EP1869739B1 - Open-chamber multi-spark plug - Google Patents

Open-chamber multi-spark plug Download PDF

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Publication number
EP1869739B1
EP1869739B1 EP06726308A EP06726308A EP1869739B1 EP 1869739 B1 EP1869739 B1 EP 1869739B1 EP 06726308 A EP06726308 A EP 06726308A EP 06726308 A EP06726308 A EP 06726308A EP 1869739 B1 EP1869739 B1 EP 1869739B1
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EP
European Patent Office
Prior art keywords
spark plug
chamber
insulator
plug according
shell
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Not-in-force
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EP06726308A
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German (de)
French (fr)
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EP1869739A1 (en
Inventor
Nadim Malek
André AGNERAY
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Renault SAS
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Renault SAS
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Publication of EP1869739A1 publication Critical patent/EP1869739A1/en
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Publication of EP1869739B1 publication Critical patent/EP1869739B1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T13/00—Sparking plugs
    • H01T13/50—Sparking plugs having means for ionisation of gap
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T13/00—Sparking plugs
    • H01T13/52—Sparking plugs characterised by a discharge along a surface

Definitions

  • the present invention relates to a spark plug for plasma generation, used in particular for igniting internal combustion engines by electric spark between the electrodes of a candle.
  • a radiofrequency spark plug of an internal combustion engine comprising two plasma generation electrodes separated by an insulator, one of the two electrodes may consist of all of the yoke and the base of the candle.
  • Plasma-generation spark plugs are high-frequency multi-spark ignition systems, capable of ensuring the ignition of spark ignition engines under the best conditions, while reducing pollutant emissions, particularly in lean mixtures. They are subject to fouling, especially cold.
  • a spark plug according to the preamble of claim 1 is known from the document WO-A-0120162 .
  • the present invention aims to adjust the thermal index of a multi-spark plug, so that it can quickly rise in temperature, without subsequent risk of pre-ignition.
  • the chamber is disposed between the base and the insulator.
  • the chamber may contain a dilation piece capable of opening or closing its inlet to hot gases.
  • the measures proposed make it possible to limit the cooling of the ceramic in the starting phase without increasing its operating temperature. This gives a non-linear thermal index, which corresponds to rapid heating of the candle without the risk of hot pre-ignition.
  • a spark plug 1 of known type comprising two electrodes 2, 3 for generating plasma separated by an insulator 4 of dielectric material such as a ceramic.
  • the two electrodes 2, 3 constitute respectively an outer cap 3 surrounding the insulator, and a central electrode 2, housed in a central bore of the insulator 4.
  • the base 3 conventionally has an external thread 3a for screwing the candle in the cylinder head of the engine.
  • carbon deposits disturb the operation of the candle, creating areas of current leakage. From a certain temperature, of the order of 400 ° C, the carbonaceous deposits are destroyed by pyrolysis.
  • the candle of the figure 2 additionally has a dead volume 6, constituting an open chamber to the outside.
  • the chamber 6 extends between the base 3 and the insulator 4.
  • the chamber may advantageously have a first tubular sector 6a connected to a second circular sector 6b open on the outside.
  • the walls of the chamber 6 may be metallized.
  • the layer, or metal sleeve 7, applied to the insulator, is then in direct contact with the hot gases, and particularly oxidants in lean mixture ("lean burn "), of the combustion chamber.
  • the metallization of the walls of the chamber 6 makes it possible in particular to prevent the creation of a plasma between the ceramic of the insulator and the base.
  • This metal layer 7 may for example consist of a sleeve brazed to the ceramic, which will ensure the resistance thereof to the oxidizing gases.
  • the thickness of the sleeve may be a compromise between its resistance to thermochemical erosion, its thermal resistance and its cost of production.
  • the sleeve may itself be protected by an inert deposition, a thin ceramic layer, or other metal deposit particularly resistant to oxidation, such as nickel.
  • the figure 3 illustrates a second embodiment of the invention, according to which the chamber 6 is a simple tubular opening formed in the mass of the base 3.
  • the chamber no longer extends between the base and the insulator, as previously but constitutes a cut in the mass of the base.
  • the application of a metal layer 7 is imperative to avoid the formation of a plasma.
  • the metallization will be applied simply on the bonding interface between the ceramic 4 and the base 3, independently of the chamber 6.
  • the Figures 4A to 5B illustrate additional provisions for automatically adapting the behavior of the chamber to the temperature conditions of the candle, so as to further improve the "non-linear" setting of the thermal index of the candle, particularly for that it behaves like a very hot candle when the engine is still cold, and like a warm candle, when the engine is hot, especially under heavy load.
  • the chamber 6 may contain a dilation piece 8, 9 capable of opening or closing its inlet to hot gases.
  • the expansion chamber is contracted, and opens the passage to hot gases that provide a thermal flow accelerating the operation of the candle.
  • the room is expanded and closes the hot gas passage.
  • the candle reaches its thermal equilibrium at a lower temperature than if the chamber had remained open.
  • the expansion piece 8 is a corrugated sleeve, one end is fixed and the other end carries a cylindrical flap 8a closing the inlet of the chamber 6 when the sleeve is expanded.
  • the expansion piece 9 is a double wall sleeve containing a metal 9a, fuse at relatively low temperature: the expansion of the liquid metal 9a causes the sleeve 9 to swell, thus blocking the passage of hot gases.

