for example in the form of fabrics or sheets, in the form of tubular braids or even in the form of powders or granules without leaving of the protective field of the invention.
  • These molds include heating means (MC) intended to heat the plastic and / or composite material to be transformed (2) to the desired temperature. They consist of a mold body (3) which has an imprint (4) in which the plastic and / or composite material (2) is arranged.
  • MC heating means
  • the heating means (MC) directly heat the material to be transformed (2) or an intermediate surface imprint (5) located at the interface between the material to be transformed (2) and the imprint (4) of the mold body (3) without using the thermal conductivity of the mold body (3) and / or of the cavity (4).
  • the molds of the invention have heating means (MC) which heat only the material or an intermediate surface imprint (5) which is directly in contact with the material, without using the thermal conduction of the mold body.
  • the heating means (MC) are of electrokinetic type such as, for example, Joule effect, as shown in Figures 2a to 2d, and consist in passing an electric current directly into the plastic or composite material if the latter is electrically conductive or else in an intermediate surface imprint (5) if the material (2) is not conductive, said imprint being made of an electrically conductive material.
  • the circulation of the current causes heating of the material (2) or the imprint (5) which is contiguous to it thanks to the resistance of the material or the imprint, but does not act in any way on the mold body (3).
  • the electric current flowing in the material (2) or in the surface imprint (5) is a current induced by magnetic fields (40) and the means of heating (MC) are said to be of the magnetodynamic or induction type, the induced current acting similarly to the first embodiment to cause heating of the material (2) or of the surface imprint (5).
  • FIGS. 1 to 4d these are formed by a mold body (3) produced in two parts: a lower part (3a) or lower base which has an imprint ( 4a) in the hollow, and an upper part (3b), also called a punch, which has an upper imprint (4b) in relief, the upper and lower imprints forming the imprint (4) of the mold.
  • a mold body (3) produced in two parts: a lower part (3a) or lower base which has an imprint ( 4a) in the hollow, and an upper part (3b), also called a punch, which has an upper imprint (4b) in relief, the upper and lower imprints forming the imprint (4) of the mold.
  • the molds (1) are intended to produce hollow sections and have a mold body (3) produced in one or more parts (3a, 3b) which each have indentations in hollow (4a, 4b) which define the external shape of the profile.
  • the mold (1) uses an internal inflatable flexible envelope (150) to produce the interior of the profile in a manner known per se as shown in FIGS. 6a to 7d.
  • the mold is closed and the lower (4a) and upper (4b) cavities define the final shape of the material (2) during its transformation.
  • the lower and upper imprints (4a, 4b) are made of a material intended to avoid the transfer of heat from the material (2) to the mold body (3, 3a, 3b) proper and vice versa.
  • the base (3a) and the punch (3b) or the two parts of the mold for hollow profiles (3a, 3b) have a base made of a rigid plastic and / or composite material such as in casting resin (6) and they have an imprint (4a, 4b) on their opposite faces made of thermally insulating material (7) such as, for example, mineral resin, this material being arranged to form a layer which prevents the transfer of heat energy, that is to say to form a barrier or a heat shield.
  • additional thermal insulation means can be provided. These means can advantageously be obtained by the addition of reflective sheets comprising a silver plating or Mica for example, said sheets being able to be disposed inside the insulating material (7) or between said material and that forming the mold body itself. .
  • these bases (3a, 3b) can be made of common composite material such as Epoxy resin (6) without being damaged during the transformation cycles even when the material (2) is transformed at high temperatures. (above 150 ° C).
  • the molds of the invention are therefore of the composite type but, unlike the composite molds of the prior art which could only process materials of the thermosetting type at maximum temperatures of 130 ° C .; they can carry out the transformation at high temperatures without being damaged, in particular thanks to their imprint (4a, 4b) of thermally insulating material (7) and to the heating means (MC) which directly heat the material (2) or an imprint of surface (5).
  • the imprints (4a, 4b) are made of mineral resin formed by the association of non-organic constituents according to several possible methods (polyaddition, polycondensation, sintering, cooking, etc.) and are for example made of inorganic ceramic resulting from a polycondensation of at least one mineral resin such as those sold under the brands FIXWOOL (PS4, EZG, AL) or Geopolymer. These mineral resins may also contain fillers (carbon, stainless steel fibers, alumina silicate) or other additives.
  • the plastic and / or composite material (2) to be transformed is electrically conductive, the molds (1) do not have an intermediate surface imprint (5), as shown in FIGS.
  • this intermediate surface imprint (5) can be produced by electrodeposition of a metal or of several layers of different metals or by shaping a strip of malleable metal alloy of thickness included between 0.01 mm to 5 mm, for example. It could also be obtained by machining from steel, alloy or any other metal, without going outside the protective field of the invention. It can also be obtained by hot spraying of metals (plasma) or conductive ceramics or by deposition of metals or ceramics in the vapor phase under vacuum or chemical.
  • the heating means (MC) of the mold (1) are formed by electrical contacts (8a, 8b) made of copper which make it possible to pass an electric current directly into the material to be transform (2).
  • the heating means are formed by inductors (9, 9a, 9b, ...) which, by the application of magnetic fields (40), cause circulation an electric current in the material (2) or in a surface imprint (5) to heat them.
  • the mold (1) has a device for pressurizing the material (2) intended to be used during the heating cycle in order to obtain a uniform transformation of the material ( 2) by imposing uniform pressure and temperature constraints on it regardless of the shape of the part to be produced and therefore of the imprint (4a, 4b).
