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EP2514052B2 - Electrode de bougie d'allumage produite à partir d'un matériau d'électrode amélioré - Google Patents

Electrode de bougie d'allumage produite à partir d'un matériau d'électrode amélioré Download PDF

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Publication number
EP2514052B2
EP2514052B2 EP10752780.6A EP10752780A EP2514052B2 EP 2514052 B2 EP2514052 B2 EP 2514052B2 EP 10752780 A EP10752780 A EP 10752780A EP 2514052 B2 EP2514052 B2 EP 2514052B2
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Prior art keywords
electrode material
electrode
weight
spark plug
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English (en)
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EP2514052B1 (fr
EP2514052A1 (fr
Inventor
Lars Menken
Jochen Boehm
Juergen Oberle
Simone Baus
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Robert Bosch GmbH
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Robert Bosch GmbH
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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
    • H01T13/20—Sparking plugs characterised by features of the electrodes or insulation
    • H01T13/39—Selection of materials for electrodes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising

Definitions

  • the invention relates to a spark plug electrode made of an alloy based electrode material.
  • the requirements for the materials of the engine components are becoming increasingly demanding.
  • the components that play a major role in the ignition of the fuel mixture, the spark plugs, and in particular the spark plug electrodes are exposed to high loads, in particular by the oxygen-rich atmosphere and high temperatures in the engine compartment. This makes it necessary to provide spark plugs that meet these high requirements.
  • nickel alloys are used because nickel has both a high melting temperature, which is indispensable for the temperature resistance of the alloy, and has a high resistance to corrosion. While pure noble metal or precious metal based materials such as platinum or platinum alloys with iridium exhibit increased resistance to spark erosion attacks and hence very high electrode lifetimes, platinum spark plug electrode materials are cost effective in economic terms no suitable alternative to commercially available nickel alloys. Under spark-erosive attacks or erosion losses is the material removal from the electrode, which is induced by the action of the arc on the electrode surface understood.
  • EP 2 012 398 A2 discloses a spark plug electrode made of an electrode material wherein the electrode material comprises a) nickel as a base material and b) at least one further element selected from the group consisting of Y, Hf, Ce, La, Zr, Ta and Yb and c) at least one element from the group consisting of: Si, Na, K, Li, Ti, Ag and Cu, wherein the total content of element b) based on the total weight of the electrode material is 0.1 to 0.3 wt.%.
  • the oxide layer which forms on the surface of the spark plug electrode according to the invention has an optimized structure.
  • an optimized structure is understood to mean that the oxide layer has a uniform and stable composite and, moreover, is relatively thin and even at the surface in comparison to oxide layers which form on conventional electrodes. This allows a low electrical resistance of the oxide layer on the electrode surface.
  • a contact resistance between the oxide layer and the base material, that is to say the unoxidized electrode material is lowered, which results in additionally improved electrical conductivity.
  • the electrical resistance on the electrode surface located oxide layer low, that is equal to or less than predetermined by the above defined equation, the electrical voltage that arises during sparkover in the combustion chamber between the electrode surfaces, quickly derived from the surface of the electrode in the interior, so that the local stress ah the surface of the electrode is significantly reduced and is also of extremely short duration.
  • the ability to conduct the current rapidly and evenly from the electrode surface into the interior of the spark plug electrode is greater the smaller the electrical resistance.
  • Another positive effect of the invention is that in that the current is dissipated so quickly, also a local heating of the material delivered to the spark is counteracted, so that the tendency of the electrode material for further formation of oxides is again significantly reduced and thus only only an extremely thin and homogeneous oxide layer is formed on the electrode surface.
  • the wear of the electrode material by spark erosion and corrosion is thereby significantly reduced, so that the wear rate of the spark plug electrode according to the invention over those of conventional electrode materials is considerably reduced.
  • the electrode material according to the invention is stable and wear-resistant, even at high temperatures under the extreme conditions prevailing in the combustion chamber.
  • the spark plug electrode according to the invention is free of noble metals, but has significantly improved service life in comparison with conventional spark plugs.
  • a resistance of the electrode material also fulfills the previously defined equation, so that a similar, particularly preferably equal, resistance of the oxide layer formed on the electrode material and of the electrode material is present.
  • the spark plug electrode is characterized by an electrode material whose oxide layer on its surface has an electric resistance R equal to or smaller than that defined by the above-mentioned equation, so that all the above-mentioned advantages are obtained with this electrode material.
