EP1875571B1 - Plasma-generating plug - Google Patents

Plasma-generating plug Download PDF

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Publication number
EP1875571B1
EP1875571B1 EP06709445A EP06709445A EP1875571B1 EP 1875571 B1 EP1875571 B1 EP 1875571B1 EP 06709445 A EP06709445 A EP 06709445A EP 06709445 A EP06709445 A EP 06709445A EP 1875571 B1 EP1875571 B1 EP 1875571B1
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EP
European Patent Office
Prior art keywords
insulator
electrode
candle
gap
plasma
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EP06709445A
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German (de)
French (fr)
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EP1875571A1 (en
Inventor
Xavier Jaffrezic
André AGNERAY
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Renault SAS
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Renault SAS
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01TSPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T13/00Sparking plugs
    • H01T13/20Sparking plugs characterised by features of the electrodes or insulation
    • H01T13/34Sparking plugs characterised by features of the electrodes or insulation characterised by the mounting of electrodes in insulation, e.g. by embedding
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01TSPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T13/00Sparking plugs
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01TSPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T13/00Sparking plugs
    • H01T13/20Sparking plugs characterised by features of the electrodes or insulation
    • H01T13/36Sparking plugs characterised by features of the electrodes or insulation characterised by the joint between insulation and body, e.g. using cement
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01TSPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T13/00Sparking plugs
    • H01T13/50Sparking plugs having means for ionisation of gap
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01TSPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T13/00Sparking plugs
    • H01T13/52Sparking plugs characterised by a discharge along a surface

Definitions

  • the invention relates to a plasma generating plug of the type used for spark ignition engines.
  • Plasma generation candles are known to undergo excitation in the radiofrequency domain (that is to say greater than 1 MHz), making it possible to obtain a larger spark than traditional candles.
  • a candle which will be called, thereafter, "radiofrequency plasma generation candle" generates large sparks from reduced potential differences.
  • the insulator 3 comprises a central bore 30 in which is housed a central electrode 4.
  • the insulator 3 separates the electrodes 2, 4 in the zone where the distance between them is the lowest; the sparks formed between the electrodes on the surface of the insulator are thus guided.
  • the parts of the candle are assembled by interlocking. There is then a gap between them. In particular, there is a gap J1 between the base 2 and the insulator 3, and a gap J2 between the insulator 3 and the central electrode 4. It is found that sparks propagate in these interstices when the central electrode of the candle is powered with a high voltage radio frequency. This leads to an expenditure of energy which is not used to the useful function of the spark which is to ignite the gaseous mixture near the candle.
  • the insulator is at a relatively high temperature, for example 400 ° C.
  • the carbon deposits disturb the proper functioning of the candle, creating current leakage lines. At this temperature, the carbonaceous deposits are destroyed by pyrolysis.
  • the thermal resistances between the parts are reduced. The parts are therefore at more homogeneous temperatures, generally lower than that desired for the insulator.
  • the candle is usually screwed by one of the electrodes in the cylinder head of the engine, itself cooled by the circulation of a coolant.
  • a spark plug according to the preamble of claim 1 is known from US-A-4,841,925 .
  • a radiofrequency plasma generation candle having at least two elements, one of the elements being a first metal electrode and the other element being an insulator, the one of the elements having a housing in which the other is mounted with a gap.
  • the surface of the insulator facing the first electrode is metallized.
  • the insulator and the electrode are housed in each other, contact inevitably occurs between the metal coating of the insulator and the electrode.
  • the surfaces facing one another and separated by the gap are therefore at the same potential, which has the effect of preventing the spread of sparks in this area.
  • the sparks therefore occur entirely outside the insulator and are used entirely for igniting the surrounding gases.
  • the partial metallization of the insulator makes it possible to reduce the point accumulation of electric charges, and thus to improve the resistance of the insulator. the insulator to breakdown phenomena. The insulator thus supports higher voltages.
  • the candle according to the invention also retains the gap between the insulator and the electrode.
  • the differential expansions do not induce mechanical stresses and the choice of materials for the electrode and the insulator is not constrained by the concern to avoid differential expansions.
  • the gap creates a thermal resistance between the insulator and the electrode, which avoids homogenizing their temperature. Even if the electrode is cooled by the fact that it is fixed on a solid element of the motor, the insulator is not cooled so intensely and can have a higher temperature, suitable for the pyrolysis of possible carbonaceous deposits.
  • the first electrode is cylindrical and housed in a bore of the insulator.
  • the metallized part is then the bore of the insulator.
  • the plug has a second electrode surrounding the insulator, the surface of the insulator facing the second electrode being metallized.
  • the insulator is, for example, ceramic.
  • a radiofrequency plasma generation candle 10 is shown on the Figures 1 and 2 . It comprises, like the candle according to the prior art, a base 12 of tubular shape, containing a dielectric insulator 13.
  • the base 12 forms an electrode, generally connected to the ground.
  • the insulator 13 comprises a central bore 130 in which is housed a central electrode 14.
  • the insulator is ceramic, for example silicon nitride, but it can be glass-ceramic, or amorphous material such as quartz.
  • the insulator 13 has surfaces coated with a metallization. These areas are represented in phantom lines on the figure 1 .
  • a first zone A extends over a cylindrical portion of the insulator facing the base 12.
  • a second zone B extends into the bore 130 of the insulator 13 facing the central electrode 14.
  • the surface 131 of frustoconical shape of the insulator 13, intended to be exposed in the cylinder of an engine, has no metal coating.
  • a gap 15 is provided between the base 12 and the isolator 13.
  • a gap 16 is provided between the central electrode 14 and the insulator 13.
  • the interstices have a width of the order of a few hundredths to a few tenths of a millimeter.
  • the insulator 13 comprises a first metal layer 132 which extends over the entire first zone A.
  • the insulator 13 comprises a second metal layer 133 which extends over the entire second zone B.
  • the metal layers 132, 133 are obtained by any conventional method of ceramic metallization.
  • metal salts are deposited on the zones A, B of the insulator 13, in the form of liquid solutions.
  • the application is made for example by brush, roller or projection.
  • the insulator 13 is passed through a reducing atmosphere furnace, for example with an atmosphere containing hydrogen. In this way, the metal salts are reduced and a thin layer of metal is formed on the zones A, B.
  • metal layers 132, 133 are typically of the order of 5 to 50 ⁇ m.