  • the pressurizing device is formed by a flexible membrane (10) and air circulation means (11, 12a, 12b) intended, in particular, to inflate said membrane (10).
  • the membrane (10) is advantageously fixed around the raised impression (4b) of the punch (3b) in order to be able to be pressurized, thus taking the shape of the impression.
  • the pressurizing means are advantageously formed by one or more pressurization chambers (11) located in the body of the punch (3b) and provided with pressurization and circulation channels (12a, 12b) which connect the chambers to the surface of the raised imprint (4b) that the membrane (10) envelops.
  • the molds (1) comprise means for cooling the material (2) intended to allow the cooling of the plastic and / or composite parts (2) in order to facilitate demolding, in particular.
  • These cooling means can be at least partially formed by the pressurizing device (10, 11, 12a, 12b) which allows, as shown in Figures 2c, 3c and 4c to circulate fresh air between l 'imprint (4b) of the punch (3b) and the membrane (10).
  • This air which can be chosen at -30 ° C., for example, makes it possible to cool the material (2) through the membrane (10) and the imprint (4b) of the punch.
  • the cooling is effected by means of a partial withdrawal of the punch which allows while maintaining the pressure in the membrane (10) to create a space between its imprint (4b) and said membrane to circulate cold air.
  • the membrane (10) can advantageously be made of silicone, or of fluorinated elastomer or any other extensible material resistant to high temperatures.
  • These additional cooling means are, for example, constituted by a spacing device intended to separate the insulating layer (7) forming the hollow imprint (4a) from the surface imprint (5) or from the transformed material ( 2) to allow the circulation of fresh air between them by means of an air circulation system located in the base (3a), as shown in Figure 4d.
  • a spacing device this is, for example, produced by an inflatable or elastomeric seal (13) disposed in a groove provided for this purpose around the recess (4a).
  • an elastomer frame (14) makes it possible to maintain the tightness of the mold, even during the cooling phase illustrated in FIGS. 2c, 3c and 4c.
  • the molds of the invention are described in a simplified diagram in which they are produced in two parts but that they could obviously be of complex shape without however going outside the protective field of the 'invention.
  • the heating means which heat the material (2) or the surface imprint (5) described are of electrokinetic or magnetodynamic type, however, they could also be of another type.
  • the molds (1) are also provided for producing hollow profiles. Also, they comprise a mold body (3) advantageously formed of several elements (3a, 3b) each having a hollow imprint (4a, 4b) in which the user arranges the material (2).
  • the material (2) is advantageously arranged around an inflatable envelope (150) called a balloon, and which is pressurized when the material is heated as shown in Figures 6b and 7a.
  • the heating means can be of the magnetodynamic type as shown in FIGS. 6b and 7a or of the electrokinetic type as shown in FIG. 8, or the like.
  • the molds also include an imprint (4a, 4b) made of thermally insulating material (7) and include a surface imprint (5) depending on the nature of the material (2) to be transformed (electrical conductivity).
  • FIG. 5 and FIGS. 6a to 7d represent a mold (1) using magnetodynamic heating means formed by inductors (9a, 9b), a first variant illustrating the transformation of an electrically non-conductive material (FIGS. 5, 6a to 6d) thanks to the surface imprint (5) and a second variant illustrates in Figures 7a to 7d the transformation of a conductive material (2).
  • the cooling means are obtained by means of a fresh air circulation device which makes it possible to establish an air circulation at a pressure P2 greater than the pressure PI prevailing in the bladder ( 150) as shown in Figures 6d and 7c.
  • additional cooling means not illustrated could also allow the cooling of the surface imprint (5) and / or of the external face of the insulating layers (4a, 4b) by separating them from the mold body as the shows figure 7d.
  • the layers (4a, 4b) of insulating material (7) and the mold body (3, 3a, 3b) are assembled by any type of fixing as by gluing or by mechanical fasteners of the Insert type.
  • These fixing means can also allow the fixing of the surface imprint
  • the molds (1) can be equipped with temperature control means capable of accurately measuring or evaluating the temperature of the material (2) and / or of the surface imprint ( 5).
  • These means can be produced by an advantageously conical measurement orifice (151) in which a laser sighting device (152) performs an infrared measurement directly on the surface imprint (5) as illustrated in FIG. 6c or on a patch. of material with high thermal conductivity (153) such as in mineral resin charged with a copper-beryllium alloy for example as shown in FIG. 7b.
  • these control means could be obtained in a different way, thus according to the variant illustrated in FIG.
  • the control can be carried out by measuring the intensity of the electric current passing through the material, said intensity being a function of the temperature of the material.
  • the invention also relates to a process for transforming plastics and / or composites such as thermoplastic, thermosetting polymers, or vulcanizable compounds, associated with the molds described above (1).
  • This process consists, in a main step illustrated in FIGS. 2a, 3a, 4a, of heating the material to be transformed (2) or a surface imprint (5) directly, without using the thermal conductivity of the mold body.
  • this method also includes an additional step of pressurizing the material, using the inflatable membrane device (10, 11, 12a, 12b) as shown in FIGS. 2b, 3b and 4b, followed by a phase of cooling of the material (2) by circulation of cold air as illustrated in FIGS. 2c, 3c and 4c and a demolding step illustrated in FIGS. 2d and 3d.
  • This demolding phase can also be accompanied by a step of additional cooling of the surface imprint (5), as shown in FIG. 4d.
  • the surface imprint (5) and / or the imprints (4, 4a, 4b) made of material forming a thermal barrier (7) can be arranged in a removable manner in the mold (1) to using suitable fixing means so that they can be changed when they are damaged or worn, without changing the entire mold body (3, 3a, 3b).

