EP1855859A1 - Batonnets de renforts concentres et leur fabrication - Google Patents
Batonnets de renforts concentres et leur fabricationInfo
- Publication number
- EP1855859A1 EP1855859A1 EP06709433A EP06709433A EP1855859A1 EP 1855859 A1 EP1855859 A1 EP 1855859A1 EP 06709433 A EP06709433 A EP 06709433A EP 06709433 A EP06709433 A EP 06709433A EP 1855859 A1 EP1855859 A1 EP 1855859A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reinforcing
- bundle
- rods
- son
- organic material
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING 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
- B29K2709/00—Use of inorganic materials not provided for in groups B29K2703/00 - B29K2707/00, for preformed parts, e.g. for inserts
- B29K2709/08—Glass
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- the present invention relates to a method of manufacturing rods of concentrated reinforcements used in particular for manufacturing composite products by molding (in particular by injection, extrusion compression, comoulage, etc.) and also relates to the products obtained.
- mixtures of organic material, fibrous reinforcements (such as glass strands) and additive (s) are used (for example to color or bring particular functions).
- Mixing can be done directly in an extruder or in an injection molding machine from reinforcing threads, which may or may not already be coated with organic material, and which are generally already cut to facilitate dosing and mixing, the other possible components being if necessary added in the extruder or in the press.
- the desired benefits can be one and / or the other of the following advantages: cost savings, better preservation of reinforcements (for example the length of the reinforcement threads) for better mechanical properties, better dispersion during molding, ease of adaptation according to the desired products, easier implementation, etc.
- the present invention therefore relates in the first place to a method for manufacturing concentrated rods in which at least one bundle of yarns having more than 70% by weight of reinforcement material (s) and at least 0.1% by weight of moisture, is heated and shaped before being cut into sticks.
- the rods obtained comprise a reinforcing material essentially in the form of son or filaments (cut to the length of the stick) advantageously linked together by at least one organic material as explained later.
- the present invention also relates to the reinforcing rods (or rod-shaped reinforcing threads) developed and obtained in particular by the above method.
- These rods have a level of material (s) of reinforcement greater than 65% and preferably greater than 70% (or even at least 80%) by weight.
- These reinforcements are bonded together or embedded in at least a first organic material, and if necessary are sheathed with at least a second material, generally at least one organic material, as explained later, the two organic materials may be identical or different .
- the yarn bundle mentioned according to the invention comprises at least one reinforcing material (glass, carbon, aramid, etc., this material preferably being glass) in the form of at least a part of said yarns or in the form of filaments (generally obtained in a known manner by stretching this material under a spinneret, these filaments being then combined into threads) forming at least a portion of said threads, the amount of reinforcing material (s) within the bundle being more than 70% by weight in accordance with to the invention, and preferably ranging from 75 to 99% by weight, or even 80 to 95% by weight.
- At least part of the yarns used also comprise at least one thermoplastic organic material, this material being for example chosen from polyolefins, in particular polyethylene (PE), polypropylene (PP), polyesters, especially polyterephthalate.
- PE polyethylene
- PP polypropylene
- PET polypropylene
- PBT polybutylene terephthalate
- EPDM polymer ethylene propylene
- PVC polyvinyl chloride
- this material is also in the beam in the form of son or filaments.
- the yarns used in the process according to the invention are composite (or co-mixed) yarns formed of reinforcing filaments (preferably glass) and filaments of at least one thermoplastic organic material, these filaments being advantageously intimately mixed, the intimate structure of these son facilitating the impregnation of the glass fibers by the thermoplastic material and, in the method according to the invention, to form, despite the high rate of reinforcements, a consolidated structure (that is to say having a cohesion and integrity that allows handling without damage) well impregnated and homogeneous.
- Advantageous composite yarns may be obtained according to a direct process such as that described in patents EP 0 367 661, WO 98/01751 or EP 0 These yarns having an excellent co-blending index inducing an excellent distribution of the glass yarns in the thermoplastic material as explained in the patent application WO00 / 24566.
- the method according to the invention uses as son forming the beam only composite son.
- son forming the beam only composite son it is not excluded in particular to combine composite son and reinforcing son to further increase the concentration of reinforcement rods.
- the inventors have also demonstrated, as it appears in the definition of the invention, the advantage of using a bundle having a humidity (water content measured for example by evaporation in an oven) of at least 0.1%, preferably at least 0.5% and particularly preferably at least 3% by weight; the presence of a certain humidity, far from impeding the implementation and the properties of the products obtained, indeed makes it possible to handle the yarns well in the rod manufacturing process according to the invention, while at the same time making it possible to obtain products with mechanical properties at least as good or better than those obtained from previously dried, and while providing an economic advantage (it is possible in particular to directly use son obtained or collected under the die without expensive intermediate step of drying).
