EP0353196A1 - Composition de cermet conducteur pour dispositifs d'allumage et de chauffage - Google Patents

Composition de cermet conducteur pour dispositifs d'allumage et de chauffage Download PDF

Info

Publication number
EP0353196A1
EP0353196A1 EP89810563A EP89810563A EP0353196A1 EP 0353196 A1 EP0353196 A1 EP 0353196A1 EP 89810563 A EP89810563 A EP 89810563A EP 89810563 A EP89810563 A EP 89810563A EP 0353196 A1 EP0353196 A1 EP 0353196A1
Authority
EP
European Patent Office
Prior art keywords
cermet
metal
sintering
particles
cermet composition
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.)
Granted
Application number
EP89810563A
Other languages
German (de)
English (en)
Other versions
EP0353196B1 (fr
Inventor
Jean-Paul Issartel
Dominique Richon
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.)
Federal Mogul Global Aftermarket EMEA BVBA
Original Assignee
Champion Spark Plug Belgium SA
Battelle Memorial Institute Inc
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 Champion Spark Plug Belgium SA, Battelle Memorial Institute Inc filed Critical Champion Spark Plug Belgium SA
Publication of EP0353196A1 publication Critical patent/EP0353196A1/fr
Application granted granted Critical
Publication of EP0353196B1 publication Critical patent/EP0353196B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23QIGNITION; EXTINGUISHING-DEVICES
    • F23Q7/00Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
    • F23Q7/001Glowing plugs for internal-combustion engines
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • 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
    • H01T13/39Selection of materials for electrodes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23QIGNITION; EXTINGUISHING-DEVICES
    • F23Q7/00Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
    • F23Q7/001Glowing plugs for internal-combustion engines
    • F23Q2007/004Manufacturing or assembling methods