Landscapes

  • Spark Plugs (AREA)
  • Ignition Installations For Internal Combustion Engines (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Plasma Technology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Discharge Heating (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Chemical Vapour Deposition (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

The plug (10) has a tubular shaped shell (12) forming an electrode and comprising a ceramic dielectric insulator (13) having metal coated surfaces opposite to the shell. A cylindrical central electrode (14) is housed in a central hole of the insulator. Two spaces are arranged between the shell and the insulator and between the electrode (14) and the insulator, respectively.

Description

L'invention concerne une bougie de génération de plasma du type utilisé pour les moteurs à allumage commandé.The invention relates to a plasma generating plug of the type used for spark ignition engines.

On connaît des bougies de génération de plasma subissant une excitation dans le domaine radiofréquence (c'est-à-dire supérieur à 1MHz) permettant d'obtenir un étincelage plus large que les bougies traditionnelles. Une telle bougie (que l'on appellera, par la suite, « bougie de génération de plasma radiofréquence ») génère des étincelles de taille importante à partir de différences de potentiel réduites. On a représenté sur la figure 3 une telle bougie 1 comportant un culot 2 de forme tubulaire, contenant un isolateur 3 diélectrique. Le culot 2 forme une électrode, en général reliée à la masse. L'isolateur 3 comporte un alésage central 30 dans lequel est logée une électrode centrale 4. L'isolateur 3 sépare les électrodes 2, 4 dans la zone où la distance les séparant est la plus faible ; on guide ainsi les étincelles formées entre les électrodes sur la surface de l'isolateur.Plasma generation candles are known to undergo excitation in the radiofrequency domain (that is to say greater than 1 MHz), making it possible to obtain a larger spark than traditional candles. Such a candle (which will be called, thereafter, "radiofrequency plasma generation candle") generates large sparks from reduced potential differences. We have shown on the figure 3 such a candle 1 having a base 2 of tubular shape, containing a dielectric insulator 3. The base 2 forms an electrode, generally connected to the ground. The insulator 3 comprises a central bore 30 in which is housed a central electrode 4. The insulator 3 separates the electrodes 2, 4 in the zone where the distance between them is the lowest; the sparks formed between the electrodes on the surface of the insulator are thus guided.