- the humidity is also chosen less than 8%, advantageously less than 5% by weight, in particular to allow good consolidation of the son and the beam in the process according to the invention.
- the son can be formed beforehand or extracted individually or in groups, at least one winding. According to a preferred embodiment of the invention, they are extracted from at least one winding, such as a roving or roving, and driven at a speed of at least 10 m / min, preferably several tens of m / min, in particular of the order of 40 to 100 m / min, in particular of the order of 50 m / min, using for example a traction device (which can be in particular a traction bench).
- a traction device which can be in particular a traction bench.
- a step of regulating the tension of the threads may be provided (for example during their gathering in bundle (x) or before gathering them) and / or the threads may be rid of any static electricity, for example before the passage of the beam in the heating zone.
- the son are gathered in the form of at least one beam as mentioned in the process according to the invention. It goes without saying that it is also possible to form several disjoint beams undergoing the same or different treatment in parallel, of which at least one undergoing the steps indicated in the process according to the invention to obtain the concentrated rods.
- At least one beam is heated (generally by passing through at least one heating device, such as an infra-red radiation oven) at a temperature enabling it to be shaped and / or consolidated, and permitting, where appropriate, the impregnation of the reinforcement filaments or filaments with the organic material, in particular at a temperature reaching at least that of melting the thermoplastic material present within the bundle of threads and preferably greater than at least 20 ° C at said melting point of the thermoplastic material, this temperature nevertheless remaining below the decomposition temperature of said material and at the melting temperature of the reinforcing material.
- at least one heating device such as an infra-red radiation oven
- the bundle of heated wires is maintained approximately in temperature until its conformation (or calibration), the conformation taking place advantageously by passing through one and preferably several calibration channels until the desired section is obtained.
- the dies chosen are advantageously of simple profile (s) in the direction of the production line and descending section (s).
- the beam may also optionally undergo a step promoting the impregnation of the reinforcing threads or filaments with the organic material present, by passing through a device such as one or more bars.
- a device such as one or more bars.
- step or steps of conformation and impregnation favor the obtaining of a consolidated bundle (or impregnated or integrated, that is to say in which the son are linked together, this consolidated bundle being also designated by the term rod or wick according to the present invention, or strand, cable or rope).
- the wire bundle is further subjected to a step of sheathing by passing through a die also fed with at least one organic material in the molten state, this material may be identical or different from the organic material forming the son.
- the cladding material may also be composite, formed of several materials, in particular at least one organic material and additive (s) (for example an additive improving resistance to ultraviolet radiation, a coupling agent to increase the performance mechanical, thermal or chemical stabilizer, dye or pigment, flame retardant, etc.) and / or filler (s) (talc, glass fibers, short or long, etc.).
- additive for example an additive improving resistance to ultraviolet radiation, a coupling agent to increase the performance mechanical, thermal or chemical stabilizer, dye or pigment, flame retardant, etc.
- filler talc, glass fibers, short or long, etc.
- the cladding material may thus advantageously make it possible to confer additional properties on the rods obtained and the composites molded from these rods (anti-UV properties, improvement of the mechanical performances, etc.). Having already functionalized products also makes it possible during molding to use only inexpensive standard dilution materials, which simplifies and reduces the cost of molding.
- the cladding also prevents the formation of fibrils or fines (fibers detached from the stick) during cutting into sticks, these fibrils may cause problems conveying or congestion of the injection members during molding (and damage the systems of conveying or said injection members), and may adversely affect the mechanical properties of the products obtained.
- the sheathed sticks are also perfectly manipulable, dosable and transportable in the supply pipes because smoothed by the sheath, the sheath also acting as a protection, and do not lose their integrity until use to form composites by molding.
- the sheathing finally makes it possible to adjust the reinforcement ratio to the control by varying the quantity of cladding material delivered during the manufacture in line and thus makes it possible to obtain rods with various concentrations of reinforcements from a product. departure which can advantageously not vary.
- the cladding material comprises at least one thermoplastic organic material, for example a polyolefin (especially polyethylene or polypropylene) or polyvinyl chloride, or an elastomer, for example a modified polypropylene SEBS (styrene ethylene butadiene styrene), etc.
- this material is advantageously chosen to be identical or similar or chemically compatible with the organic material of the yarns (so that there is a good adhesion or even continuity between the two materials), this material possibly being loaded with additives as mentioned previously.
- the cladding material introduced into the die can come for example from an extrusion device.
- the beam may also be coated with several identical or different materials supplying the die (or if necessary several dies in series or in parallel), this mode further widening the range of products obtained.
- the cladding material may vary from one beam to another as appropriate.
- the thickness of the sheath may be variable; as an example for a rod of the order of 3 mm thick, the sheath may be of the order of 0.1 mm or one tenth of the thickness of the stick, or more.