  • the heat-conducting properties of the oxides and thus of the overall alloy are also excellent so that the material also has an extremely high temperature resistance and, associated therewith, significantly reduced spark erosive wear or electrode erosion.
  • the oxidation and corrosion resistance of the material is also very good under continuous load.
  • the element b) is characterized by excellent electrical and physical properties and supports the formation of a thin and even oxide layer on the electrode surface. Concentration of element b) above 0.3% by weight lead to precipitations of this element, so that the corrosion resistance and erosion resistance of the material decreases again. On the other hand, concentration of element b) of less than 0.1% by weight does not have a sufficiently stabilizing effect on the electrode material.
  • the electrode material is preferably free of aluminum. This makes it easier to process the material with respect to known aluminum-containing materials, which can reduce the expense of producing such electrode materials.
  • a low-cost electrode material for spark plug electrodes is provided, which allows change intervals, which were previously achieved only with electrode materials of precious metal and precious metal alloys.
  • the oxide layer forming on the surface of the electrode has a thermal conductivity of more than 6 W / mK and preferably more than 8 W / mK and particularly preferably more than 10 W / mK, the thermal conductivity being 20 ° C is measured.
  • the spark plug electrode according to the invention is characterized by an extremely thin and uniform oxide layer, so that the spark plug electrode has excellent stability even in continuous operation of the spark plug.
  • the thermal conductivity of the forming oxide layer is less than 6 W / mK, locally high temperatures are produced in the spark plasma which are not dissipated sufficiently quickly to the surroundings, so that oxide layers deposit preferentially at these locations, so that the oxide layers are precisely at these locations To be formed very quickly. This increases the erosion and corrosion tendency of the material and thus its wear and it increasingly leads to heat build-up, which further promotes wear.
  • the electrode material has a thermal conductivity of more than 6 W / mK, and more preferably, the thermal conductivities of the oxide layer and the electrode material are the same.
  • the oxide layer formed on the surface of the electrode material has a thickness of less than 10 microns or more preferably has a thickness in a range of 5 to 8 microns. According to the invention, therefore, such materials are combined with one another to form an electrode material which is distinguished by a reduced tendency to form oxides under the prevailing extreme conditions. If the oxide layer forming is 10 ⁇ m or thicker, the oxide layer is insulating both in terms of heat and in terms of conductivity. This in turn promotes the formation of further oxides and thus also the wear rate of the electrode material. The smaller the thickness of the oxide layer, the more resistant the material is to spark erosion and, in particular, oxidative corrosion.
  • the proportion of oxygen in the electrode material is at most 0.002 wt .-%.
  • the formation of metallic oxides in the electrode material prior to starting the spark plug is so low that the electrode is optimally protected from oxidation and thus from destabilization by corrosion and erosion even at high temperatures.
  • the total amount of oxidized elements b) in the electrode material based on the total weight of the electrode material is less than 15 mol .-% and preferably less than 10 mol .-%. If the proportion of oxidic element b) before starting the electrode is higher than 10 mol% or even 15 mol%, its proportion is already so high that the reactive element b) is no longer sufficient for stabilizing the electrode material in the event of a spark It is already present in its oxidized form and thus can not be further Bind oxygen.
  • the base material, and in particular the nickel base material, to which at least one of the elements c) is alloyed is subject to stronger oxidation, and the electrode material wears out noticeably.
  • second intermetallic phases has proven to be particularly disadvantageous in terms of the stability of the electrode material, ie its resistance to oxidation and corrosion and erosion.
  • Intermetallic secondary phases form, as already stated, in particular when large proportions of reactive element b) are present in the alloy material, which are then present in the form of an intermetallic second phase not due to incompatibilities with the base material in dissolved form.
  • These second intermetallic phases lead to destabilization of the electrode material, since they do not insert themselves homogeneously into the alloy matrix but are precipitated out of it, so that the bonds between the alloying elements are locally reduced and also over further regions. The alloy structure is disturbed by second-phase intermetallics.
  • the electrical resistance of the material is increased and thus in particular the thermal conductivity and the electrical conductivity of the material is reduced, or they are inhomogeneous over the entire area, so that locally high temperature fluctuations can occur, which widen the material at these locations and a chipping of the material.
  • the disorder of the alloy structure is particularly large when the proportion of intermetallic phases in the electrode material is 15 mol% or more. It has been found that intermetallic phases, with a fraction of less than 15 mol%, and preferably less than 10 mol%, based on the total composition, are still tolerable, so that their destabilizing effects do not have an essential effect and the alloy matrix is sufficient is formed stable. The lower the proportion of intermetallic phases, the more stable the alloy structure is. It is therefore particularly preferable if substantially no intermetallic phases are present in the electrode material.