Selon une première technique d'assemblage, les pièces de la bougie sont assemblées par emboîtement. Il subsiste alors un interstice entre elles. En particulier, il existe un interstice J1 entre le culot 2 et l'isolateur 3, et un interstice J2 entre l'isolateur 3 et l'électrode centrale 4. On constate que des étincelles se propagent dans ces interstices lorsque l'électrode centrale de la bougie est alimentée avec une haute tension en radiofréquences. Ceci conduit à une dépense d'énergie qui n'est pas utilisée à la fonction utile de l'étincelle qui est d'enflammer le mélange gazeux à proximité de la bougie.According to a first assembly technique, the parts of the candle are assembled by interlocking. There is then a gap between them. In particular, there is a gap J1 between the base 2 and the insulator 3, and a gap J2 between the insulator 3 and the central electrode 4. It is found that sparks propagate in these interstices when the central electrode of the candle is powered with a high voltage radio frequency. This leads to an expenditure of energy which is not used to the useful function of the spark which is to ignite the gaseous mixture near the candle.

On connaît également une technique d'assemblage de l'électrode d'une bougie traditionnelle selon laquelle l'interstice entre l'électrode et l'isolateur est comblé par un matériau diélectrique tel que du verre, réalisant un collage. Si une telle technique est adoptée pour combler les interstices J1 et J2, des contraintes de cisaillement risquent d'apparaître entre les pièces du fait de dilatations thermiques différentielles. Pour diminuer ses contraintes, il est possible de choisir des matériaux ayant des coefficients de dilatation thermique relativement proches.Also known is a technique of assembling the electrode of a traditional candle according to which the gap between the electrode and the insulator is filled by a dielectric material such as glass, bonding. If such a technique is adopted to fill the interstices J1 and J2, shear stresses may appear between the parts due to differential thermal expansion. To reduce its stresses, it is possible to choose materials having relatively close thermal expansion coefficients.

Par ailleurs, pour éviter la formation de dépôts carbonés sur l'isolateur exposé à l'atmosphère de la chambre de combustion, il est utile que l'isolateur soit à une température relativement élevée, par exemple 400 °C. Les dépôts carbonés perturbent le bon fonctionnement de la bougie, en créant des lignes de fuite de courant. A cette température, les dépôts carbonés sont détruits par pyrolyse. En comblant les interstices J1 et J2, on diminue les résistances thermiques entre les pièces. Les pièces sont donc à des températures plus homogènes, généralement plus basses que celle souhaitée pour l'isolateur. En effet, la bougie est généralement vissée par l'une des électrodes dans la culasse du moteur, elle-même refroidie par la circulation d'un liquide de refroidissement.Furthermore, to avoid the formation of carbon deposits on the insulator exposed to the atmosphere of the combustion chamber, it is useful for the insulator to be at a relatively high temperature, for example 400 ° C. The carbon deposits disturb the proper functioning of the candle, creating current leakage lines. At this temperature, the carbonaceous deposits are destroyed by pyrolysis. By filling gaps J1 and J2, the thermal resistances between the parts are reduced. The parts are therefore at more homogeneous temperatures, generally lower than that desired for the insulator. Indeed, the candle is usually screwed by one of the electrodes in the cylinder head of the engine, itself cooled by the circulation of a coolant.