- the resulting beam is generally cooled (by passage for example in a water tank or a cold die), if necessary dried (by blowing or suction), then cut or sectioned (for example using a milling cutter or granulator with rotating blades) in rods, of length generally between 1 and 40 mm, preferably between 5 and 30 mm, for example of the order of 12 mm.
- the method and the products according to the invention have the advantage of being adaptable without changing the starting materials.
- the method according to the invention is easy and quick to implement, and is economical.
- the rods according to the invention have a high level of reinforcement as previously defined, while being intact and if necessary well impregnated, and may have a sheath as mentioned above.
- these rods in particular sheathed
- the rods according to the invention generally have a reinforcing son length of between 1 and 40 mm, preferably between 5 and 30 mm, for example of the order of 12 mm.
- the present invention also relates to a device for implementing an advantageous embodiment of the aforementioned method.
- This device comprises one or more means for providing at least one bundle of wires, at least one means for heating said bundle, at least one shaping device, at least one sheathing die, fed by at least one molten material and having to receive simultaneously the bundle of wires and the molten material in contact with said bundle, and at least one cutting device, for cutting the sheathed bundle into rods.
- the device may also comprise (in combination or in addition to the preceding means) one or more of the following means, in particular:
- one or more means for assembling the wires in the form of at least one bundle of parallel wires for example of plate type (s) with eyelets and / or roller (s) and / or grooves (s));
- one or more means for regulating the tension of the threads for example upstream aforementioned gathering means;
- the son may be from windings, these windings can be placed on a creel from which the son are unwound.
- the heating means or means generally comprise one or more ovens, for example of the infrared type, preferably operating with lamps regulated in power as a function of the temperature of the beam, this kind of oven having the advantage of being at the energy efficient and easy to regulate.
- impregnation device it is possible, for example, to use a device comprising three members arranged in a triangle and between which the beam travels, the height of separation of the members being adapted to establish an appropriate pressure on the surface of the bundle, these members possibly being cylinders or bars.
- the conformation devices strictly speaking may for example comprise a heating die, and / or rollers between which the wire bundle circulates, etc.
- the dies used advantageously have a simple profile with a section, for example varying gradually (for example decreasing) and then constant according to the locations, around an axis parallel to the direction of the production line.
- the cladding die may also comprise one or more means for supplying the cladding material by applying an overpressure thereto. Said material can come into contact with the rod by different channels in the die. Depending on the section of the die and / or the presence of different channels and / or the application of overpressure (s) and / or the positioning of the beam in the die, the quantity of material (s) delivered (s) may be different at different points of the beam section.
- the sheath melt generally comes from at least one extruder.
- the cutting device may in particular be a granulator or a bur, as mentioned above.
- the various elements of the device according to the invention may be fixed or possibly mobile (in translation and / or in rotation).
- the invention also relates to a composite product obtained by molding from the rods according to the invention.
- the rods according to the invention make it possible to obtain, at high rates, complex parts (possibly comprising ribs, bosses, etc.) having a satisfactory distribution of the reinforcing material, the composites obtained from these rods further having good mechanical properties.
- the composites obtained from the rods according to the invention can be, for example, automobile body parts such as front faces, dashboards, door modules, engine screens, tailgate linings, etc.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Moulding By Coating Moulds (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
- Processing Of Solid Wastes (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0550618A FR2882958B1 (fr) | 2005-03-09 | 2005-03-09 | Batonnets de renforts concentres et leur fabrication |