Definitions

  • the present invention relates to electrically conductive cermet compositions which can be used in the manufacture of ignition and heating appliances, inter alia spark-plugs or plasma-discharge plugs for gasoline engines, and glow-plugs for Diesel engines or external combustion engines, e.g. Stir­ling engines.
  • the distinction between electrically conductive cermets and electroconductive ceramics should be acknowledged at this stage of the disclosure:
  • the electrically conductive cermets are binary compositions in which electroconductive particulate elements (e.g. grains of a metal powder) are intermixed with an insulating ceramic material.
  • electroconductive ceramics consist of electroconducting minerals such as car­bides, nitrides, borides, silicides, oxides of selected me­tals, for instance ZrC; WC; SiC; TiN, Mo2N; TaN; NbN; ScB2; TiB2; MoB; ZrB; (Y,Ca)(Cr,Mn)O3; (La,Sr)(Cr,Mn)O3; doped BaTiO3, etc., either alone or in admixture with other mi­nerals.
  • electrically conductive cermets may be tech­nically and economically advantageous over electroconductive ceramics in many applications, namely because they require milder sintering conditions and demonstrate wider electrical properties versatility (due to better composition control at the formulation stage); also, in some cases, the costs of cermet starting materials may be lower than for electrocon­ductive ceramics.
  • electroconductive ceramics and cermet compositions useful in the field of ignition and heating appliances. Some of these compositions can actually be considered as intermediate between electroconductive cermets and ceramics as they comprise mixtures of insulating and conducting ceramic particles as well as metallic particles.
  • JIDOSHA BUHIN Japanese Patent Publication JP-A-­ 150,579/1980 discloses ignition spark plugs in which the center electrode is made of cermet compositions containing insulating or conducting ceramics such as Al2O3, TiO2, TiC, Cr2O3, NbC, WC, SiC, TaC, MoSi2 and metal parti­cles, e.g. Cr, Co, Fe, Al, W, Mo, and other like metals.
  • JP-A-44391/1986 discloses ignition spark plugs whose central electrode is made in part of cermets which result from the sintering of compositions containing ceramics selected from Al2O3, TiO2, Cr2O3, ZrO2, SiO2, Y2O3, La2O3, NiO, CaO, TiC, SiC, B4C, Cr2C2, WC, TiN, AlN, BN and MoSi2 together with metal particles selected from Cr. Co, Mo, Mn, Pt and Pd.
  • electroconductive cermets and ceramics known in the art for making the electrodes or the incandescent bodies of ignition plugs have merit, it was desirable to further improve some of their working properties, inter alia the resistance to hot corrosion and the resistance to elec­troerosion by spark discharge.
  • these electroconductive cermet compositions which demonstrate significantly improved resistance to hot corrosion and to erosion by spark discharge comprise an alumi­na based ceramic and 30-60% by weight of metal particles which provide adequate electroconductivity to the compositions.
  • the main improvement here over the achievements of the prior art is that said metal particles are in a partly oxidized state, the weight ratio oxygen/metal of these particles being in the range of 0.3 to 10% (ie. 0.003 - 0.1).
  • the oxide of the particulate metals has a degree of solubility in the ceramic phase (Al2O3) which reduces strongly the dis­continuity barrier between the metal grains and the ceramic phase; thus, the presence of this oxide layer adherent to the metal grains and interposed between said grains and the cera­mic matrix provides enhanced compatibility with the cermet body and ensures appropriate reinforcement and improved mecha­nical properties.
  • the grade or mesh-size of the metallic powders of the present cermet composition can be in the order of 0.5 to 50 ⁇ m, a grade around 1 ⁇ m being preferred.
  • the metals suitable for making the powders are of course the metals normally used for making cermets and disclosed in the prior art, namely Cr, Ni, Co, Fe, Mo, W, Ti and the like.
  • the ceramic phase can be supplemented with other minerals, inter alia 1 to 20% by weight of a vitreous silicate phase.
  • This glassy phase comprises SiO2 and, at will, one or more oxides selected from MgO, CaO, BaO, Na2O, K2O, Fe2O3, TiO2, ZrO2, ZnO, PbO2, B2O3 and further oxides conventionally used for making glasses.
  • the ceramic of the cermet composition consists, at least in part, of Mullite, i.e. a mixed aluminosilicate of formula 3Al2O3.2SiO2.
  • a formulation is first prepared by admixing together the cermet ingredients (or precursor com­pounds) and adding molding or casting and sintering additives. Then the resulting blend is formed or molded into a "green" object or article which can thereafter be safely handled and heated with substantially no risk of mechanical attrition. Then the "green” article is sintered at high temperature (e.g. around 1200-1600°C) so as to furnish the article made of the desired electroconductive cermet composition.
  • high temperature e.g. around 1200-1600°C