C'est un objectif de l'invention de proposer une bougie de génération de plasma radiofréquence dépourvue d'ionisation de l'air entre électrode et isolant et produisant des étincelles entièrement utiles à l'allumage des gaz environnant la bougie et dont l'isolateur puisse avoir une température de fonctionnement relativement haute. C'est aussi un objectif d'avoir un grand choix dans les matériaux constituant les électrodes et l'isolateur.It is an object of the invention to provide a radiofrequency plasma generation candle devoid of ionization of the air between electrode and insulator and producing sparks entirely useful for igniting the gases surrounding the candle and whose isolator can have a relatively high operating temperature. It is also a goal to have a great choice in the materials constituting the electrodes and the insulator.

Une bougie d'allumage, selon le préambule de la revendication 1 est connue de US-A-4 841 925 .A spark plug according to the preamble of claim 1 is known from US-A-4,841,925 .

Avec ces objectifs en vue, l'invention a pour objet selon la revendication 1, une bougie de génération de plasma radiofréquence comportant au moins deux éléments, l'un des éléments étant une première électrode métallique et l'autre élément étant un isolateur, l'un des éléments comportant un logement dans lequel l'autre est monté avec un interstice. La surface de l'isolateur en regard de la première électrode est métallisée.With these objectives in view, the object of the invention according to claim 1, a radiofrequency plasma generation candle having at least two elements, one of the elements being a first metal electrode and the other element being an insulator, the one of the elements having a housing in which the other is mounted with a gap. The surface of the insulator facing the first electrode is metallized.

Comme l'isolateur et l'électrode sont logés l'un dans l'autre, il se produit inévitablement un contact entre le revêtement métallique de l'isolateur et l'électrode. Les surfaces en regard l'une de l'autre et séparées par l'interstice sont donc au même potentiel, ce qui a pour conséquence d'éviter la propagation d'étincelles dans cette zone. Les étincelles se produisent donc entièrement à l'extérieur de l'isolateur et servent entièrement à l'allumage des gaz environnants. De plus, la métallisation partielle de l'isolateur permet de réduire l'accumulation ponctuelle de charges électriques, et donc d'améliorer la résistance de l'isolateur à des phénomènes de claquage. L'isolateur supporte donc des tensions plus élevées.Since the insulator and the electrode are housed in each other, contact inevitably occurs between the metal coating of the insulator and the electrode. The surfaces facing one another and separated by the gap are therefore at the same potential, which has the effect of preventing the spread of sparks in this area. The sparks therefore occur entirely outside the insulator and are used entirely for igniting the surrounding gases. In addition, the partial metallization of the insulator makes it possible to reduce the point accumulation of electric charges, and thus to improve the resistance of the insulator. the insulator to breakdown phenomena. The insulator thus supports higher voltages.

La bougie selon l'invention conserve aussi l'interstice entre l'isolateur et l'électrode. Ainsi, les dilatations différentielles n'induisent pas de contraintes mécaniques et le choix des matériaux pour l'électrode et l'isolateur n'est pas contraint par le souci d'éviter les dilatations différentielles. De plus, l'interstice crée une résistance thermique entre l'isolateur et l'électrode, ce qui évite d'homogénéiser leur température. Même si l'électrode est refroidie par le fait qu'elle est fixée sur un élément massif du moteur, l'isolateur n'est pas refroidi aussi intensément et peut avoir une température supérieure, propice à la pyrolyse d'éventuels dépôts carbonés.The candle according to the invention also retains the gap between the insulator and the electrode. Thus, the differential expansions do not induce mechanical stresses and the choice of materials for the electrode and the insulator is not constrained by the concern to avoid differential expansions. In addition, the gap creates a thermal resistance between the insulator and the electrode, which avoids homogenizing their temperature. Even if the electrode is cooled by the fact that it is fixed on a solid element of the motor, the insulator is not cooled so intensely and can have a higher temperature, suitable for the pyrolysis of possible carbonaceous deposits.

De manière particulière, la première électrode est cylindrique et logée dans un alésage de l'isolateur. La partie métallisée est alors l'alésage de l'isolateur.In particular, the first electrode is cylindrical and housed in a bore of the insulator. The metallized part is then the bore of the insulator.