  • the electrode material for spark plug electrodes according to the invention can be used both for the production of the center, as well as the ground electrode as well as both electrodes simultaneously.
  • the spark plugs formed therefrom are approximately in the same range in terms of their life as they are obtained with Edelmetallmaterialzündkerzen, but without containing precious metal.
  • the life of the conventional non-precious spark plugs is only about 60,000 km
  • the life of the spark plug electrodes of the present invention is significantly higher, that is, in the range of 90,000 km. This creates a much better market acceptance and is beneficial for both environmental and economic reasons.
  • spark plugs which comprise at least one spark plug electrode according to the invention and which thus have improved oxidation and corrosion resistance as well as spark erosion resistance and thermal conductivity.
  • Electrode material 1.5 to 18 wt .-% and preferably 2 to 15 wt .-% is. It should be noted that the value for the total content of element b) may also be zero.
  • the electrode material of the second listed alternative according to the invention has particularly preferably, based on the total weight of the electrode material, an oxygen content of at most 0.003 wt .-%, and the electrode material according to the invention according to the first and the second alternative listed here in particular has an oxygen content of not more than 0.002 wt .-% on.
  • FIGS. 1 . 3 . 4 and 5 a spark plug electrode according to an embodiment of the invention described.
  • Figures 1 and 2 are micrographs with a scanning electron microscope at 500x magnification of part of an electrode.
  • reference numeral 1 denotes the respective electrode base material.
  • Reference numeral 2 denotes the surface of the electrode material on which an oxide layer 3 has been formed. Above it is a gas space 4 into which the electrode is inserted.
  • FIG. 1 is a microscope image of a nickel alloy according to the invention, which contains 0.2 wt .-% hafnium as element b) and 1 wt .-% silicon as element c), and an oxygen content of less than 0.0015 wt .-%, each based on the total weight of the electrode material.
  • the oxide layer 3 in the electrode material according to the invention is very thin and uniform and on average about 5 to 8 ⁇ m thick. This clearly shows the positive influence of the reactive elements b) on the formation of the oxide protective layer, which is according to the invention thin and stable pronounced. Oxidized areas inside the electrode material are practically nonexistent.
  • FIG. 2 shows a micrograph of a conventional nickel alloy, which has 1 wt .-% Al, 1 wt .-% Si and 0.2 wt .-% Y and an oxygen content of 0.0033 wt .-%.
  • the oxide layer 3 located on the surface of the electrode is formed non-uniformly and porous and shows widely large subregions 6 in which the oxide regions extend deep into the interior of the electrode material.
  • the oxide layer formed on the surface of the electrode is formed significantly thicker and is on average between 12 and 20 microns.
  • the reactive element b although in the optimal concentration, but not in a dissolved state, but in the form of isolated aggregates or intermetallic second phases 5 are present, which are eliminated from the nickel matrix.
  • the nickel structure is faulty and the surrounding oxygen oxidizes on the one hand the nickel at the electrode surface significantly stronger and on the other penetrates the oxygen into the electrode interior and oxidized here both more nickel and the intermetallic second phases of reactive element b).
  • the electrode material is therefore characterized by a high wear rate.
  • FIG. 3 shows measurement results of the electrical resistance R in ⁇ of oxide layers of two electrodes logarithmically as a function of the temperature T in ° C.
  • the underlying curve 11, whose measured values are marked with crosses, is that of the electrode according to the invention ( FIG. 1 ).
  • the electrical resistance R in the entire temperature spectrum is significantly lower than in a conventional electrode material due to the thinner oxide protective layer according to the invention on the electrode surface.
  • the electrode material according to the invention thus has excellent electrical conductivities, without precious metal being used in the electrode material.
  • FIG. 4 shows different wear rates of electrode materials of different composition, as summarized in the following overview.
  • the wear V in ⁇ m 3 per spark for the different electrode materials is shown.
  • the diamonds represent the mean values of the measured values and the vertical lines their dispersion.
  • electrode material A according to the invention B standard Reactive element b) Hf Y Amount of reactive element b) in% by weight 0.2 0.2 Element c) Si Si Amount of element c) in% by weight 1 1 Oxygen content in% by weight 0.0015 0.0033 base material Ni Ni more elements --- Al (1% by weight)
  • the electrode material according to the invention causes a reduction of the wear of about 25%.
  • FIG. 5 is an Arrhenius plot, the electrical resistance R to the temperature T 'is shown, wherein the temperature T' by the quotient 1000 / T in K -1 is shown.
  • the electrical resistance of the oxide layer of the spark plug electrode according to the invention (curve 13) is significantly smaller than the resistance of conventional oxide layers of electrodes without precious metals (curve 12).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spark Plugs (AREA)
  • Ceramic Products (AREA)