  • the simplest route is to use preoxidized metal particles in the cermet composition; otherwise a particle surface oxidation may take place during sintering.
  • the oxygen required for this oxidation may arise, either from an additional oxidant added to the formulation blend before molding and which will ultimately be decomposed by heat during sintering and release its oxygen for oxidizing the metal particles, or from the atmosphere under which sintering is performed, this atmosphere containing oxygen or an oxygen containing gas.
  • the techniques to be used for forming or molding the green objects or articles made of, or comprising the cermet composition of the invention are conventional.
  • the aforementioned formulation blend can be placed in a mold and the latter is subjected to pressure (isostatic pressure or otherwise) in the order of 1 to several T/cm2.
  • a dip-coating technique can also be used when it is desired to deposit a layer of electroconductive cermet on a substrate; in this case, the substrate is immersed for a given time in a slurry of the formulated cermet ingredients, withdrawn, and allowed to dry before sintering.
  • the green article can be heated in an oven under an atmosphere of controlled composition, e.g. a neutral gas (argon, helium) or under hydrogen or nitrogen, or mixtures thereof.
  • controlled composition e.g. a neutral gas (argon, helium) or under hydrogen or nitrogen, or mixtures thereof.
  • the metal grains of the composition be superficially oxidized during sintering, the latter is effected in an atmosphere having an oxygen partial pressure which can be controlled by introducing an oxygen releasing gas, for instance a 20/80 (v/v) H2/H2O mixture.
  • This oxidation can also be accomplished independently of the sinte­ring operation, at lower temperatures, for instance between about 500 and 1200°C.
  • this oxidation agent can be selected from organic oxidizers (which pyrolyse at sintering temperature) or mineral oxidants which release oxy­gen during sintering.
  • organic oxidizers which pyrolyse at sintering temperature
  • mineral oxidants which release oxy­gen during sintering.
  • oxidizing agents the following can be non-exhaustively recited: metal oxides, metal hydroxides and peroxides, e.g. Al(OH)3, Fe(OH)3, Na2O2, as well as salt, for example nitrates, oxalates, carbonates, titanates, etc.
  • the weight proportion of such oxidants in the formulation may essentially vary depending on the degree of oxidation of the metal particles which is desired; generally, this amount is between about 0.5 and 20% by weight.
  • preoxidized metallic powders When preoxidized metallic powders are used in formulating the cermets of the invention, such preoxidized powders can be obtained by oxidation techniques. For instance, for superfi­cially oxidizing the particles of a chromium powder, the latter can be contacted with a heated oxygen flow or with a bichromate solution. Generally speaking, the techniques for superficially oxidizing metal powders are well known in the art and need not be further developped here.
  • the extent of oxidation of the metal powders used in the present invention, i.e. the amount by weight of oxygen incorporated to the metal grains is preferably 0.3 to 20%.
  • alumina ball-mill with 400 g of alumina beads of 12 mm diame­ter: 59.5 g of alumina powder (grade about 1 ⁇ m) containing about 10% by weight of a glassy phase constituted by about 80% of SiO2, the remainder being a mixture of MgO, CaO and Na2O; 40.5 g of chromium powder (oxidized beforehand by an oxygen flow at 300°C and containing, by weight, about 1-3% of oxy­gen); 1.5 g of fish-oil (dispersing agent); 50 g of butanol (solvent); and 8 g of camphor (binder).
  • the blend was thereafter dried and sieved on a 300 ⁇ m screen. Then the powder was molded into disks (diameter 15 mm, height 3mm) under a pressure of 1.1 T/cm2.
  • the disks were sintered for 2 hrs at 1550°C under argon, after which they were cut (with a diamond saw) into little bars, or blocks, of 2x2x5 mm.
  • Example 1 The operations reported in Example 1 were repeated, but replacing in the formulation the oxidized chromium powder by regular (non-oxidized) chromium powder of the same grade.
  • An ignition spark-plug was constructed using the cermet composition of Example 1; this spark-plug is schematically represented in Figure 1.
  • This plug comprises a conventional metal shell 1 integral with a ground electrode 4, an insulating body (of vitrified alumina ceramic) and, located in a hollow axial portion of this body, the following elements : A terminal rod 9, a con­ducting gasket 7, an interference-supressor resistor 8 and a center electrode 6 made of a cermet composition according to the invention.
  • This electrode 6 was obtained by molding and sintering according to usual means under the conditions dis­closed in Example 1. The several plug components were assem­bled together according to usual techniques of spark-plug manufacture.
  • the ground electrode 4 of the plug repre­sented in Figure 1 can be provided, by welding or brazing, with a small bar or cap 5 made of a cermet composition which is identical with that of the center electrode. In this case the useful life of the plug is still further extended.