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  • Ignition Installations For Internal Combustion Engines (AREA)
  • Spark Plugs (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

An internal combustion engine radio frequency spark plug including two plasma-generating electrodes, separated by an insulator, that constitute respectively an outer shell enclosing the insulator and a central electrode housed in a central bore of the insulator. The spark plug includes a deep opening over the entire circumference of the shell, forming a heat-exchanger chamber inside the spark plug shell, opening outwards.

Description

La présente invention concerne une bougie de génération de plasma, utilisée notamment pour l'allumage de moteurs à combustion interne par étincelles électriques entre les électrodes d'une bougie.The present invention relates to a spark plug for plasma generation, used in particular for igniting internal combustion engines by electric spark between the electrodes of a candle.

Plus précisément, elle concerne une bougie d'allumage radiofréquence de moteur à combustion interne comprenant deux électrodes de génération de plasma séparées par un isolateur, une des deux électrodes pouvant être constituée de la totalité de la culasse et du culot de la bougie.More specifically, it relates to a radiofrequency spark plug of an internal combustion engine comprising two plasma generation electrodes separated by an insulator, one of the two electrodes may consist of all of the yoke and the base of the candle.

Les bougies à génération de plasma constituent des systèmes d'allumage multi-étincelles à haute fréquence, capables d'assurer dans les meilleures conditions l'allumage des moteurs à allumage commandé, tout en réduisant les émissions polluantes, notamment en mélange pauvre. Elles sont sujettes à l'encrassement, notamment à froid.Plasma-generation spark plugs are high-frequency multi-spark ignition systems, capable of ensuring the ignition of spark ignition engines under the best conditions, while reducing pollutant emissions, particularly in lean mixtures. They are subject to fouling, especially cold.

Comme toutes les bougies, elles sont caractérisées par un indice thermique. Cet indice prend en compte leur comportement thermique sur des points de fonctionnement moteur particuliers. Il traduit notamment leur capacité à supporter des températures suffisamment élevées pour éliminer l'encrassement par pyrolyse, sans faire de « pré-allumage ».Like all candles, they are characterized by a thermal index. This index takes into account their thermal behavior on particular engine operating points. It reflects in particular their ability to withstand temperatures high enough to eliminate fouling by pyrolysis, without doing "pre-ignition".

Par les publications FR 2859830 , FR 2859869 , et FR 2859831 , on connaît une bougie multi-étincelles dite froide, car elle ne monte pas suffisamment vite en température pour éviter l'encrassement. Sur de telles bougies, on a constaté en effet l'accumulation d'un dépôt de carbone sur les électrodes, qui réduit significativement l'isolation nécessaire entre la pointe de l'électrode centrale et le culot. Avec une mauvaise isolation, l'alimentation haute tension de la bougie risque alors d'être insuffisante, pour pouvoir provoquer les nécessaires « claquages », déclencheurs d'étincelles.By publications FR 2859830 , FR 2859869 , and FR 2859831 we know a so-called cold spark plug, because it does not rise quickly enough to prevent fouling. On such candles, it has been found indeed the accumulation of a carbon deposit on the electrodes, which significantly reduces the necessary insulation between the tip of the central electrode and the base. With poor insulation, high power tension of the candle may then be insufficient, to be able to cause the necessary "breakdowns", spark triggers.