Claims (8)

  1. Electrode de bougie d'allumage réalisée en un matériau d'électrode, une couche d'oxyde présente sur une surface du matériau d'électrode présentant une résistance électrique R inférieure ou égale à celle définie par l'équation ci-dessous : logR = a + b * 1000 T ,
    Figure imgb0004
     dans laquelle 0,6 ≤ à ≤ 0,8 et en particulier 0,7, 3,1 ≤ b ≤ 3,3 et en particulier 3,2 et T étant la température en Kelvin,
    le matériau d'électrode consistant
    a) du nickel comme matériau de base et
    b) au moins un autre élément sélectionné dans l'ensemble constitué de Y, Hf, Ce, La, Zr, Ta et Yb et
    c) au moins un autre élément sélectionné dans l'ensemble constitué de Si, Na, K, Li, Ti, Ag et Cu,
    la teneur totale en élément b) par rapport au poids total du matériau d'électrode étant de 0,1 à 0,3 % en poids, de préférence de 0,1 à 0,2 % en poids et de façon particulièrement préférable de 0,13 à 0,17 % en poids,
    la teneur totale en élément c) par rapport au poids total du matériau d'électrode étant de 0,5 à 3 % en poids et de préférence de 1,0 à 2,5 % en poids, et
    le matériau d'électrode présente par rapport au poids total du matériau d'électrode une teneur en oxygène d'au plus 0,003 % en poids et en particulier de 0,002 % en poids,
    ou le matériau d'électrode contenant
    a) du nickel comme matériau de base et
    b) au moins un autre élément sélectionné dans l'ensemble constitué de Y, Hf, Ce, La, Zr, Ta et Yb et
    d) au moins un autre élément sélectionné dans l'ensemble constitué de V, Zn et Ti,
    la teneur totale en élément b) par rapport au poids total du matériau d'électrode étant ≤ 0,3 % en poids et
    la teneur totale en élément d) par rapport au poids total du matériau d'électrode étant de 1,5 à 18 % en poids et de préférence de 2 à 15 % en poids.
  2. Electrode de bougie d'allumage selon la revendication 1, caractérisée en ce que la couche d'oxyde présente à la surface du matériau d'électrode présente à 20°C une conductivité thermique supérieure à 6 W/m.K, de préférence à 8 W/m.K et de façon particulièrement préférable à 10 W/m.K.
  3. Electrode de bougie d'allumage selon l'une des revendications précédentes, caractérisée en ce que la couche d'oxyde présente une épaisseur d'au moins 10 µm et de préférence une épaisseur de l'ordre de 5 à 8 µm.
  4. Electrode de bougie d'allumage selon l'une des revendications précédentes, caractérisée en ce que le matériau d'électrode contient
    a) du nickel comme matériau de base et
    b) au moins un autre élément sélectionné dans l'ensemble constitué de Y, Hf, Ce, La, Zr, Ta et Yb et
    d) au moins un autre élément sélectionné dans l'ensemble constitué de V, Zn et Ti,
    la teneur totale en élément b) par rapport au poids total du matériau d'électrode étant ≤ 0,3 % en poids et
    la teneur totale en élément d) par rapport au poids total du matériau d'électrode étant de 1,5 à 18 % en poids et de préférence de 2 à 15 % en poids, et
    le matériau d'électrode présente par rapport au poids total du matériau d'électrode une teneur en oxygène d'au plus 0,003 % en poids et en particulier de 0,002 % en poids.
  5. Electrode de bougie d'allumage selon la revendication 1, caractérisée en ce que la teneur totale en élément oxydé b) dans le matériau d'électrode par rapport au poids total du matériau d'électrode est inférieure à 15 % en moles et de préférence inférieure à 10 % en moles.
  6. Electrode de bougie d'allumage selon l'une des revendications précédentes, caractérisée en ce que la teneur en phase intermétallique dans le matériau d'électrode par rapport à la composition globale du matériau d'électrode est inférieure à 15 % en mole et de préférence inférieure à 10 % en mole.
  7. Electrode de bougie d'allumage selon l'une des revendications précédentes, caractérisée en ce que le matériau d'électrode ne contient essentiellement pas de phases intermétalliques.
  8. Bougie d'allumage comprenant au moins une électrode de bougie d'allumage selon l'une des revendications précédentes.
EP10752780.6A 2009-10-26 2010-09-06 Electrode de bougie d'allumage produite à partir d'un matériau d'électrode amélioré Active EP2514052B2 (fr)