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
EP01993535A 2000-11-08 2001-11-07 Formwerkzeuge zur verarbeitung von kunststoff- und verbundmaterialien und verwandte verarbeitungsverfahren Ceased EP1347869A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0014324 2000-11-08
FR0014324A FR2816237B1 (fr) 2000-11-08 2000-11-08 Moules pour la transformation des matieres plastiques et composites et procede de transformation associe
PCT/FR2001/003460 WO2002038355A1 (fr) 2000-11-08 2001-11-07 Moules pour la transformation des matieres plastiques et composites et procede de transformation associe

Publications (1)

Publication Number Publication Date
EP1347869A1 true EP1347869A1 (de) 2003-10-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP01993535A Ceased EP1347869A1 (de) 2000-11-08 2001-11-07 Formwerkzeuge zur verarbeitung von kunststoff- und verbundmaterialien und verwandte verarbeitungsverfahren

Country Status (6)

Country Link
US (1) US7419631B2 (de)
EP (1) EP1347869A1 (de)
JP (1) JP4242644B2 (de)
CA (1) CA2428113C (de)
FR (1) FR2816237B1 (de)
WO (1) WO2002038355A1 (de)

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CA2428113C (fr) 2010-10-12
JP4242644B2 (ja) 2009-03-25
FR2816237B1 (fr) 2003-09-19
US7419631B2 (en) 2008-09-02
WO2002038355A1 (fr) 2002-05-16
CA2428113A1 (fr) 2002-05-16
FR2816237A1 (fr) 2002-05-10
US20040058027A1 (en) 2004-03-25

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