De manière particulière, la bougie comporte une deuxième électrode entourant l'isolateur, la surface de l'isolateur en regard de la deuxième électrode étant métallisée.In particular, the plug has a second electrode surrounding the insulator, the surface of the insulator facing the second electrode being metallized.

L'isolateur est, par exemple, en céramique.The insulator is, for example, ceramic.

L'invention sera mieux comprise et d'autres particularités et avantages apparaîtront à la lecture de la description qui va suivre, la description faisant référence aux dessins annexés parmi lesquels :

  • la figure 1 est une vue en coupe d'une bougie de génération de plasma conforme à l'invention ;
  • la figure 2 est une vue du détail II de la figure 1 ;
  • la figure 3 est une vue similaire à la figure 1 d'une bougie selon l'art antérieur, et décrite précédemment.
The invention will be better understood and other features and advantages will appear on reading the description which follows, the description referring to the appended drawings among which:
  • the figure 1 is a sectional view of a plasma generation candle according to the invention;
  • the figure 2 is a detail view II of the figure 1 ;
  • the figure 3 is a view similar to the figure 1 of a candle according to the prior art, and described above.

Une bougie de génération de plasma radiofréquence 10 selon l'invention est montrée sur les figures 1 et 2. Elle comporte, comme la bougie selon l'art antérieur, un culot 12 de forme tubulaire, contenant un isolateur 13 diélectrique. Le culot 12 forme une électrode, en général reliée à la masse. L'isolateur 13 comporte un alésage central 130 dans lequel est logée une électrode centrale 14.A radiofrequency plasma generation candle 10 according to the invention is shown on the Figures 1 and 2 . It comprises, like the candle according to the prior art, a base 12 of tubular shape, containing a dielectric insulator 13. The base 12 forms an electrode, generally connected to the ground. The insulator 13 comprises a central bore 130 in which is housed a central electrode 14.

L'isolateur est en céramique, par exemple en nitrure de silicium, mais il peut être en vitrocéramique, ou en matériau amorphe comme du quartz.The insulator is ceramic, for example silicon nitride, but it can be glass-ceramic, or amorphous material such as quartz.

Conformément à l'invention, l'isolateur 13 comporte des surfaces revêtues d'une métallisation. Ces zones sont représentées en traits mixtes sur la figure 1. Une première zone A s'étend sur une partie cylindrique de l'isolateur en regard du culot 12. Une deuxième zone B s'étend dans l'alésage 130 de l'isolateur 13 en regard de l'électrode centrale 14. La surface 131 de forme tronconique de l'isolateur 13, destinée à être exposée dans le cylindre d'un moteur, ne comporte aucun revêtement métallique.According to the invention, the insulator 13 has surfaces coated with a metallization. These areas are represented in phantom lines on the figure 1 . A first zone A extends over a cylindrical portion of the insulator facing the base 12. A second zone B extends into the bore 130 of the insulator 13 facing the central electrode 14. The surface 131 of frustoconical shape of the insulator 13, intended to be exposed in the cylinder of an engine, has no metal coating.

Comme on le voit en détail sur la figure 2, un interstice 15 est prévu entre le culot 12 et l'isolateur 13. De même, un interstice 16 est prévu entre l'électrode centrale 14 et l'isolateur 13. Les interstices ont une largeur de l'ordre de quelques centièmes à quelques dixièmes de millimètres. Le long de l'interstice 15, l'isolateur 13 comporte une première couche métallique 132 qui s'étend sur toute la première zone A. De même, le long de l'interstice 16, l'isolateur 13 comporte une deuxième couche métallique 133 qui s'étend sur toute la deuxième zone B.As we see in detail on the figure 2 a gap 15 is provided between the base 12 and the isolator 13. Similarly, a gap 16 is provided between the central electrode 14 and the insulator 13. The interstices have a width of the order of a few hundredths to a few tenths of a millimeter. Along the gap 15, the insulator 13 comprises a first metal layer 132 which extends over the entire first zone A. Similarly, along the gap 16, the insulator 13 comprises a second metal layer 133 which extends over the entire second zone B.

Les couches métalliques 132, 133 sont obtenues par tout procédé classique de métallisation de céramique. Par exemple, on dépose des sels métalliques sur les zones A, B de l'isolateur 13, sous la forme de solutions liquides. L'application est faite par exemple au pinceau, au rouleau ou par projection. Après séchage, l'isolateur 13 est passé dans un four à atmosphère réductrice, par exemple avec une atmosphère contenant de l'hydrogène. De la sorte, les sels métalliques sont réduits et une couche mince de métal est formée sur les zones A, B.The metal layers 132, 133 are obtained by any conventional method of ceramic metallization. For example, metal salts are deposited on the zones A, B of the insulator 13, in the form of liquid solutions. The application is made for example by brush, roller or projection. After drying, the insulator 13 is passed through a reducing atmosphere furnace, for example with an atmosphere containing hydrogen. In this way, the metal salts are reduced and a thin layer of metal is formed on the zones A, B.

On utilise par exemple de l'argent pour former les couches métalliques, ou un alliage de molybdène et de manganèse, mais d'autres métaux ou alliages peuvent être utilisés. L'épaisseur des couches métalliques 132, 133 est typiquement de l'ordre de 5 à 50 µm.For example, silver is used to form the metal layers, or an alloy of molybdenum and manganese, but other metals or alloys may be used. The thickness of the metal layers 132, 133 is typically of the order of 5 to 50 μm.

Claims (4)

  1. Plasma-generating spark plug (10) undergoing excitation in the radiofrequency domain, comprising at least two elements, one of the elements being a first metal electrode (12, 14) and the other being an insulator (13), one of the elements comprising a recess (130) into which the other (13, 14) is fitted with a gap (15, 16), characterized in that the surface of the insulator (13) facing the first electrode (12, 14) is metallized.
  2. Plug according to Claim 1, in which the first electrode (14) is cylindrical and housed in a bore (130) of the insulator (13).
  3. Plug according to Claim 2, characterized in that it comprises a second electrode (12) surrounding the insulator (13), the surface of the insulator (13) facing the second electrode (12) being metallized.
  4. Plug according to Claim 1, in which the insulator is made of ceramic.
EP06709445A 2005-01-26 2006-01-26 Plasma-generating plug Active EP1875571B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0500777A FR2881281B1 (en) 2005-01-26 2005-01-26 PLASMA GENERATION CANDLE
PCT/FR2006/050061 WO2006079753A1 (en) 2005-01-26 2006-01-26 Plasma-generating plug

Publications (2)

Publication Number Publication Date
EP1875571A1 EP1875571A1 (en) 2008-01-09
EP1875571B1 true EP1875571B1 (en) 2010-08-18

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Application Number Title Priority Date Filing Date
EP06709445A Active EP1875571B1 (en) 2005-01-26 2006-01-26 Plasma-generating plug

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US (1) US7843117B2 (en)
EP (1) EP1875571B1 (en)
JP (1) JP4859846B2 (en)
KR (1) KR101211257B1 (en)
CN (1) CN101366154B (en)
AT (1) ATE478456T1 (en)
DE (1) DE602006016261D1 (en)
ES (1) ES2347816T3 (en)
FR (1) FR2881281B1 (en)
WO (1) WO2006079753A1 (en)

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FR2965984B1 (en) * 2010-10-12 2012-10-12 Renault Sa PREVENTION AGAINST A SHORT CIRCUIT OF THE RF CANDLE
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Publication number Publication date
WO2006079753A1 (en) 2006-08-03
EP1875571A1 (en) 2008-01-09
FR2881281B1 (en) 2011-04-22
FR2881281A1 (en) 2006-07-28
KR101211257B1 (en) 2012-12-11
JP2008529229A (en) 2008-07-31
CN101366154A (en) 2009-02-11
ATE478456T1 (en) 2010-09-15
KR20070097588A (en) 2007-10-04
ES2347816T3 (en) 2010-11-04
US20090033194A1 (en) 2009-02-05
DE602006016261D1 (en) 2010-09-30
US7843117B2 (en) 2010-11-30
JP4859846B2 (en) 2012-01-25
CN101366154B (en) 2013-05-22

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