EP0353196B1 - Zusammensetzungen von elektroleitendem Cermet für Zündungs- und Heizungsanordnungen - Google Patents

Zusammensetzungen von elektroleitendem Cermet für Zündungs- und Heizungsanordnungen Download PDF

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Publication number
EP0353196B1
EP0353196B1 EP89810563A EP89810563A EP0353196B1 EP 0353196 B1 EP0353196 B1 EP 0353196B1 EP 89810563 A EP89810563 A EP 89810563A EP 89810563 A EP89810563 A EP 89810563A EP 0353196 B1 EP0353196 B1 EP 0353196B1
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EP
European Patent Office
Prior art keywords
cermet
sintering
cermet composition
particles
metal
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.)
Expired - Lifetime
Application number
EP89810563A
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English (en)
French (fr)
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EP0353196A1 (de
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 Europe SA
Champion Spark Plug Belgium SA
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Publication date
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Publication of EP0353196A1 publication Critical patent/EP0353196A1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23Q—IGNITION; EXTINGUISHING-DEVICES
    • F23Q7/00—Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
    • F23Q7/001—Glowing plugs for internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • 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
    • H01T13/20—Sparking plugs characterised by features of the electrodes or insulation
    • H01T13/39—Selection of materials for electrodes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23Q—IGNITION; EXTINGUISHING-DEVICES
    • F23Q7/00—Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
    • F23Q7/001—Glowing plugs for internal-combustion engines
    • F23Q2007/004—Manufacturing 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.
  • 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
  • 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 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.
  • NNK Electrically conductive cermet compositions somewhat similar to that of the foregoing document, but in which the metal particles are distributed anisotropically, i.e. the concentration of said particles within the ceramic matrix varies directionally according to a given pattern.
  • 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%.
  • Figure 1 schematically represents an ignition spark-plug for gasoline engines in which some components are made of electroconductive cermets in conformity with the composition according to the invention.
  • Figure 2 schematically represents a glow-plug for Diesel engines of which some components are made of electroconductive cermets achieved according to the invention.
  • Figure 3 is a microphotograph showing the internal structure of a cermet composition according to the invention.
  • Figure 4 is a microphotograh which shows, comparatively, the structure of a cermet composition from the prior art.
  • 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.
  • the cermet samples which resulted from the sintering of this control composition were tested identically and the results are gathered in Table 1.
  • 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 2 (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 phtalate; 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. Naturally 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 against 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:
  • 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.
  • 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.
  • the metal grains are intimately incorporated into the ceramic phase, no significant sharp transition borderline being visible.
  • 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.
  • a control was prepared as indicated above, using a chromium powder with no chromium oxide or a negligible quantity (POUDNET chromium powder). The results are also in Table 2.
  • 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

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  • 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)
  • Spark Plugs (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Resistance Heating (AREA)
  • Non-Adjustable Resistors (AREA)
  • Ignition Installations For Internal Combustion Engines (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (10)