PCT/FR2006/050049 WO2006095101A1 (fr) | 2005-03-09 | 2006-01-24 | Batonnets de renforts concentres et leur fabrication |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1855859A1 true EP1855859A1 (fr) | 2007-11-21 |
Family
ID=35058715
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06709433A Withdrawn EP1855859A1 (fr) | 2005-03-09 | 2006-01-24 | Batonnets de renforts concentres et leur fabrication |
Country Status (10)
Country | Link |
---|---|
US (1) | US20080171200A1 (ru) |
EP (1) | EP1855859A1 (ru) |
JP (1) | JP5153612B2 (ru) |
KR (1) | KR20070108235A (ru) |
CN (1) | CN101137476B (ru) |
BR (1) | BRPI0607814A2 (ru) |
FR (1) | FR2882958B1 (ru) |
MX (1) | MX2007010777A (ru) |
RU (1) | RU2404052C2 (ru) |
WO (1) | WO2006095101A1 (ru) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2606438C2 (ru) * | 2011-11-07 | 2017-01-10 | Тейджин Арамид Гмбх | Гранула, содержащая арамидную пульпу и материал-наполнитель |
DE102013101188A1 (de) * | 2013-02-07 | 2014-08-07 | Rehau Ag + Co | Verfahren zur Herstellung eines PVC-Langfaserthermoplasts |
EP3068600B1 (en) * | 2013-11-15 | 2020-02-19 | SABIC Global Technologies B.V. | Process for producing a glass fibre-reinforced thermoplastic polymer composition |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL279948A (ru) * | 1961-06-20 | 1900-01-01 | ||
DE1900541C3 (de) * | 1969-01-07 | 1982-05-27 | Bayer Ag, 5090 Leverkusen | Verfahren zur kontinuierlichen Herstellung von homogenen faserverstärkten Polyamidformmassen |
FR2031719A5 (ru) * | 1969-02-05 | 1970-11-20 | Verre Textile Ste | |
US4037011A (en) * | 1972-02-15 | 1977-07-19 | Dart Industries Inc. | Glass fiber reinforced thermoplastic composition and process for its preparation |
US4169186A (en) * | 1978-04-17 | 1979-09-25 | Asahi-Dow Limited | Molding material structure |
US4487797A (en) * | 1983-12-01 | 1984-12-11 | Ppg Industries, Inc. | Glass fibers to reinforce polymeric materials |
JPS60154029A (ja) * | 1984-01-24 | 1985-08-13 | Ube Nitto Kasei Kk | 棒状連続押出成形体の整形方法および整形装置 |
US5989710A (en) * | 1988-10-21 | 1999-11-23 | Toyo Boseki Kabushiki Kaisha | Molding material for thermoplastic composites |
FR2638467B1 (ru) * | 1988-10-28 | 1991-11-08 | Saint Gobain Vetrotex | |
JPH03146443A (ja) * | 1989-10-31 | 1991-06-21 | Asahi Fiber Glass Co Ltd | 成型材料を製造する方法 |
JP2983569B2 (ja) * | 1990-03-02 | 1999-11-29 | ポリプラスチックス株式会社 | 長繊維強化熱可塑性ポリエステル樹脂の製造法及び該樹脂よりなる成形品 |
PL332698A1 (en) * | 1996-10-14 | 1999-09-27 | Dsm Nv | Small stick-shaped pellets |
US6090319A (en) * | 1997-01-14 | 2000-07-18 | Ticona Celstran, Inc. | Coated, long fiber reinforcing composite structure and process of preparation thereof |
US5868982A (en) * | 1997-04-01 | 1999-02-09 | Owens-Corning Fiberglas Technology, Inc. | System for preparing glass fiber pellets |
US6093359A (en) * | 1997-11-06 | 2000-07-25 | Gauchel; James V. | Reinforced thermoplastic composite systems |
DE10209420A1 (de) * | 2002-03-05 | 2003-09-18 | Ticona Gmbh | Langfaserverstärkte thermoplastische Kunststoffstrukturen |
US7138023B2 (en) * | 2003-10-17 | 2006-11-21 | Owens-Corning Fiberglas Technology, Inc. | Development of thermoplastic composites using wet use chopped strand (WUCS) |
US20060147707A1 (en) * | 2004-12-30 | 2006-07-06 | Jian Meng | Compacted, chopped fiber glass strands |
-
2005
- 2005-03-09 FR FR0550618A patent/FR2882958B1/fr not_active Expired - Fee Related
-
2006
- 2006-01-24 MX MX2007010777A patent/MX2007010777A/es unknown
- 2006-01-24 JP JP2008500237A patent/JP5153612B2/ja not_active Expired - Fee Related
- 2006-01-24 RU RU2007137114/05A patent/RU2404052C2/ru not_active IP Right Cessation
- 2006-01-24 WO PCT/FR2006/050049 patent/WO2006095101A1/fr active Application Filing
- 2006-01-24 US US11/817,834 patent/US20080171200A1/en not_active Abandoned
- 2006-01-24 KR KR1020077020504A patent/KR20070108235A/ko active IP Right Grant
- 2006-01-24 BR BRPI0607814-1A patent/BRPI0607814A2/pt not_active IP Right Cessation
- 2006-01-24 EP EP06709433A patent/EP1855859A1/fr not_active Withdrawn
- 2006-01-24 CN CN2006800074441A patent/CN101137476B/zh not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO2006095101A1 * |
Also Published As
Publication number | Publication date |
---|---|
RU2007137114A (ru) | 2009-04-20 |
FR2882958A1 (fr) | 2006-09-15 |
US20080171200A1 (en) | 2008-07-17 |
MX2007010777A (es) | 2007-09-25 |
JP5153612B2 (ja) | 2013-02-27 |
JP2008532799A (ja) | 2008-08-21 |
CN101137476B (zh) | 2012-12-05 |
CN101137476A (zh) | 2008-03-05 |
RU2404052C2 (ru) | 2010-11-20 |
KR20070108235A (ko) | 2007-11-08 |
FR2882958B1 (fr) | 2011-03-18 |
BRPI0607814A2 (pt) | 2010-03-23 |
WO2006095101A1 (fr) | 2006-09-14 |
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