  • a glow-plug useful in Diesel engines was constructed using a cermet formulation like that of Example 1.
  • a plug of this kind is schematically illustrated in Fig. 2.
  • This plug comprises a metal outer-shell 12 provided (as in the case of the plug of Example 4) with a threaded portion 13; this shell surrounds a hollow insulating body of two axially abutting parts 14 and 15.
  • the hollow portion of in­sulating part 14 contains a metal terminal rod 16 which is in contact with the internal annular area of part 15 and which is retained, in part 14, by a shouldered base 17 of larger cross-section.
  • the hollow cylindrical insulating element 15 is coated on its internal and external lateral surface with a cermet layer 18 of a composition according to the invention.
  • This layer 18 extends without transition over the full free surface of element 15 including the external terminal face 19 of insulator 15 as shown in the drawing and hence constituting a continuous electric resistor whose respective ends are elec­trically in contact, on one hand with the base 17 of rod 16 and, on the other hand by its peripheral area 20, with the metal sheath 12.
  • an appropriate voltage is set across the sheath 12 (ground terminal) and the terminal rod 16 (plug terminal) an electric current will circulate in layer 18 which heats up and becomes incandescent. Since the cermet composi­tion used for making this layer 18 has an improved resistance to thermal corrosion, the present glow-plug demonstrate a much extended working life when used in a Diesel engine.
  • Example 1 In order to accomplish the deposit of the layer 18,19,20 on the hollow insulating body 15, one preferably uses the dip-­coating technique.
  • the formulation of Exemple 1 is used but containing by weight, instead of the solvent, dispersant and binder indicated, 50 g of a 1:1 mixture of trichlorethylene and ethanol (solvent); 5-10% of polyethylene-butyral (binder); 6% of a 1:1 mixture of polyethylene glycol and dioctyl phta­ late; and 0,5-1% of FLUORAD (3M)(surfactant).
  • solvent dispersant and binder indicated, 50 g of a 1:1 mixture of trichlorethylene and ethanol (solvent); 5-10% of polyethylene-butyral (binder); 6% of a 1:1 mixture of polyethylene glycol and dioctyl phta­ late; and 0,5-1% of FLUORAD (3M)(surfactant).
  • the amount of solvent can be varied and will depend on the viscosity to be imparted to the slurry and, as a consequence, of the thickness to be given to the deposited layer of cermet 18,19,20.
  • one dip-coating operation provides a layer of about 100-300 ⁇ m after drying.
  • the dip-­coating operation can be repeated after drying the first layer if thicker deposit are desired.
  • the dip-coating layer is dried in air (hot or at room temperature) until the solvents have evaporated and thereafter it is sintered at about 1550°C in the conditions set up at example 1.
  • the glow-plug components are assembled together conven­tionally, i.e. the rod 16 is inserted into insulated body 14, the base 17 of of the rod is pressed aginst body 15 which has been provided beforehand with the sintered cermet layer so that a good electrical contact is achieved between said cermet layer and the said base 17 (for ensuring a better contact, a soft electrically conductive gasket can be used there if desired, for instance an annealed copper washer); then the assembly is set integrally into shell 12 by crimping.
  • a cermet formulation was prepared by milling together for 24 hrs in a ball-mill, using 200 g of alumina balls, the following ingredients: Mullite powder 28.5 g Oxidized (5%) chromium powder 21.5 g Fish oil (dispersant) 0.75 g 1:2 mixture of tert-butanol-petroleum ether (solvent) 50 g Camphor (molding binder) 4,0 g
  • Disks were molded with this formulation like disclosed in example 1 and the green disks were sintered for 2 hrs at 1480°C under argon. The sintered composition was then tested exactly as in the previous Examples. Results can be found in Table 1.
  • Example 6 The operation disclosed in Example 6 were repeated except for the following differences: to the formulation were added 0.85 g of talc powder (4SiO2.3MgO.H2O); sintering temperature 1450°C. The results of the tests are gathered in Table 1.
  • Example 7 The operations of Example 7 were duplicated, the only difference being to replace the oxidized Cr powder by pure chromium powder. For the results, see Table 1. TABLE 1 Electrical properties and resistance to thermal corrosion and to spark discharge erosion of the cermets of Exemple 1-3 and 6-8.
  • Figure 3 is a microscope picture of the structure of the cermet of Exemple 7, while figure 4 depicts, comparatively, the structure of the control cermet of Exemple 8.
  • Example 4 the blend was dried by evaporation under reduced pressure and sieved on a 300 ⁇ m screen; then it was molded in the form of spark-plugs electrodes as indicated in Example 4 and sintered at 1560°C.
  • Cermet electrodes were prepared as in Example 9 from the following formulation : Al2O3 (same grade as in Example 1) 53,36 g Chromium powder (3,5% O2 as Cr2O3) 46.64 g