  1. Elektrisch leitende Cermet-Zusammensetzung mit verbesserter Korrosions- und/oder Erosionsbeständigkeit, enthaltend eine auf Aluminiumoxid basierende Keramik und 30 bis 60 Gew.-% Metallteilchen, in der die Metallteilchen teilweise oxidiert sind und das Gewichts-Verhältnis von Sauerstoff zu Metall in diesen Teilchen etwa 0,3 bis 10% beträgt.
  2. Cermet-Zusammensetzung nach Anspruch 1, worin das Metalloxid der Teilchen in der Form eines anhaftenden Filmes auf zumindest einem Teil der Oberfläche der Teilchen ist.
  3. Cermet-Zusammensetzung nach Anspruch 2, welche weiter 2 bis 20 Gew.-% einer auf Silicat basierenden glasartigen Phase enthält.
  4. Cermet-Zusammensetzung nach Anspruch 3, in welcher die glasartige Phase SiO₂ und zumindest eines der Oxide MgO, CaO, Na₂O, Fe₂O₃, TiO₂, ZnO, PbO₂, B₂O₃ enthält.
  5. Cermet-Zusammensetzung nach Anspruch 2, in der die keramische Phase zumindest teilweise aus Mullit der Formel 3Al2O₃.2SiO₂.
  6. Verfahren zur Herstellung elektrisch leitender Cermet-Zusammensetzungen nach Anspruch 1, welches die Schritte
    (1) des Vermischens der Bestandteile der Cermet-Zusammensetzung oder deren Precursor in einer Formulierung in Mischung mit Form- und Sinter-Zusatzstoffen,
    (2) des Bildens oder Formens von "grünen" Gegenständen oder Erzeugnissen aus der gemischten Formulierung und
    (3) des Sinterns der "grünen" Gegenstände bei hohen Temperaturen, um Gegenstände mit der gewünschten Cermet-Zusammensetzung zu erhalten, wobei die teilweise Oxidation der Metallteilchen entweder vor dem Mischen der Stufe (1) oder während dem Sintern durchgeführt wird, umfaßt.
  7. Verfahren nach Anspruch 6 unter Einschluß der teilweisen Oxidation der Metallteilchen während dem Sintern, worin die letztere sich aus dem durch ein Oxidationsmittel der Mischung freigesetzten Sauerstoff ergibt, welches sich durch Erwärmen bei der Sintertemperatur zersetzt.
  8. Verfahren nach Anspruch 6, in welchem die teilweise Oxidation der Metallteilchen während dem Sintern bewirkt wird, durch Durchführen des Sinterns in einer oxidierenden Atmosphäre, so daß die teilweise Oxidation sich aus der oxidierender Wirkung der Atmosphäre ergibt.
  9. Verfahren zum Herstellen von Funken- oder Plasma-Entladungszündkerzen für Benzinmotoren, welches zumindest teilweise die Realisierung einer oder mehrerer der Elektroden der Zündkerzen nach dem Verfahren gemäß Anspruch 6 umfaßt.
  10. Verfahren zum Herstellen von Glühkerzen für Dieselmotoren, welches die Realisierung des als ein Glühelement dienenden Kerzenteils durch Überziebhen eines isolierenden keramisches Fangmittels mit einer Schicht einer elektrisch leitenden Cermet-Zusammensetzung nach Anspruch 1 und anschließendem Sintern der Überzugsschicht umfaßt.
EP89810563A 1988-07-28 1989-07-24 Zusammensetzungen von elektroleitendem Cermet für Zündungs- und Heizungsanordnungen Expired - Lifetime EP0353196B1 (de)

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

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EP0353196A1 EP0353196A1 (de) 1990-01-31
EP0353196B1 true EP0353196B1 (de) 1993-05-19

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

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US8165786B2 (en) 2005-10-21 2012-04-24 Honeywell International Inc. System for particulate matter sensor signal processing

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JPH07109783B2 (ja) * 1989-05-29 1995-11-22 日本特殊陶業株式会社 内燃機関用スパークプラグ
DE19756988C1 (de) * 1997-12-20 1999-09-02 Daimler Benz Ag Elektrisch beheizbare Glühkerze oder Glühstab für Verbrennungsmotoren
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
DE10031893A1 (de) 2000-06-30 2002-01-10 Bosch Gmbh Robert Glühstiftkerze mit Ionenstromsensor sowie Verfahren zum Betreiben einer derartigen Glühstiftkerze
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
US7275415B2 (en) 2003-12-31 2007-10-02 Honeywell International Inc. Particulate-based flow sensor
US6971258B2 (en) 2003-12-31 2005-12-06 Honeywell International Inc. Particulate matter sensor
DE102005043415A1 (de) * 2005-09-13 2007-03-15 Robert Bosch Gmbh Glühstiftkerze
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 (de) * 2017-02-01 2018-08-08 Kistler Holding AG Zuendkerze und verfahren zu deren fertigung
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

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JPS5657282A (en) * 1979-10-13 1981-05-19 Ngk Spark Plug Co Ignition plug
JPS5712221A (en) * 1980-06-25 1982-01-22 Hitachi Ltd Glow plug for diesel engine
US4659960A (en) * 1984-05-09 1987-04-21 Ngk Spark Plug Co., Ltd. Electrode structure for a spark plug
EP0171153A1 (de) * 1984-07-09 1986-02-12 General Motors Corporation Zündkerze

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8165786B2 (en) 2005-10-21 2012-04-24 Honeywell International Inc. System for particulate matter sensor signal processing

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AR241806A1 (es) 1992-12-30
ZA895656B (en) 1990-07-25
EP0353196A1 (de) 1990-01-31
AU3899189A (en) 1990-05-03
JPH02250938A (ja) 1990-10-08
MX170365B (es) 1993-08-18
DE68906610D1 (de) 1993-06-24
CH676525A5 (de) 1991-01-31
DE68906610T2 (de) 1993-11-25
KR920000219B1 (ko) 1992-01-10
AU603737B2 (en) 1990-11-22
KR900002344A (ko) 1990-02-28

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