Pour éviter la formation de dépôts carbonés, notamment à froid, sur l'électrode de la bougie exposée à l'atmosphère de la chambre de combustion, on peut chercher à augmenter la température de l'isolant, de manière à favoriser la destruction des dépôts par le phénomène de pyrolyse. Cette température dépend de la résistance thermique de l'ensemble de la bougie, y compris celle de l'isolant.To avoid the formation of carbonaceous deposits, especially cold, on the electrode of the candle exposed to the atmosphere of the combustion chamber, we can seek to increase the temperature of the insulator, so as to promote the destruction of deposits by the phenomenon of pyrolysis. This temperature depends on the thermal resistance of the entire candle, including that of the insulation.

Les mesures prises habituellement pour augmenter la température de l'isolant trouvent leur limite dans l'apparition de « pré-allumage » sur les bougies, lorsqu'elles atteignent des températures trop élevées en fonctionnement. Une bougie d'allumage selon le préambule de la revendication 1 est connue du document WO-A-0120162 .The measures usually taken to increase the temperature of the insulation find their limit in the appearance of "pre-ignition" on the candles, when they reach temperatures too high in operation. A spark plug according to the preamble of claim 1 is known from the document WO-A-0120162 .

La présente invention vise à régler l'indice thermique d'une bougie multi-étincelles, pour qu'elle puisse monter rapidement en température, sans risque ultérieur de pré-allumage.The present invention aims to adjust the thermal index of a multi-spark plug, so that it can quickly rise in temperature, without subsequent risk of pre-ignition.

Dans ce but, elle prévoit selon la revendication 1, de ménager une ouverture profonde sur toute la circonférence du culot, cette ouverture formant une chambre d'échanges thermiques à l'intérieur du culot de la bougie, ouverte sur l'extérieur.For this purpose, it provides according to claim 1, to provide a deep opening on the entire circumference of the base, this opening forming a heat exchange chamber inside the base of the candle, open on the outside.

Selon un mode de réalisation de l'invention, la chambre est disposée entre le culot et l'isolateur.According to one embodiment of the invention, the chamber is disposed between the base and the insulator.

Conformément à l'invention, la chambre peut renfermer une pièce de dilatation capable d'ouvrir ou de fermer son entrée aux gaz chauds.According to the invention, the chamber may contain a dilation piece capable of opening or closing its inlet to hot gases.

Les mesures proposées permettent de limiter le refroidissement de la céramique en phase de démarrage sans augmenter sa température de fonctionnement. On obtient ainsi un indice thermique non linéaire, qui correspond à un chauffage rapide de la bougie sans risque de pré-allumage à chaud.The measures proposed make it possible to limit the cooling of the ceramic in the starting phase without increasing its operating temperature. This gives a non-linear thermal index, which corresponds to rapid heating of the candle without the risk of hot pre-ignition.

La présente invention sera mieux comprise à la lecture de la description suivante de modes de réalisation non limitatifs de celle-ci, en se reportant aux dessins annexés, sur lesquels :

  • la figure 1 illustre l'état de la technique connu,
  • les figures 2, 3, 4A-4B, et 5A-5B, illustrent quatre modes de réalisation de l'invention.
The present invention will be better understood on reading the following description of non-limiting embodiments thereof, with reference to the accompanying drawings, in which:
  • the figure 1 illustrates the known state of the art,
  • the Figures 2, 3 , 4A-4B , and 5A-5B , illustrate four embodiments of the invention.

Sur la figure 1, on a représenté une bougie multi-étincelles 1 de type connu, comprenant deux électrodes 2, 3, de génération de plasma séparées par un isolateur 4 en matériau diélectrique tel qu'une céramique. Les deux électrodes 2, 3 constituent respectivement un culot extérieur 3 entourant l'isolateur, et une électrode 2 centrale, logée dans un perçage central de l'isolateur 4. Le culot 3 présente de façon conventionnelle un filetage extérieur 3a permettant de visser la bougie dans la culasse du moteur. Comme indiqué précédemment, lorsque l'isolateur 4 n'a pas atteint une température suffisante, des dépôts carbonés perturbent le fonctionnement de la bougie, en créant des zones de fuite de courant. A partir d'une certaine température, de l'ordre de 400 °C, les dépôts carbonés sont détruits par pyrolyse.On the figure 1 , there is shown a spark plug 1 of known type, comprising two electrodes 2, 3 for generating plasma separated by an insulator 4 of dielectric material such as a ceramic. The two electrodes 2, 3 constitute respectively an outer cap 3 surrounding the insulator, and a central electrode 2, housed in a central bore of the insulator 4. The base 3 conventionally has an external thread 3a for screwing the candle in the cylinder head of the engine. As indicated above, when the insulator 4 has not reached a sufficient temperature, carbon deposits disturb the operation of the candle, creating areas of current leakage. From a certain temperature, of the order of 400 ° C, the carbonaceous deposits are destroyed by pyrolysis.

La bougie de la figure 2 présente en plus un volume mort 6, constituant une chambre ouverte vers l'extérieur. La chambre 6 s'étend entre le culot 3 et l'isolateur 4. Conformément au schéma, la chambre peut avantageusement présenter un premier secteur tubulaire 6a raccordé à un deuxième secteur circulaire 6b ouvert sur l'extérieur.The candle of the figure 2 additionally has a dead volume 6, constituting an open chamber to the outside. The chamber 6 extends between the base 3 and the insulator 4. According to the diagram, the chamber may advantageously have a first tubular sector 6a connected to a second circular sector 6b open on the outside.

Selon une autre caractéristique de l'invention, mise en évidence sur la figure 2, les parois de la chambre 6 peuvent être métallisées. La couche, ou manchon de métal 7, appliqué sur l'isolateur, se retrouve alors en contact direct avec les gaz chauds, et particulièrement oxydants en mélange pauvre (« lean burn »), de la chambre de combustion. La métallisation des parois de la chambre 6 permet en particulier d'empêcher la création d'un plasma entre la céramique de l'isolateur et le culot. Cette couche métallique 7 peut être par exemple constituée d'un manchon brasé sur la céramique, qui permettra d'assurer la résistance de celle-ci aux gaz oxydants. Dans la pratique, l'épaisseur du manchon pourra être un compromis entre sa tenue à l'érosion thermochimique, sa résistance thermique et son coût de réalisation. En effet, si le manchon est trop épais, sa résistance thermique sera trop faible, et la céramique ne s'échauffera pas assez pour détruire les dépôts par pyrolyse. Le matériau du manchon sera par ailleurs choisi en fonction de sa conductivité et de son coefficient de dilatation, qui doit être compatible avec celui de la céramique et les propriétés mécaniques de cette dernière. Enfin, sans sortir du cadre de l'invention, la couche métallique peut être elle-même être protégée par un dépôt inerte, une fine couche de céramique, ou un autre dépôt métallique particulièrement résistant à l'oxydation, comme le nickel.According to another characteristic of the invention, highlighted on the figure 2 the walls of the chamber 6 may be metallized. The layer, or metal sleeve 7, applied to the insulator, is then in direct contact with the hot gases, and particularly oxidants in lean mixture ("lean burn "), of the combustion chamber. The metallization of the walls of the chamber 6 makes it possible in particular to prevent the creation of a plasma between the ceramic of the insulator and the base. This metal layer 7 may for example consist of a sleeve brazed to the ceramic, which will ensure the resistance thereof to the oxidizing gases. In practice, the thickness of the sleeve may be a compromise between its resistance to thermochemical erosion, its thermal resistance and its cost of production. Indeed, if the sleeve is too thick, its thermal resistance will be too low, and the ceramic will not heat up enough to destroy the deposits by pyrolysis. The material of the sleeve will also be chosen according to its conductivity and its coefficient of expansion, which must be compatible with that of the ceramic and the mechanical properties of the latter. Finally, without departing from the scope of the invention, the metal layer may itself be protected by an inert deposition, a thin ceramic layer, or other metal deposit particularly resistant to oxidation, such as nickel.

La figure 3 illustre un second mode de réalisation de l'invention, selon lequel la chambre 6 est une simple ouverture tubulaire ménagée dans la masse du culot 3. Dans ce cas, la chambre ne s'étend plus entre le culot et l'isolateur, comme précédemment, mais constitue une découpe dans la masse du culot. L'application d'une couche métallique 7 est impérative pour éviter la formation d'un plasma. Ici, la métallisation sera appliquée simplement sur l'interface de liaison entre la céramique 4 et le culot 3, indépendamment de la chambre 6.The figure 3 illustrates a second embodiment of the invention, according to which the chamber 6 is a simple tubular opening formed in the mass of the base 3. In this case, the chamber no longer extends between the base and the insulator, as previously but constitutes a cut in the mass of the base. The application of a metal layer 7 is imperative to avoid the formation of a plasma. Here, the metallization will be applied simply on the bonding interface between the ceramic 4 and the base 3, independently of the chamber 6.

Les figures 4A à 5B illustrent des dispositions supplémentaires permettant d'adapter automatiquement le comportement de la chambre aux conditions de température de la bougie, de manière à améliorer encore le réglage « non linéaire » de l'indice thermique de la bougie, en particulier pour qu'elle se comporte comme une bougie très chaude lorsque le moteur est encore froid, et comme une bougie tiède, lorsque le moteur est chaud, particulièrement sous forte charge.The Figures 4A to 5B illustrate additional provisions for automatically adapting the behavior of the chamber to the temperature conditions of the candle, so as to further improve the "non-linear" setting of the thermal index of the candle, particularly for that it behaves like a very hot candle when the engine is still cold, and like a warm candle, when the engine is hot, especially under heavy load.

Comme indiqué sur ces figures, la chambre 6 peut renfermer une pièce de dilatation 8, 9 capable d'ouvrir ou de fermer son entrée aux gaz chauds. Lorsque la température est basse, la pièce de dilatation est contractée, et ouvre le passage aux gaz chauds qui fournissent un flux thermique accélérant le fonctionnement de la bougie. Une fois que la bougie a atteint sa température de fonctionnement, la pièce est dilatée et ferme le passage aux gaz chauds. Ainsi, la bougie atteint son équilibre thermique à une température plus basse que si la chambre était restée ouverte.As shown in these figures, the chamber 6 may contain a dilation piece 8, 9 capable of opening or closing its inlet to hot gases. When the temperature is low, the expansion chamber is contracted, and opens the passage to hot gases that provide a thermal flow accelerating the operation of the candle. Once the candle has reached its operating temperature, the room is expanded and closes the hot gas passage. Thus, the candle reaches its thermal equilibrium at a lower temperature than if the chamber had remained open.

Sur les figures 4A et 4B, la pièce de dilatation 8 est un manchon ondulé, dont une extrémité est fixe et l'autre extrémité porte un volet cylindrique 8a fermant l'entrée de la chambre 6 lorsque le manchon est dilaté.On the Figures 4A and 4B , the expansion piece 8 is a corrugated sleeve, one end is fixed and the other end carries a cylindrical flap 8a closing the inlet of the chamber 6 when the sleeve is expanded.

Sur les figures 5A et 5B, la pièce de dilatation 9 est un manchon double paroi renfermant un métal 9a, fusible à température relativement basse : la dilatation du métal liquide 9a fait enfler le manchon 9, bloquant ainsi le passage des gaz chauds.On the Figures 5A and 5B , the expansion piece 9 is a double wall sleeve containing a metal 9a, fuse at relatively low temperature: the expansion of the liquid metal 9a causes the sleeve 9 to swell, thus blocking the passage of hot gases.

Ces deux dispositions ne sont pas limitatives, et on peut bien entendu envisager d'autres types d'obturateurs basés par exemple sur des collerettes faisant office de volets, ou sur l'utilisation d'alliages à mémoire de forme ou d'un bilame.These two provisions are not limiting, and one can of course consider other types of shutters based for example on flanges serving as shutters, or the use of shape memory alloys or bimetallic.

En conclusion, il faut souligner que l'ensemble des mesures proposées par l'invention, repose sur la création d'un espace libre, ou chambre ouverte, entre l'isolateur et le culot, qui permettent de régir l'indice thermique de la bougie, et plus particulièrement d'obtenir un indice thermique non linéraire. En outre la métallisation des parois de la chambre est particulièrement adaptée au fonctionnement en mélange pauvre, car elle protège la céramique contre les agents oxydants des gaz de combustion.In conclusion, it should be emphasized that all the measures proposed by the invention, is based on the creation of a free space, or open chamber, between the insulator and the base, which govern the thermal index of the candle, and more particularly to obtain a nonlinear thermal index. In in addition to the metallization of the walls of the chamber is particularly suitable for operation lean mixture, because it protects the ceramic against the oxidizing agents of the combustion gases.

Claims (11)

  1. Internal combustion engine radio-frequency spark plug (1) comprising two plasma-generating electrodes (2, 3) separated by an insulator (4), the two electrodes respectively constituting an outer shell (3) surrounding a peripheral surface of the insulator, and a central electrode (2) housed in a central bore of the insulator, and having around the entire circumference of the shell (3), an opening (6) extending depth-wise in the axial direction and open to the combustion chamber of the engine, characterized in that the said peripheral surface of the insulator is metalized and in that the chamber, forming a thermal regulation chamber, is made in the shell or is made between the shell and a metalized base of the insulator.
  2. Spark plug according to Claim 1, characterized in that a portion of the chamber is concentric with a threaded portion of the shell.
  3. Spark plug according to Claim 2, in which the chamber is made between the shell and a metalized face of the insulator and has a tubular first sector (6a) connected to a circular second sector (6b) that is open to the outside.
  4. Spark plug according to Claim 1, 2 or 3, characterized in that all the walls of the chamber (6) are metalized.
  5. Spark plug according to Claim 1, characterized in that the chamber (6) is a simple tubular opening made in the mass of the shell (3).
  6. Spark plug according to Claim 5, characterized in that the interface between the shell (3) and the insulator (4) is metalized.
  7. Spark plug according to one of the preceding claims, characterized in that the metalization is obtained by brazing a thin metal sleeve (7) onto the ceramic.
  8. Spark plug according to Claims 1 to 4, or Claims 1 to 4 combined with Claim 7, characterized in that the metalization (7) is protected by a coating that is resistant to high-temperature oxidizing atmospheres.
  9. Spark plug according to one of the preceding claims, characterized in that the chamber (6) contains an expansion piece (8, 9) capable of opening or closing its inlet to hot gases.
  10. Spark plug according to Claim 9, characterized in that the expansion piece (8) is a corrugated sleeve, one end of which is fixed and the other end of which carries a shutter (8a) that closes off the inlet to the chamber (6) when the sleeve has expanded.
  11. Spark plug according to Claim 9, characterized in that the expansion piece (9) is a double-walled sleeve containing a metal (9a) that melts at a relatively low temperature, the expansion of which causes the sleeve to swell in such a way as to block off the inlet of the hot gases.
EP06726308A 2005-04-08 2006-04-05 Open-chamber multi-spark plug Not-in-force EP1869739B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0550905A FR2884365B1 (en) 2005-04-08 2005-04-08 MULTI-SPARK CANDLE WITH OPEN BEDROOM
PCT/FR2006/050302 WO2006106267A1 (en) 2005-04-08 2006-04-05 Open-chamber multi-spark plug

Publications (2)

Publication Number Publication Date
EP1869739A1 EP1869739A1 (en) 2007-12-26
EP1869739B1 true EP1869739B1 (en) 2011-09-07

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Application Number Title Priority Date Filing Date
EP06726308A Not-in-force EP1869739B1 (en) 2005-04-08 2006-04-05 Open-chamber multi-spark plug

Country Status (10)

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US (2) US7928642B2 (en)
EP (1) EP1869739B1 (en)
JP (1) JP4841619B2 (en)
KR (1) KR20070120575A (en)
CN (1) CN101189771B (en)
AT (1) ATE523931T1 (en)
BR (1) BRPI0609731A2 (en)
ES (1) ES2371030T3 (en)
FR (1) FR2884365B1 (en)
WO (1) WO2006106267A1 (en)

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KR20070120575A (en) 2007-12-24
WO2006106267A1 (en) 2006-10-12
JP4841619B2 (en) 2011-12-21
ATE523931T1 (en) 2011-09-15
CN101189771B (en) 2012-06-27
FR2884365A1 (en) 2006-10-13
FR2884365B1 (en) 2013-10-11
BRPI0609731A2 (en) 2011-10-18
US20090189504A1 (en) 2009-07-30
US7928642B2 (en) 2011-04-19
US8294346B2 (en) 2012-10-23
JP2008535195A (en) 2008-08-28
ES2371030T3 (en) 2011-12-26
US20110163654A1 (en) 2011-07-07
CN101189771A (en) 2008-05-28
EP1869739A1 (en) 2007-12-26

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