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Powder Metallurgy (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Spark Plugs (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Resistance Heating (AREA)
  • Non-Adjustable Resistors (AREA)
  • Ignition Installations For Internal Combustion Engines (AREA)
EP89810563A 1988-07-28 1989-07-24 Composition de cermet conducteur pour dispositifs d'allumage et de chauffage Expired - Lifetime EP0353196B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2876/88A CH676525A5 (fr) 1988-07-28 1988-07-28
CH2876/88 1988-07-28

Publications (2)

Publication Number Publication Date
EP0353196A1 true EP0353196A1 (fr) 1990-01-31
EP0353196B1 EP0353196B1 (fr) 1993-05-19

Family

ID=4243560

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89810563A Expired - Lifetime EP0353196B1 (fr) 1988-07-28 1989-07-24 Composition de cermet conducteur pour dispositifs d'allumage et de chauffage

Country Status (9)

Country Link
EP (1) EP0353196B1 (fr)
JP (1) JPH02250938A (fr)
KR (1) KR920000219B1 (fr)
AR (1) AR241806A1 (fr)
AU (1) AU603737B2 (fr)
CH (1) CH676525A5 (fr)
DE (1) DE68906610T2 (fr)
MX (1) MX170365B (fr)
ZA (1) ZA895656B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0400950B1 (fr) * 1989-05-29 2000-02-09 Ngk Spark Plug Co., Ltd Bougie d'allumage
US6043459A (en) * 1997-12-20 2000-03-28 Daimlerchrysler Ag And Beru Ag Electrically heatable glow plug with oxygen getter material
WO2002002933A1 (fr) * 2000-06-30 2002-01-10 Robert Bosch Gmbh Bougie crayon de prechauffage a detecteur de courant ionique et procede pour faire fonctionner une telle bougie
WO2005066611A2 (fr) * 2003-12-31 2005-07-21 Honeywell International Inc. Capteurs de matieres particulaires
WO2007031371A1 (fr) * 2005-09-13 2007-03-22 Robert Bosch Gmbh Bougie-crayon de prechauffage
US7275415B2 (en) 2003-12-31 2007-10-02 Honeywell International Inc. Particulate-based flow sensor
CN116477953A (zh) * 2023-05-15 2023-07-25 西安交通大学 一种SiC半导体点火材料、制备方法及应用

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19900698C2 (de) * 1999-01-04 2001-04-26 Gabor Keresztury Ballonkatheter mit anpaßbarem Mittelteil
US6582629B1 (en) * 1999-12-20 2003-06-24 Saint-Gobain Ceramics And Plastics, Inc. Compositions for ceramic igniters
DE10104121C2 (de) 2001-01-29 2003-03-06 Bosch Gmbh Robert Verfahren zur Herstellung eines Startelementes
DE10348778B3 (de) * 2003-10-21 2005-07-07 Robert Bosch Gmbh Elektrode für eine Zündkerze und Verfahren zum Herstellen einer Elektrode
US7765792B2 (en) 2005-10-21 2010-08-03 Honeywell International Inc. System for particulate matter sensor signal processing
US7572480B2 (en) * 2006-10-19 2009-08-11 Federal-Mogul World Wide, Inc. Method of fabricating a multilayer ceramic heating element
JP5650179B2 (ja) * 2012-10-02 2015-01-07 日本特殊陶業株式会社 スパークプラグ
EP3358686A1 (fr) * 2017-02-01 2018-08-08 Kistler Holding AG Bougie et méthode de fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3038649A1 (de) * 1979-10-13 1981-04-23 Ngk Spark Plug Co., Ltd., Nagoya, Aichi Zuendkerze und verfahren zu ihrer herstellung
EP0171153A1 (fr) * 1984-07-09 1986-02-12 General Motors Corporation Bougie d'allumage
US4659960A (en) * 1984-05-09 1987-04-21 Ngk Spark Plug Co., Ltd. Electrode structure for a spark plug

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5712221A (en) * 1980-06-25 1982-01-22 Hitachi Ltd Glow plug for diesel engine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3038649A1 (de) * 1979-10-13 1981-04-23 Ngk Spark Plug Co., Ltd., Nagoya, Aichi Zuendkerze und verfahren zu ihrer herstellung
US4659960A (en) * 1984-05-09 1987-04-21 Ngk Spark Plug Co., Ltd. Electrode structure for a spark plug
EP0171153A1 (fr) * 1984-07-09 1986-02-12 General Motors Corporation Bougie d'allumage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 6, no. 74 (M-127)(952) 11 May 1982, & JP-A-57 012 221 (HITACHI SEISAKUSHO K.K.) 22 January 1982, *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0400950B1 (fr) * 1989-05-29 2000-02-09 Ngk Spark Plug Co., Ltd Bougie d'allumage
US6043459A (en) * 1997-12-20 2000-03-28 Daimlerchrysler Ag And Beru Ag Electrically heatable glow plug with oxygen getter material
US6121577A (en) * 1997-12-20 2000-09-19 Daimlerchrysler Ag Electrically heatable glow plug with oxygen getter material
WO2002002933A1 (fr) * 2000-06-30 2002-01-10 Robert Bosch Gmbh Bougie crayon de prechauffage a detecteur de courant ionique et procede pour faire fonctionner une telle bougie
US6927362B2 (en) 2000-06-30 2005-08-09 Robert Bosch Gmbh Sheath type glowplug with ion current sensor and method for operation thereof
WO2005066611A2 (fr) * 2003-12-31 2005-07-21 Honeywell International Inc. Capteurs de matieres particulaires
WO2005066611A3 (fr) * 2003-12-31 2005-10-27 Honeywell Int Inc Capteurs de matieres particulaires
US6971258B2 (en) 2003-12-31 2005-12-06 Honeywell International Inc. Particulate matter sensor
US7275415B2 (en) 2003-12-31 2007-10-02 Honeywell International Inc. Particulate-based flow sensor
US7549317B2 (en) 2003-12-31 2009-06-23 Honeywell International Inc. Particle-based flow sensor
WO2007031371A1 (fr) * 2005-09-13 2007-03-22 Robert Bosch Gmbh Bougie-crayon de prechauffage
CN116477953A (zh) * 2023-05-15 2023-07-25 西安交通大学 一种SiC半导体点火材料、制备方法及应用