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DE102009046005A DE102009046005A1 (de) 2009-10-26 2009-10-26 Zündkerzenelektrode, hergestellt aus verbessertem Elektrodenmaterial
PCT/EP2010/063021 WO2011054561A1 (fr) 2009-10-26 2010-09-06 Electrode de bougie d'allumage produite à partir d'un matériau d'électrode amélioré

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EP2514052A1 EP2514052A1 (fr) 2012-10-24
EP2514052B1 EP2514052B1 (fr) 2015-02-25
EP2514052B2 true EP2514052B2 (fr) 2018-08-22

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EP (1) EP2514052B2 (fr)
JP (1) JP5826182B2 (fr)
CN (1) CN102598443B (fr)
BR (1) BR112012010819A2 (fr)
DE (1) DE102009046005A1 (fr)
WO (1) WO2011054561A1 (fr)

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DE102011007532A1 (de) * 2011-04-15 2012-10-18 Robert Bosch Gmbh Zündkerzenelektrodenmaterial und Zündkerze, sowie Verfahren zur Herstellung des Zündkerzenelektrodenmaterials
DE102011007496A1 (de) 2011-04-15 2012-10-18 Robert Bosch Gmbh Zündkerzenelektrodenmaterial und Zündkerze, sowie Verfahren zur Herstellung des Zündkerzenelektrodenmaterials und einer Elektrode für die Zündkerze
JP6065580B2 (ja) 2012-12-25 2017-01-25 住友電気工業株式会社 内燃機関用材料の評価試験方法
JP6438249B2 (ja) * 2014-09-16 2018-12-12 株式会社東芝 電極材料およびそれを用いた電極層、電池並びにエレクトロクロミック素子
JP6312723B2 (ja) 2016-01-18 2018-04-18 日本特殊陶業株式会社 スパークプラグ

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DE10224891A1 (de) * 2002-06-04 2003-12-18 Bosch Gmbh Robert Legierung auf Nickelbasis
JP4699867B2 (ja) * 2004-11-04 2011-06-15 日立金属株式会社 点火プラグ用電極材料
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US4684505A (en) † 1985-06-11 1987-08-04 Howmet Turbine Components Corporation Heat resistant alloys with low strategic alloy content
EP0933848A1 (fr) † 1998-01-28 1999-08-04 Ngk Spark Plug Co., Ltd Bougie d'allumage à résistance incorporée
EP1065290A1 (fr) † 1999-06-30 2001-01-03 Sumitomo Metal Industries, Ltd. Alliage à base de nickel résistant à la chaleur
JP2007092139A (ja) † 2005-09-29 2007-04-12 Hitachi Metals Ltd 点火プラグ用電極材料
US20080050264A1 (en) † 2006-08-28 2008-02-28 Federal-Mogul World Wide, Inc. Ignition Device Electrode Composition
JP2009245640A (ja) † 2008-03-28 2009-10-22 Ngk Spark Plug Co Ltd スパークプラグ

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EP2514052B1 (fr) 2015-02-25
JP5826182B2 (ja) 2015-12-02
EP2514052A1 (fr) 2012-10-24
JP2013508557A (ja) 2013-03-07
BR112012010819A2 (pt) 2017-12-19
DE102009046005A1 (de) 2011-04-28
WO2011054561A1 (fr) 2011-05-12
CN102598443B (zh) 2015-05-06

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