Also Published As

Publication number Publication date
EP0353196B1 (fr) 1993-05-19
MX170365B (es) 1993-08-18
KR920000219B1 (ko) 1992-01-10
CH676525A5 (fr) 1991-01-31
ZA895656B (en) 1990-07-25
AU603737B2 (en) 1990-11-22
DE68906610D1 (de) 1993-06-24
AR241806A1 (es) 1992-12-30
AU3899189A (en) 1990-05-03
DE68906610T2 (de) 1993-11-25
KR900002344A (ko) 1990-02-28
JPH02250938A (ja) 1990-10-08

Similar Documents

Publication Publication Date Title
EP0353196B1 (fr) Composition de cermet conducteur pour dispositifs d'allumage et de chauffage
US5233166A (en) Ceramic heater
EP0377938A2 (fr) Construction de bougie d'allumage
EP0427675B1 (fr) Bougie d'allumage à incandescence pour moteurs diesel et procédé de fabrication de cette bougie
EP0763693A1 (fr) Dispositif de chauffage en céramique et sa méthode de fabrication, et bougie à incandescence comportant un tel dispositif de chauffage en céramique
EP1669333A1 (fr) Composition de ceramique alumineuse et bougie d'allumage contenant une telle composition
US3558959A (en) Silicon carbide semi-conductor igniter structure
EP0335382B1 (fr) Matériau céramique électroconducteur
US4692657A (en) Spark plug for an otto-type internal combustion engine
JPH0712969B2 (ja) アルミナ磁器および点火プラグ
EP2190085A1 (fr) Isolateur et procédé de fabrication d'un isolateur
US5997998A (en) Resistance element
US3037140A (en) Electrically semi-conducting ceramic body
JP6366555B2 (ja) スパークプラグ
EP1250554B1 (fr) Allumeurs en ceramique, procedes d'utilisation et de production correspondants
JPH1025162A (ja) セラミック焼結体
US7247260B2 (en) Method for preparing a semi-conductive ceramic material, semi-conductive ceramic material and ignition plug using this ceramic material
US4418327A (en) Arc limiting refractory resistive element
US3737718A (en) Ignition noise suppression center electrode assembly for spark plugs
GB2302335A (en) Sintered semiconductor body
US20070077846A1 (en) Method for manufacturing an ignition plug and ignition plug produced in that manner
WO2000048279A1 (fr) Composition de verre a contact pour bougies d'allumage
GB2097469A (en) Igniters for internal combustion engines
US2268903A (en) Spark plug
US4487733A (en) Method of fabricating arc limiting refractory resistive element

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT

17P Request for examination filed

Effective date: 19900302

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CHAMPION SPARK PLUG EUROPE S.A.

17Q First examination report despatched

Effective date: 19920716

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19930519

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19930519

REF Corresponds to:

Ref document number: 68906610

Country of ref document: DE

Date of ref document: 19930624

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: CHAMPION SPARK PLUG BELGIUM S.A.

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19930803

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930819

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930819

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19940731

BERE Be: lapsed

Owner name: S.A. CHAMPION SPARK PLUG BELGIUM

Effective date: 19940731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000707

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000727

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST