EP2514052B2 - Spark plug electrode produced from improved electrode material - Google Patents

Spark plug electrode produced from improved electrode material 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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EP
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Prior art keywords
electrode material
electrode
weight
spark plug
und
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German (de)
French (fr)
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EP2514052B1 (en
EP2514052A1 (en
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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).

Description

Stand der TechnikState of the art

Die Erfindung betrifft eine Zündkerzenelektrode, die aus einem Elektrodenmaterial auf Legierungsbasis hergestellt wird.The invention relates to a spark plug electrode made of an alloy based electrode material.

Aufgrund der steten Weiterentwicklung von Kraftfahrzeugmotoren und deren Komponenten zur Steigerung der Leistungsfähigkeit und Motorkraft, werden auch an die Materialien der Motorbauteile immer höhere Anforderungen gestellt. Insbesondere die Bauteile, die eine tragende Rolle bei der Zündung des Brennstoffgemisches spielen, die Zündkerzen, und insbesondere die Zündkerzenelektroden, sind hohen Belastungen insbesondere durch die Sauerstoffreiche Atmosphäre und hohe Temperaturen im Motorraum, ausgesetzt. Dies macht es erforderlich Zündkerzen bereitzustellen, die diesen hohen Anforderungen genügen.Due to the constant development of motor vehicle engines and their components for increasing the efficiency and engine power, the requirements for the materials of the engine components are becoming increasingly demanding. In particular, 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.

Als Basismaterial für Zündkerzenelektroden werden unter anderem Nickellegierungen verwendet, da Nickel sowohl eine hohe Schmelztemperatur aufweist, die für die Temperaturbeständigkeit der Legierung unabdingbar ist, sowie eine hohe Beständigkeit gegenüber Korrosion aufweist. Zwar zeigen Werkstoffe aus reinen Edelmetallen oder auf Edelmetallbasis, wie Platin oder Platinlegierungen mit Iridium, hinsichtlich der Verschleißbeständigkeit gegen funkenerosive Angriffe eine gesteigerte Beständigkeit und damit sehr hohe Lebenszeiten der Elektroden, jedoch stellen Zündkerzenelektrodenmaterialien aus Platin, im Hinblick auf die enormen Kosten, aus wirtschaftlichen Gründen keine geeignete Alternative zu handelsüblichen Nickellegierungen dar. Unter funkenerosiven Angriffen bzw. Erosionsverlusten wird dabei der Materialabtrag von der Elektrode, der durch die Einwirkung des Lichtbogens auf die Elektrodenoberfläche induziert wird, verstanden.As the base material for spark plug electrodes, among others, 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.

In herkömmlichen Zündkerzenelektroden, z.B. aus Nickellegierungen, oxidiert unterIn conventional spark plug electrodes, e.g. made of nickel alloys, oxidized under

Betriebsbedingungen im Motorraum eines Fahrzeugs ein Großteil der Nickeloberfläche sowie auch ein Teil des Nickels im Inneren des Elektrodenmaterials durch Reaktion mit dem umgebenden Sauerstoff. Dadurch wird eine dicke, sowohl wärmeisolierende wie auch die elektrische Leitfähigkeit unterbindende bzw. reduzierende Nickeloxidschicht gebildet, die schon nach einiger Zeit aufgrund fehlenden Verbundes mit dem nicht oxidierten Nickelbasismaterial zu Korrosion bzw. zu funkenerosiver Erosion neigt.Operating conditions in the engine compartment of a vehicle, a large part of the nickel surface as well as a part of the nickel inside the electrode material by reaction with the surrounding oxygen. As a result, a thick, both heat-insulating as well as the electrical conductivity-inhibiting or reducing nickel oxide layer is formed, which tends after some time due to lack of association with the unoxidized nickel base material to corrosion or spark erosive erosion.

EP 2 012 398 A2 offenbart eine Zündkerzenelektrode, hergestellt aus einem Elektrodenmaterial wobei das Elektrodenmaterial a) Nickel als Basismaterial und b) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb und c) mindestens ein Element ausgewählt aus der Gruppe bestehend aus: Si, Na, K, Li, Ti, Ag und Cu enthält, wobei der Gesamtanteil an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials 0,1 bis 0,3 Gew.% beträgt. 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.%.

Offenbarung der ErfindungDisclosure of the invention

Es sei den weiteren Ausführungen vorangestellt, dass sich alle nachstehenden Gew.-%- Angaben, sofern nicht ausdrücklich anders gekennzeichnet, immer auf das Gesamtgewicht der Zusammensetzung des Elektrodenmaterials beziehen.It is preceded by the further statements that all the following wt .-% - information, unless expressly indicated otherwise, always refer to the total weight of the composition of the electrode material.

Die erfindungsgemäße Zündkerzenelektrode mit den Merkmalen des Anspruches 1 zeichnet sich durch eine extrem hohe Temperaturbeständigkeit und einen deutlich reduzierten funkenerosiven Verschleiß bzw. Elektrodenabbrand aus und weist eine einzigartige Oxidations- und Korrosionsbeständigkeit auf. Somit wird ein kostengünstiges Elektrodenmaterial für Zündkerzenelektroden bereitgestellt, das Wechselintervalle erlaubt, die bislang nur mit Elektrodenmaterialien aus Edelmetall- und Edelmetalllegierungen erzielt wurden. Erfindungsgemäß wird dies dadurch erreicht, dass eine an der Oberfläche des Elektrodenmaterials gebildete Oxidschicht einen elektrischen Widerstand R aufweist, der kleiner oder gleich ist, als durch nachfolgende Gleichung definiert: logR = a + b * 1000 T ,

Figure imgb0001
wobei 0,6 ≤ a ≤ 0,8, insbesondere 0,7, ist, wobei 3,1 ≤ b ≤ 3,3, insbesondere 3,2, ist
und wobei T die Temperatur in Kelvin ist,
wobei das Elektrodenmaterial aus

  1. a) Nickel als Basismaterial,
  2. b) mindestens einem weiteren Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb, und
  3. c) mindestens einem weiteren Element ausgewählt aus der Gruppe bestehend aus: Si, Na, K, Li, Ti, Ag und Cu besteht, wobei
der Gesamtanteil an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials 0,1 bis 0,3 Gew.-%, bevorzugt 0,1 bis 0,2 Gew.-% und besonders bevorzugt 0,13 bis 0,17 Gew.-% beträgt,
wobei der Gesamtanteil an Element c) bezogen auf das Gesamtgewicht des Elektrodenmaterials 0,5 bis 3 Gew.-% und bevorzugt 1,0 bis 2,5 Gew.-% beträgt, und
wobei
das Elektrodenmaterial bezogen auf das Gesamtgewicht des Elektrodenmaterials einen Sauerstoffgehalt von maximal 0,003 Gew.-% und insbesondere 0,002 Gew.-% aufweist
oder
wobei das Elektrodenmaterial
  • a) Nickel als Basismaterial und
  • b) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb und
  • d) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus V, Zn und Ti enthält, wobei
der Gesamtgehalt an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials ≤ 0,3 Gew.-% beträgt und wobei
der Gesamtgehalt an Element d) bezogen auf das Gesamtgewicht des Elektrodenmaterials 1,5 bis 18 Gew.-% und bevorzugt 2 bis 15 Gew.-% beträgt.The spark plug electrode according to the invention with the features of claim 1 is characterized by an extremely high temperature resistance and a significantly reduced spark erosive wear or electrode erosion and has a unique oxidation and corrosion resistance. Thus, 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. According to the invention, this is achieved in that an oxide layer formed on the surface of the electrode material has an electrical resistance R which is less than or equal to, as defined by the following equation: log R = a + b * 1000 T .
Figure imgb0001
 where 0.6 ≤ a ≤ 0.8, in particular 0.7, wherein 3.1 ≤ b ≤ 3.3, in particular 3.2
and where T is the temperature in Kelvin,
wherein the electrode material made
  1. a) nickel as base material,
  2. b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb, and
  3. c) at least one further element selected 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 0.1 to 0.3 wt .-%, preferably 0.1 to 0.2 wt .-% and particularly preferably 0.13 to 0.17 wt .-% is,
wherein the total content of element c) based on the total weight of the electrode material is 0.5 to 3 wt .-% and preferably 1.0 to 2.5 wt .-%, and
in which
the electrode material based on the total weight of the electrode material has an oxygen content of at most 0.003 wt .-% and in particular 0.002 wt .-%
or
wherein the electrode material
  • a) nickel as base material and
  • b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb and
  • d) at least one further element selected from the group consisting of V, Zn and Ti contains, wherein
the total content of element b) is ≦ 0.3% by weight, based on the total weight of the electrode material, and wherein
the total content of element d) based on the total weight of the electrode material is 1.5 to 18% by weight and preferably 2 to 15% by weight.

Die Oxidschicht, die sich an der Oberfläche der erfindungsgemäßen Zündkerzenelektrode bildet, weist eine optimierte Struktur auf. Unter einer optimierten Struktur wird dabei verstanden, dass die Oxidschicht einen gleichmäßigen und stabilen Verbund aufweist und zudem relativ dünn und an der Oberfläche ebenmäßig ist im Vergleich zu sich auf herkömmlichen Elektroden bildenden Oxidschichten. Dies ermöglicht einen geringen elektrischen Widerstand der Oxidschicht an der Elektrodenoberfläche. Erfindungsgemäß wird ferner ein Übergangswiderstand zwischen der Oxidschicht und dem Grundmaterial, also dem unoxidierten Elektrodenmaterial, gesenkt, was eine zusätzlich verbesserte elektrische Leitfähigkeit zur Folge hat. Ist der elektrische Widerstand an der Elektrodenoberfläche befindlichen Oxidschicht gering, also gleich oder kleiner als durch oben definierte Gleichung vorgegeben, so wird die elektrische Spannung, die beim Funkenüberschlag im Brennraum zwischen den Elektrodenoberflächen entsteht, schnell von der Oberfläche der Elektrode in deren Inneres abgeleitet, so dass die lokale Belastung ah der Oberfläche der Elektrode deutlich vermindert wird und auch nur von extrem kurzer Dauer ist. Die Fähigkeit, den Strom schnell und gleichmäßig von der Elektrodenoberfläche in das Innere der Zündkerzenelektrode zu leiten, ist umso größer, je kleiner der elektrische Widerstand ist. Ein weiterer positiver Effekt der Erfindung ist, dass dadurch, dass der Strom so schnell abgeleitet wird, außerdem einer lokalen Erwärmung des dem Funken ausgelieferten Materials entgegengewirkt wird, so dass die Neigung des Elektrodenmaterials zur weiteren Bildung von Oxiden wiederum deutlich vermindert wird und somit lediglich nur eine extrem dünne und homogene Oxidschicht an der Elektrodenoberfläche gebildet wird. Der Verschleiß des Elektrodenmaterials durch Funkenerosion und Korrosion wird dadurch deutlich verringert, so dass die Verschleißrate der erfindungsgemäßen Zündkerzenelektrode gegenüber solchen aus herkömmlichen Elektrodenmaterialien erheblich reduziert ist. Das erfindungsgemäße Elektrodenmaterial ist auch bei hohen Temperaturen unter den extremen Bedingungen, wie sie im Brennraum herrschen, stabil und verschleißresistent. Die erfindungsgemäße Zündkerzenelektrode ist edelmetallfrei, weist jedoch signifikant verbesserte Standzeiten im Vergleich mit herkömmlichen Zündkerzen auf. Besonders bevorzugt erfüllt auch ein Widerstand des Elektrodenmaterials die vorhergehend definierte Gleichung, so dass ein ähnlicher, besonders bevorzugt gleicher, Widerstand der am Elektrodenmaterial gebildeten Oxidschicht und des Elektrodenmaterials vorhanden ist.The oxide layer which forms on the surface of the spark plug electrode according to the invention has an optimized structure. In this context, 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. Furthermore, according to the invention, 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. If 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. Particularly preferably, 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.

Gemäß der Erfindung besteht das Elektrodenmaterial, das die erfindungsgemäße Zündkerzenelektrode bildet, aus:

  1. 1. a) Nickel als Basismaterial und
  2. 2. b) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb, und
  3. 3. c) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Si, Na, K, Li, Ti, Ag und Cu, wobei
der Gesamtanteil an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials 0,1 bis 0,3 Gew.-%, bevorzugt 0,1 bis 0,2 Gew.-% und besonders bevorzugt 0,13 bis 0,17 Gew.-% beträgt, wobei das Elektrodenmaterial bezogen auf das Gesamtgewicht des Elektrodenmaterials einen Sauerstoffgehalt von maximal 0,003 Gew.-% und insbesondere 0,002 Gew.-% aufweist. Diese erfindungsgemäßeAccording to the invention, the electrode material forming the spark plug electrode according to the invention consists of:
  1. 1. a) nickel as base material and
  2. 2. b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb, and
  3. 3. c) at least one further element selected 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 0.1 to 0.3 wt .-%, preferably 0.1 to 0.2 wt .-% and particularly preferably 0.13 to 0.17 wt .-% is, wherein the electrode material based on the total weight of the electrode material has an oxygen content of not more than 0.003 wt .-% and in particular 0.002 wt .-%. This invention

Zündkerzenelektrode zeichnet sich durch ein Elektrodenmaterial aus, dessen an seiner Oberfläche befindliche Oxidschicht einen elektrischen Widerstand R aufweist, der gleich oder kleiner ist als derjenige, der durch oben angeführte Gleichung definiert wird, so dass alle oben erwähnten Vorteile mit diesem Elektrodenmaterial erzielt werden. Auch die wärmeleitenden Eigenschaften der Oxide und damit der Gesamtlegierung sind ausgezeichnet so dass das Material ferner auch eine extrem hohe Temperaturbeständigkeit und einen damit einhergehend deutlich reduzierten funkenerosiven Verschleiß bzw. Elektrodenabbrand aufweist. Die Oxidations- und Korrosionsbeständigkeit des Materials ist auch unter Dauerbelastung sehr gut. Das Element b) zeichnet sich durch hervorragende elektrische und physikalische Eigenschaften aus und unterstützt die Bildung einer dünnen und ebenmäßigen Oxidschicht an der Elektrodenoberfläche. Konzentration an Element b) von über 0,3 Gew.-% führen zu Ausscheidungen dieses Elements, so dass die Korrosionsbeständigkeit und Erosionsbeständigkeit des Materials wieder sinkt. Konzentration an Element b) von weniger als 0,1 Gew.-% hingegen wirken nicht ausreichend stabilisierend auf das Elektrodenmaterial.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.

Demnach bevorzugt ist das Elektrodenmaterial frei von Aluminium. Dadurch lässt sich das Material in Bezug auf bekannte, Aluminium-haltige Materialien, leichter verarbeiten, was den Aufwand für die Produktion solcher Elektrodenmaterialien senken kann. Somit wird ein kostengünstiges Elektrodenmaterial für Zündkerzenelektroden bereitgestellt, das Wechselintervalle erlaubt, die bislang nur mit Elektrodenmaterialien aus Edelmetall- und Edelmetalllegierungen erzielt wurden.Accordingly, 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. Thus, 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.

Gemäß einer Alternative der Erfindung enthält das Elektrodenmaterial, das die erfindungsgemäße Zündkerzenelektrode bildet:

  • a) Nickel als Basismaterial und
  • b) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb, und
  • d) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus V, Zn und Ti, wobei
der Gesamtgehalt an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials ≤0,5 Gew.-% und bevorzugt ≤0,3 Gew.-% beträgt und wobei der Gesamtgehalt an Element d) bezogen auf das Gesamtgewicht des Elektrodenmaterials 1,5 bis 18 Gew.-% und bevorzugt 2 bis 15 Gew.-% beträgt. Auch diese erfindungsgemäße Zündkerzenelektrode zeichnet sich durch ein Elektrodenmaterial aus, dessen an seiner Oberfläche befindliche Oxidschicht einen elektrischen Widerstand R aufweist, der kleiner ist als derjenige, der durch oben angeführte Gleichung definiert wird, so dass alle oben erwähnten Vorteile auch mit diesem Elektrodenmaterial erzielt werden. Die Elemente d), also V, Zn und Ti, fügen sich besonders homogen in eine Nickelmatrix ein. Das Elektrodenmaterial zeichnet sich durch einen geringen Übergangswiderstand zwischen Oxidschicht und dem Elektrodengrundmaterial aus, so dass dessen elektrische Leitfähigkeit stark erhöht ist. Auch die wärmeleitenden Eigenschaften sind ausgezeichnet, so dass verschleißresistentes Material gebildet wird. Die elektrischen Eigenschaften und auch die Wärmeleitfähigkeit der Oxide der Elemente V, Zn und Ti sind dabei so ausgezeichnet, dass vorzugsweise sogar auf das reaktive Element b) verzichtet werden kann. Besonders bevorzugt ist aber, wenn mindestens ein weiteres Element aus der Gruppe bestehend aus Y, Hf, Ce, La, Zr, Ta und Yb zulegiert bzw. zudotiert wird. Auch in diesem Legierungsmaterial zeichnen sich die Elemente b) durch hervorragende elektrische und physikalische Eigenschaften aus und bilden dieselben positiven Strukturen aus, wie bereits oben im Detail ausgeführt. Ist der Anteil an Element d) geringer als 1,5 Gew.-% bezogen auf das Gesamtgewicht des Elektrodenmaterials, so ist die elektrische Leitfähigkeit im Elektrodengrundmaterial geringer, da zu wenig Metalloxid des Elements d) gebildet ist, das den Übergangswiderstand in dem Elektrodenmaterial senkt. Ein Anteil an Element d) von mehr als 15 Gew.-% oder sogar 18 Gew.-% hat keinen wesentlichen Einfluss mehr auf die Verbesserung der elektrischen Eigenschaften und die Struktur des Elektrodenmaterials.According to an alternative of the invention, the electrode material forming the spark plug electrode according to the invention comprises:
  • a) nickel as base material and
  • b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb, and
  • d) at least one further element selected from the group consisting of V, Zn and Ti, wherein
the total content of element b) is ≦ 0.5% by weight and preferably ≦ 0.3% by weight, based on the total weight of the electrode material, and wherein the total content of element d) based on the total weight of the electrode material is from 1.5 to 18 Wt .-% and preferably 2 to 15 wt .-% is. This spark plug electrode according to the invention is also characterized by an electrode material whose oxide layer on its surface has an electrical resistance R which is smaller than that defined by the equation given above, so that all the above-mentioned advantages are also achieved with this electrode material. The elements d), ie V, Zn and Ti, integrate themselves particularly homogeneously into a nickel matrix. The electrode material is characterized by a low contact resistance between the oxide layer and the Base electrode material, so that its electrical conductivity is greatly increased. The heat-conducting properties are also excellent, so that wear-resistant material is formed. The electrical properties and also the thermal conductivity of the oxides of the elements V, Zn and Ti are so excellent that preferably even the reactive element b) can be dispensed with. However, it is particularly preferred if at least one further element from the group consisting of Y, Hf, Ce, La, Zr, Ta and Yb is added or added. Also in this alloy material, the elements b) are characterized by excellent electrical and physical properties and form the same positive structures, as already detailed above. If the proportion of element d) is less than 1.5% by weight based on the total weight of the electrode material, the electric conductivity in the electrode base material is lower because too little metal oxide of the element d) is formed, lowering the contact resistance in the electrode material , A content of element d) of more than 15% by weight or even 18% by weight no longer has any significant influence on the improvement of the electrical properties and the structure of the electrode material.

Gemäß einer nicht erfindungsgemäßen Alternative enthält ein Elektrodenmaterial die nachfolgenden Elemente:

  • a) Eisen als Basismaterial und
  • b) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb und
  • e) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus Al, Cr, Ni und Mo, wobei
der Gesamtgehalt an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials ≤0,5 Gew.-% und bevorzugt ≤0,3 Gew.-% beträgt und wobei der Gesamtgehalt an Element e) bezogen auf das Gesamtgewicht des Elektrodenmaterials 1,5 bis 29 Gew.-% und bevorzugt 2 bis 25 Gew.-% beträgt. Auch diese Zündkerzenelektrode zeichnet sich durch ein Elektrodenmaterial aus, dessen an seiner Oberfläche befindliche Oxidschicht einen elektrischen Widerstand R aufweist, der kleiner ist als derjenige, der durch oben angeführte Gleichung definiert wird, so dass alle oben erwähnten Vorteile auch mit diesem Elektrodenmaterial erzielt werden. Während hingegen eine Kombination Nickel mit Aluminium oder auch Chrom nicht zu einem ausreichend niedrigen elektrischen Widerstand führt, weist dieses Elektrodenmaterial das Element Eisen in Kombination mit den Elementen e), also Al, Cr, Ni und Mo auf, wodurch eine sehr stabile und homogene Struktur gebildet wird. Auch die wärmeleitenden Eigenschaften der Oxide und damit der Gesamtlegierung sind ausgezeichnet. Die elektrischen Eigenschaften der Oxide der Elemente Al, Cr, Ni und Mo sind dabei so ausgesprochen gut, dass gegebenenfalls bevorzugt sogar auf das reaktive Element b) verzichtet werden kann. Besonders bevorzugt ist aber, wenn mindestens ein weiteres Element aus der Gruppe bestehend aus Y, Hf, Ce, La, Zr, Ta und Yb zulegiert bzw. zudotiert wird. Auch in diesem Legierungsmaterial zeichnen sich die Elemente b) durch hervorragende elektrische und physikalische Eigenschaften aus und bilden dieselben positiven Strukturen aus, wie bereits oben im Detail ausgeführt. Ist der Anteil an Element e) geringer als 1,5 Gew.-% bezogen auf das Gesamtgewicht des Elektrodenmaterials, so ist die elektrische Leitfähigkeit im Elektrodengrundmaterial geringer, da zu wenig Metalloxid des Elements e) gebildet ist, das den Übergangswiderstand in dem Elektrodenmaterial senkt. Ein Anteil an Element e) von mehr als 25 Gew.-% oder sogar 29 Gew.-% hat keinen wesentlichen Einfluss mehr auf die Verbesserung der elektrischen Eigenschaften und die Struktur des Elektrodenmaterials.According to an alternative not according to the invention, an electrode material contains the following elements:
  • a) iron as base material and
  • b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb and
  • e) at least one further element selected from the group consisting of Al, Cr, Ni and Mo, wherein
the total content of element b) based on the total weight of the electrode material is ≦ 0.5% by weight and preferably ≦ 0.3% by weight and wherein the total content of element e) based on the total weight of the electrode material is from 1.5 to 29 Wt .-% and preferably 2 to 25 wt .-% is. Also, this spark plug electrode is characterized by an electrode material whose oxide layer on its surface has an electric resistance R smaller than that defined by the above-mentioned equation, so that all the above-mentioned advantages are also obtained with this electrode material. Whereas a combination of nickel with aluminum or even chromium does not lead to a sufficiently low electrical resistance, this electrode material has the element iron in combination with the elements e), ie Al, Cr, Ni and Mo, resulting in a very stable and homogeneous structure is formed. The heat-conducting properties of the oxides and thus of the overall alloy are also excellent. The electrical properties of the oxides of the elements Al, Cr, Ni and Mo are so extremely good that possibly optionally even the reactive element b) can be dispensed with. However, it is particularly preferred if at least one further element from the group consisting of Y, Hf, Ce, La, Zr, Ta and Yb is added or added. Also in this alloy material, the elements b) are characterized by excellent electrical and physical properties and form the same positive structures, as already detailed above. If the proportion of element e) is less than 1.5% by weight, based on the total weight of the electrode material, Thus, the electrical conductivity in the electrode base material is lower because too little metal oxide of the element e) is formed, which lowers the contact resistance in the electrode material. A content of element e) of more than 25% by weight or even 29% by weight no longer has any significant influence on the improvement of the electrical properties and the structure of the electrode material.

Die Unteransprüche zeigen bevorzugte Weiterbildungen und Verbesserungen der Erfindung.The dependent claims show preferred developments and improvements of the invention.

Besonders bevorzugt ist es, wenn die sich auf der Oberfläche der Elektrode bildende Oxidschicht eine Wärmeleitfähigkeit von mehr als 6 W/mK und bevorzugt von mehr als 8 W/mK und besonders bevorzugt von mehr als 10 W/mK aufweist, wobei die Wärmeleitfähigkeit bei 20 °C gemessen wird. Wird die Wärme von der oxidhaltigen Elektrodenoberfläche sehr schnell in das Innere der Elektrode abgeleitet, so wird die Bildung einer dicken, stark ausgeprägten und unregelmäßig geformten Oxidschicht an der Elektrodenoberfläche verhindert. Die erfindungsgemäße Zündkerzenelektrode zeichnet sich durch eine extrem dünne und gleichmäßige Oxidschicht aus, so dass die Zündkerzenelektrode über eine ausgezeichnete Stabilität auch im Dauerbetrieb der Zündkerze verfügt. Ist die Wärmeleitfähigkeit der sich bildenden Oxidschicht geringer als 6 W/mK, so entstehen im Funkenplasma lokal hohe Temperaturen, die nicht ausreichend schnell an die Umgebung abgegeben werden, so dass sich gerade an diesen Stellen bevorzugt Oxidschichten abscheiden, so dass die Oxidschichten gerade an diesen Stellen besonders schnell gebildet werden. Hierdurch erhöht sich die Erosions- und Korrosionsneigung des Materials und somit dessen Verschleiß und es kommt verstärkt zu Hitzestaus, was den Verschleiß weiter begünstigt. Weiter bevorzugt weist auch das Elektrodenmaterial eine Wärmeleitfähigkeit von mehr als 6 W/mK auf und besonders bevorzugt sind die Wärmeleitfähigkeiten der Oxidschicht und des Elektrodenmaterials gleich.It is particularly preferred if 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. When the heat from the oxide-containing electrode surface is dissipated very rapidly into the interior of the electrode, the formation of a thick, strongly shaped and irregularly shaped oxide layer on the electrode surface is prevented. 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. If 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. More preferably, 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.

In einer bevorzugten Ausführungsform hat die an der Oberfläche des Elektrodenmaterials gebildete Oxidschicht eine Dicke von weniger als 10 µm bzw. weist besonders bevorzugt eine Dicke in einem Bereich von 5 bis 8 µm auf. Erfindungsgemäß werden also solche Materialien miteinander zu einem Elektrodenmaterial kombiniert, die sich durch eine reduzierte Neigung zur Bildung von Oxiden unter den vorherrschenden Extrembedingungen auszeichnen. Ist die sich bildende Oxidschicht 10 µm oder stärker, so wirkt die Oxidschicht sowohl gegenüber Wärme als auch in Bezug auf die Leitfähigkeit isolierend. Dies fördert wiederum die Bildung weiterer Oxide und damit auch die Verschleißrate des Elektrodenmaterials. Je geringer also die Dicke der Oxidschicht ist, desto beständiger ist das Material in Bezug auf Funkenerosion und insbesondere oxidative Korrosion.In a preferred embodiment, 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 μm 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.

Besonders bevorzugt ist es, wenn das Elektrodenmaterial

  • a) Nickel als Basismaterial und
  • b) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb und
  • d) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus V, Zn und Ti enthält, wobei
der Gesamtgehalt an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials ≤ 0,3 Gew.-% beträgt und wobei der Gesamtgehalt an Element d) bezogen auf das Gesamtgewicht des Elektrodenmaterials 1,5 bis 18 Gew.-% und bevorzugt 2 bis 15 Gew.-% beträgt und wobei der Anteil an Sauerstoff in dem Elektrodenmaterial weniger als 0,003 Gew.-% bezogen auf das Gesamtgewicht des Elektrodenmaterials beträgt. Unter Sauerstoff im Elektrodenmaterial wird in Bezug auf die vorliegende Erfindung nicht nur jeglicher gasförmig oder gelöst vorliegende molekulare Sauerstoff verstanden, sondern auch jeglicher in Form von Oxiden gebundene Sauerstoff. Das bedeutet mit anderen Worten, dass das erfindungsgemäße Elektrodenmaterial und damit auch eine daraus hergestellte Zündkerzenelektrode vor Inbetriebnahme der Zündkerzenelektrode, d.h., ohne Oxidschicht, einen Sauerstoffanteil von weniger als 0,003 Gew.-% aufweist. Es wurde gefunden, dass wenn der Sauerstoffanteil vor Inbetriebnahme der Zündkerzenelektrode über der Grenze von 0,003 Gew.-% liegt, insbesondere die sogenannten reaktiven metallischen Elemente Y, Hf, Ce, La, Zr, Ta und Yb, also die Elemente b), bereits zu einem großen Anteil in Form ihrer Oxide vorliegen. Diese Oxide der reaktiven Elemente liegen somit überwiegend als Oxidpartikel oder oxidische intermetallische Phasen vor und sind damit aus der Legierungsmatrix ausgeschieden. Sie können also bei Inbetriebnahme der Zündkerze keinen Sauerstoff mehr binden und tragen damit nicht mehr zur Erhöhung der Oxidationsbeständigkeit des Legierungsmaterials bei. Ferner leidet hierunter auch die Erosionsbeständigkeit und Stabilität des Materials, so dass die Verschleißrate eines solchen Elektrodenmaterials gegenüber einem solchen, gemäß der vorliegenden Erfindung, deutlich erhöht ist. Je geringer der initiale Sauerstoffgehalt vor Inbetriebnahme der Zündkerzenelektrode ist, desto geringer ist auch der Anteil an destabilisierenden Oxidpartikeln, Oxidaggregaten oder sogar oxidischen Phasen, desto besser ist das Material gegenüber Korrosion und Funkenerosion bei Inbetriebnahme der Zündkerze geschützt. Der Grenzwert von 0,003 Gew.-% für den Sauerstoffanteil scheint hierbei ein Schwellenwert zu sein, so dass Sauerstoffgehalte unter diesem Wert zu einem guten und dauerhaft beständigem Elektrodenmaterial führen. Es wurde gefunden, dass dieser geringe Sauerstoffgehalt besonders wichtig ist für die mindestens ein Element c) enthaltende Nickelbasislegierung. Bei Nickelbasislegierungen, die mindestens eines der Elemente d) enthalten oder aber bei besagter Eisenbasislegierung scheint die Anfälligkeit des Materials gegenüber Oxidation geringer ausgebildet zu sein, so dass auch höhere Sauerstoffgehalte im Legierungsmaterial tolerierbar sind. Der Sauerstoffgehalt in dem Elektrodenmaterial kann dabei durch Heißextraktion einer Probe des Legierungsmaterials nach herkömmlichen Methoden bestimmt werden.It is particularly preferred if the electrode material
  • a) nickel as base material and
  • b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb and
  • d) at least one further element selected from the group consisting of V, Zn and Ti contains, wherein
the total content of element b) is ≦ 0.3% by weight, based on the total weight of the electrode material, and wherein the total content of element d) based on the total weight of the electrode material 1.5 to 18 wt .-% and preferably 2 to 15 wt .-% and wherein the proportion of oxygen in the electrode material less than 0.003 wt .-% based on the Total weight of the electrode material is. By oxygen in the electrode material is meant, with reference to the present invention, not only any gaseous or dissolved molecular oxygen, but also any oxygen bound in the form of oxides. In other words, this means that the electrode material according to the invention and thus also a spark plug electrode produced therefrom before starting the spark plug electrode, ie, without an oxide layer, has an oxygen content of less than 0.003% by weight. It has been found that if the oxygen content before the start of the spark plug electrode is above the limit of 0.003% by weight, in particular the so-called reactive metallic elements Y, Hf, Ce, La, Zr, Ta and Yb, ie elements b), already to a large extent in the form of their oxides. These oxides of the reactive elements are thus predominantly present as oxide particles or oxidic intermetallic phases and are thus eliminated from the alloy matrix. So they can no longer bind oxygen when commissioning the spark plug and thus no longer contribute to increase the oxidation resistance of the alloy material. Furthermore, this also suffers from the erosion resistance and stability of the material, so that the wear rate of such an electrode material compared to such, according to the present invention, is significantly increased. The lower the initial oxygen content before starting the spark plug electrode, the lower the proportion of destabilizing oxide particles, oxide aggregates or even oxidic phases, the better the material is protected against corrosion and spark erosion when the spark plug is put into operation. The limit of 0.003 wt .-% for the oxygen content seems to be a threshold, so that oxygen levels below this value lead to a good and durable electrode material. It has been found that this low oxygen content is particularly important for the nickel-based alloy containing at least one element c). For nickel-based alloys containing at least one of elements d) or for said iron-based alloy, the susceptibility of the material to oxidation appears to be lower, so that higher oxygen contents in the alloy material are tolerable. The oxygen content in the electrode material can be determined by hot extraction of a sample of the alloy material by conventional methods.

Besonders bevorzugt liegt der Anteil an Sauerstoff in dem Elektrodenmaterial bei maximal 0,002 Gew.-%. Unterhalb dieser Grenze ist die Ausbildung von metallischen Oxiden in dem Elektrodenmaterial vor Inbetriebnahme des Zündkerze so gering, dass die Elektrode auch bei hohen Temperaturen optimal vor Oxidation und damit vor Destabilisierung durch Korrosion und Erosion geschützt ist.Particularly preferably, the proportion of oxygen in the electrode material is at most 0.002 wt .-%. Below this limit, 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.

Als weiterhin vorteilhaft hat sich herausgestellt, wenn vor Inbetriebnahme der Zündkerze der Gesamtanteil an oxidierten Elementen b) in dem Elektrodenmaterial bezogen auf das Gesamtgewicht des Elektrodenmaterials geringer ist als 15 Mol.-% und bevorzugt geringer als 10 Mol.-%. Liegt der Anteil an oxidischem Element b) vor Inbetriebnahme der Elektrode höher als 10 Mol.-% oder sogar 15 Mol.-%, so ist dessen Anteil bereits so hoch, dass das reaktive Element b) nicht mehr ausreichend zur Stabilisierung des Elektrodenmaterials bei Funkenschlag beitragen kann, denn es liegt bereits in seiner oxidierten Form vor und kann somit keinen weiteren Sauerstoff binden. Damit unterliegt nun das Basismaterial und insbesondere das Nickelbasismaterial, dem mindestens eines der Elemente c) zulegiert ist, einer stärkeren Oxidation und das Elektrodenmaterial verschleißt zusehends. Je höher der Anteil an oxidiertem Element b), desto geringer ist der stabilisierende Effekt, den es auf das Elektrodenmaterial ausüben kann. Je geringer der Anteil an oxidiertem Element b), desto höher ist hingegen folglich die stabilisierende Wirkung, die das reaktive Element in dem Nickelgefüge bewirkt.As further advantageous has been found, if before commissioning of the spark plug, 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. As a result, 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. The higher the proportion of oxidized element b), the lower the stabilizing effect that it can exert on the electrode material. On the other hand, the lower the proportion of oxidized element b), the higher the stabilizing effect which the reactive element brings about in the nickel structure.

Als besonders nachteilig in Bezug auf die Stabilität des Elektrodenmaterials, also dessen Oxidations- sowie Korrosions- und Erosionsbeständigkeit, hat sich die Bildung von intermetallischen Zweitphasen gezeigt. Intermetallische Zweitphasen bilden sich, wie bereits ausgeführt, insbesondere dann, wenn große Anteile an reaktivem Element b) in dem Legierungsmaterial vorliegen, die dann aufgrund von Unverträglichkeiten mit dem Basismaterial nicht in gelöster Form, sondern in Form einer intermetallischen Zweitphase vorliegen. Diese intermetallischen Zweitphasen führen zur Destabilisierung des Elektrodenmaterials, da sie sich nicht homogen in die Legierungsmatrix einfügen, sondern aus dieser ausgeschieden vorliegen, so dass die Bindungen zwischen den Legierungselementen lokal und auch über weitere Bereiche reduziert werden. Das Legierungsgefüge wird durch intermetallische Zweitphasen gestört. Damit ist der elektrische Widerstand des Materials erhöht und folglich insbesondere die Wärmeleitfähigkeit und die elektrische Leitfähigkeit des Materials reduziert, bzw. werden diese inhomogen über den gesamten Bereich, so dass lokal hohe Temperaturschwankungen auftreten können, die das Material an diesen Stellen aufweiten und zu einem Abplatzen des Materials führen können. Dies fördert den Verschleiß des Elektrodenmaterials. Die Störung des Legierungsgefüges ist besonders groß, wenn der Anteil an intermetallischen Phasen in dem Elektrodenmaterial 15 Mol.-% oder mehr beträgt. Es wurde gefunden, dass intermetallische Phasen, mit einem Anteil von weniger als 15 Mol.-% und bevorzugt von weniger als 10 Mol.-% bezogen auf die Gesamtzusammensetzung noch tolerierbar sind, so dass sich deren destabilisierende Wirkungen nicht essentiell auswirken und die Legierungsmatrix ausreichend stabil gebildet ist. Je geringer der Anteil an intermetallischen Phasen, desto stabiler ausgeprägt ist das Legierungsgefüge. Besonders bevorzugt ist es deshalb, wenn im Wesentlichen keine intermetallischen Phasen im Elektrodenmaterial vorliegen.The formation of 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. Thus, 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. This promotes the wear of the electrode 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.

Das erfindungsgemäße Elektrodenmaterial für Zündkerzenelektroden kann sowohl für die Herstellung der Mittel-, wie auch für die Masseelektrode wie auch beider Elektroden gleichzeitig, verwendet werden. Die daraus gebildeten Zündkerzen liegen in Bezug auf ihre Standzeiten in etwa in demselben Bereich wie sie mit Edelmetallmaterialzündkerzen erzielt werden, ohne jedoch Edelmetall zu enthalten. Während hingegen die Standzeiten der herkömmlichen edelmetallfreien Zündkerzen lediglich etwa bis 60.000 km betragen, liegen die Standzeiten der erfindungsgemäßen Zündkerzenelektroden bedeutend höher, d.h., im Bereich von 90.000 km. Dies erzeugt eine wesentlich bessere Akzeptanz auf dem Markt und ist sowohl aus umwelttechnischen wie auch aus wirtschaftlichen Gründen von Vorteil.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. On the other hand, while 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.

Erfindungsgemäß werden Zündkerzen bereitgestellt, die mindestens eine erfindungsgemäße Zündkerzenelektrode umfassen, und die somit eine verbesserte Oxidations- und Korrosionsbeständigkeit, sowie Funkenerosionsbeständigkeit und Wärmeleitfähigkeit aufweisen.According to the invention, spark plugs are provided 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.

Die Erfindung betrifft eine Zündkerzenelektrode, gekennzeichnet durch ein Elektrodenmaterial, das aus

  1. a) Nickel als Basismaterial,
  2. b) mindestens einem weiteren Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb, und
  3. c) mindestens einem weiteren Element ausgewählt aus der Gruppe bestehend aus: Si, Na, K, Li, Ti, Ag und Cu besteht, wobei
der Gesamtanteil an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials 0,1 bis 0,3 Gew.-%, bevorzugt 0,1 bis 0,2 Gew.-% und besonders bevorzugt 0,13 bis 0,17 Gew.-% beträgt,
wobei der Gesamtanteil an Element c) bezogen auf das Gesamtgewicht des Elektrodenmaterials 0,5 bis 3 Gew.-% und bevorzugt 1,0 bis 2,5 Gew.-% beträgt, und wobei
das Elektrodenmaterial bezogen auf das Gesamtgewicht des Elektrodenmaterials einen Sauerstoffgehalt von maximal 0,003 Gew.-% und insbesondere 0,002 Gew.-% aufweist.
Das vorstehend definierte Elektrodenmaterial weist, bezogen auf das Gesamtgewicht des Elektrodenmaterials, einen Sauerstoffgehalt von weniger als 0,003 Gew.-% auf. In dieser Ausführungsform ist das Elektrodenmaterial sowohl in struktureller als auch in chemisch-physikalischer Hinsicht optimal ausgebildet. Es weist einen kleinen elektrischen Widerstand auf, ist gut wärmeleitend und damit oxidationsstabil und ferner resistent gegenüber Funkenerosion und Korrosion, insbesondere auch bei erhöhten Temperaturen, wie sie z.B. im Motorraum eines Fahrzeugs an Zündkerzen vorliegen können. Das Material lässt sich hervorragend verarbeiten und ist in sich homogen. Eine sich bildende Oxidschicht an der Oberfläche der Elektrode ist aufgrund der gut abgestimmten Materialien stabil aber ausreichend dünn, um die Wärmeleitfähigkeit und elektrische Leitfähigkeit nicht wesentlich nachteilig zu beeinflussen. Das Material ist dauerhaft, also auch bei langen Standzeiten stabil, und zeichnet sich durch eine extrem niedrige Verschleißrate aus.The invention relates to a spark plug electrode, characterized by an electrode material, the
  1. a) nickel as base material,
  2. b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb, and
  3. c) at least one further element selected 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 0.1 to 0.3 wt .-%, preferably 0.1 to 0.2 wt .-% and particularly preferably 0.13 to 0.17 wt .-% is,
wherein the total content of element c) based on the total weight of the electrode material is 0.5 to 3 wt .-%, and preferably 1.0 to 2.5 wt .-%, and wherein
the electrode material based on the total weight of the electrode material has an oxygen content of at most 0.003 wt .-% and in particular 0.002 wt .-%.
The above-defined electrode material has, based on the total weight of the electrode material, an oxygen content of less than 0.003 wt .-%. In this embodiment, the electrode material is optimally formed in both structural and chemical-physical terms. It has a low electrical resistance, is good thermal conductivity and thus stable to oxidation and also resistant to spark erosion and corrosion, especially at elevated temperatures, such as may be present in the engine compartment of a vehicle to spark plugs. The material can be processed excellently and is homogeneous in itself. A forming oxide layer on the surface of the electrode is stable but sufficiently thin due to the well-tuned materials so as not to significantly adversely affect the thermal conductivity and electrical conductivity. The material is durable, therefore stable even with long service life, and is characterized by an extremely low wear rate.

Weiterhin betrifft die Erfindung eine Zündkerzenelektrode, gekennzeichnet durch ein Elektrodenmaterial, enthaltend:

  • a) Nickel als Basismaterial und
  • b) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus: Y, Hf, Ce, La, Zr, Ta und Yb, und
  • d) mindestens ein weiteres Element ausgewählt aus der Gruppe bestehend aus V, Zn und Ti, wobei
der Gesamtgehalt an Element b) bezogen auf das Gesamtgewicht des Elektrodenmaterials ≤0,5 Gew.-% und bevorzugt ≤0,3 Gew.-% beträgt und wobei
der Gesamtgehalt an Element d) bezogen auf das Gesamtgewicht desFurthermore, the invention relates to a spark plug electrode, characterized by an electrode material comprising:
  • a) nickel as base material and
  • b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb, and
  • d) at least one further element selected from the group consisting of V, Zn and Ti, wherein
the total content of element b) is ≦ 0.5% by weight and preferably ≦ 0.3% by weight, based on the total weight of the electrode material, and wherein
the total content of element d) based on the total weight of

Elektrodenmaterials 1,5 bis 18 Gew.-% und bevorzugt 2 bis 15 Gew.-% beträgt. Es sei angemerkt, dass der Wert für den Gesamtgehalt an Element b) auch Null sein kann.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.

Das erfindungsgemäße Elektrodenmaterial der zweiten aufgeführten Alternative weist dabei besonders bevorzugt, bezogen auf das Gesamtgewicht des Elektrodenmaterials, einen Sauerstoffgehalt von maximal 0,003 Gew.-%, und das erfindungsgemäße Elektrodenmaterial gemäß der ersten und der zweiten aufgeführten Alternative weist dabei insbesondere einen Sauerstoffgehalt von maximal 0,002 Gew.-% auf.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.

Zeichnungdrawing

Nachfolgend werden bevorzugte Ausführungsbeispiele der Erfindung unter Bezugnahme auf die begleitende Zeichnung beschrieben.

Figur 1
zeigt einen Querschnitt durch eine erfindungsgemäße Zündkerzenelektrode,
Figur 2
zeigt einen Querschnitt durch eine Zündkerzenelektrode gemäß dem Stand der Technik,
Figur 3
ist eine logarithmische Darstellung, die den elektrischen Widerstand von Elektroden in Abhängigkeit von der Temperatur zeigt,
Figur 4
zeigt Verschleißreduktionen an Zündkerzenelektrode in Abhängigkeit der Zusammensetzung, und
Figur 5
ist eine Arrhenius-Auftragung, die den elektrischen Widerstand von Elektroden in Abhängigkeit von der Temperatur zeigt.
Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
FIG. 1
shows a cross section through a spark plug electrode according to the invention,
FIG. 2
shows a cross section through a spark plug electrode according to the prior art,
FIG. 3
is a logarithmic plot showing the electrical resistance of electrodes as a function of temperature,
FIG. 4
shows wear reductions at spark plug electrode depending on the composition, and
FIG. 5
is an Arrhenius plot showing the electrical resistance of electrodes as a function of temperature.

Beschreibung der AusführungsformDescription of the embodiment

Nachfolgend wird unter Bezugnahme auf die Figuren 1, 3, 4 und 5 eine Zündkerzenelektrode gemäß einen Ausführungsbeispiel der Erfindung beschrieben.The following is with reference to the FIGS. 1 . 3 . 4 and 5 a spark plug electrode according to an embodiment of the invention described.

Veranschaulicht werden die Vorteile des erfindungsgemäßen Elektrodenmaterials bzw. der erfindungsgemäßen Zündkerze durch einen Vergleich der Figuren 1 und 2. Figuren 1 und 2 sind mikroskopische Aufnahmen mit einem Rasterelektronenmikroskop in 500facher Vergrößerung eines Teils einer Elektrode. In den Figuren 1 und 2 bezeichnet das Bezugszeichen 1 das jeweilige Elektrodengrundmaterial. Bezugszeichen 2 bezeichnet die Oberfläche des Elektrodenmaterials, auf der sich eine Oxidschicht 3 gebildet hat. Darüber befindet sich ein Gasraum 4, in den die Elektrode eingebracht ist.The advantages of the electrode material according to the invention or of the spark plug according to the invention are illustrated by comparing the Figures 1 and 2. Figures 1 and 2 are micrographs with a scanning electron microscope at 500x magnification of part of an electrode. In the Figures 1 and 2 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.

Figur 1 ist eine Mikroskopaufnahme einer erfindungsgemäßen Nickellegierung, die 0,2 Gew.-% Hafnium als Element b) und 1 Gew.-% Silicium als Element c) enthält, sowie einem Sauerstoffgehalt von weniger als 0,0015 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Elektrodenmaterials. Deutlich zu erkennen ist, dass die Oxidschicht 3 in dem erfindungsgemäßen Elektrodenmaterial sehr dünn und gleichmäßig ausgebildet und im Durchschnitt etwa 5 bis 8 µm dick ist. Dies zeigt deutlich den positiven Einfluss der reaktiven Elemente b) auf die Ausbildung der oxidischen Schutzschicht, die erfindungsgemäß dünn und stabil ausgeprägt ist. Oxidierte Bereiche im Inneren des Elektrodenmaterials sind praktisch nicht vorhanden. 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. It can be clearly seen that the oxide layer 3 in the electrode material according to the invention is very thin and uniform and on average about 5 to 8 μm 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.

Dies zeigt die Stabilität und damit Korrosions- und Erosionsbeständigkeit des erfindungsgemäßen Elektrodenmaterials.This shows the stability and thus corrosion and erosion resistance of the electrode material according to the invention.

Figur 2 zeigt eine Mikroskopaufnahme einer herkömmlichen Nickellegierung, die 1 Gew.-% Al, 1 Gew.-% Si und 0,2 Gew.-% Y sowie einen Sauerstoffgehalt von 0,0033 Gew.-% aufweist. Hier ist die an der Oberfläche der Elektrode befindliche Oxidschicht 3 ungleichmäßig und porös ausgebildet und zeigt weitläufig große Teilbereiche 6, in denen sich die oxidischen Bereiche bis tief ins Innere des Elektrodenmaterials ziehen. Die an der Oberfläche der Elektrode gebildete Oxidschicht ist bedeutend dicker ausgebildet und liegt im Mittel zwischen 12 und 20 µm. Diese destabilisierenden Effekte sind direkt auf die Zusammensetzung des Elektrodenmaterials zurückzuführen. Hier ist das reaktive Element b) zwar in der optimalen Konzentration, jedoch nicht in gelöstem Zustand, sondern in Form isolierter Aggregate bzw. intermetallische Zweitphasen 5 vorhanden, die aus der Nickelmatrix ausgeschieden sind. So ist das Nickelgefüge fehlerhaft und der umgebende Sauerstoff oxidiert zum Einen das Nickel an der Elektrodenoberfläche bedeutend stärker und zum Anderen dringt der Sauerstoff ins Elektrodeninnere ein und oxidiert hier sowohl weiteres Nickel als auch die intermetallischen Zweitphasen aus reaktivem Element b). Das Elektrodenmaterial zeichnet sich folglich durch eine hohe Verschleißrate aus. 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 .-%. Here, 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. These destabilizing effects are directly attributable to the composition of the electrode material. Here, 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. Thus, 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.

Figur 3 zeigt Messergebnisse des elektrischen Widerstands R in Ω von Oxidschichten zweier Elektroden logarithmisch in Abhängigkeit der Temperatur T in °C. Der obere Kurvenverlauf 10, dessen Messpunkte durch Quadrate gezeichnet sind, wurde an der Elektrode des Standes der Technik (Figur 2) gemessen. Die darunter liegende Kurve 11, deren Messwerte mit Kreuzen gekennzeichnet sind, ist diejenige der erfindungsgemäßen Elektrode (Figur 1). Hier ist deutlich zu erkennen, dass durch die erfindungsgemäße dünnere oxidische Schutzschicht an der Elektrodenoberfläche der elektrische Widerstand R im gesamten Temperaturspektrum bedeutend geringer ist als in einem herkömmlichen Elektrodenmaterial. Das erfindungsgemäße Elektrodenmaterial weist also hervorragende elektrische Leitfähigkeiten auf, ohne dass dabei Edelmetall im Elektrodenmaterial verwendet wurde. FIG. 3 shows measurement results of the electrical resistance R in Ω of oxide layers of two electrodes logarithmically as a function of the temperature T in ° C. The upper curve 10, whose measuring points are drawn by squares, was applied to the electrode of the prior art ( FIG. 2 ). The underlying curve 11, whose measured values are marked with crosses, is that of the electrode according to the invention ( FIG. 1 ). Here it can clearly be seen that 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.

Figur 4 zeigt verschiedene Verschleißraten von Elektrodenmaterialien unterschiedlicher Zusammensetzung, wie sie in der nachfolgenden Übersicht zusammengestellt sind. In Figur 4 ist dabei der Verschleiß V in µm3 pro Funke für die verschiedenen Elektrodenmaterialien dargestellt. Dabei stellen die Rauten die Mittelwerte der gemessenen Werte dar und die vertikalen Striche deren Streuung. Elektrodenmaterial A erfindungsgemäß B Standard Reaktives Element b) Hf Y Menge an reaktivem Element b) in Gew.-% 0,2 0,2 Element c) Si Si Menge an Element c) in Gew.-% 1 1 Sauerstoffgehalt in Gew.-% 0,0015 0,0033 Basismaterial Ni Ni weitere Elemente --- Al(1 Gew.-%) FIG. 4 shows different wear rates of electrode materials of different composition, as summarized in the following overview. In FIG. 4 In this case, the wear V in μm 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)

Gut zu erkennen ist, dass das erfindungsgemäße Elektrodenmaterial eine Reduktion des Verschleißes von etwa 25 % bewirkt.It can be clearly seen that the electrode material according to the invention causes a reduction of the wear of about 25%.

In Figur 5 ist eine Arrhenius-Auftragung, welche den elektrischen Widerstand R über der Temperatur T' dargestellt ist, wobei die Temperatur T' durch den Quotienten 1000/T in K-1 dargestellt ist. Hierdurch kann die Gleichung logR = a+b* 1000/T definiert werden, wobei a zwischen 0,6 und 0,8 liegt, b zwischen 3,1 und 3,2 liegt und T die entsprechende Elektrodentemperatur in Kelvin ist. Wie aus Figur 5 deutlich ersichtlich ist, ist der elektrische Widerstand der Oxidschicht der erfindungsgemäßen Zündkerzenelektrode (Kurve 13) deutlich kleiner als der Widerstand der herkömmlichen Oxidschichten von Elektroden ohne Edelmetalle (Kurve 12).In 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. Hereby, the equation logR = a + b * 1000 / T can be defined, where a is between 0.6 and 0.8, b is between 3.1 and 3.2, and T is the corresponding electrode temperature in Kelvin. How out FIG. 5 is clearly seen, 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).

Claims (8)

  1. Spark plug electrode produced from an electrode material, wherein an oxide layer present on a surface of the electrode material has an electrical resistance R which is less than or equal to that defined by the below equation: logR = a + b * 1000 T ,
    Figure imgb0003
     where 0.6 ≤ a ≤ 0.8, in particular a is 0.7,
    where 3.1 ≤ b ≤ 3.3, in particular b is 3.2, and where T is the temperature in Kelvin,
    wherein the electrode material consists of
    a) nickel as 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 further element selected from the group consisting of: Si, Na, K, Li, Ti, Ag and Cu, wherein
    the total proportion of element b) in relation to the total weight of the electrode material is 0.1 to 0.3% by weight, preferably 0.1 to 0.2% by weight and particularly preferably 0.13 to 0.17% by weight,
    wherein the total proportion of element c) in relation to the total weight of the electrode material is 0.5 to 3% by weight and preferably 1.0 to 2.5% by weight, and
    wherein the electrode material has an oxygen content of at most 0.003% by weight and in particular 0.002% by weight, in relation to the total weight of the electrode material
    or
    wherein the electrode material contains
    a) nickel as base material and
    b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb, and
    d) at least one further element selected from the group consisting of: V, Zn and Ti, wherein
    the total content of element b) in relation to the total weight of the electrode material is ≤ 0.3% by weight, and wherein
    the total content of element d) in relation to the total weight of the electrode material is 1.5 to 18% by weight and preferably 2 to 15% by weight.
  2. Spark plug electrode according to Claim 1, characterized in that the oxide layer on the surface of the electrode material has a thermal conductivity of more than 6 W/mK and preferably 8 W/mK and particularly preferably 10 W/mk at 20°C.
  3. Spark plug electrode according to either of the preceding claims, characterized in that the oxide layer has a thickness of less than 10 µm and preferably a thickness in a range of 5 to 8 µm.
  4. Spark plug electrode according to one of the preceding claims, characterized in that the electrode material contains
    a) nickel as base material and
    b) at least one further element selected from the group consisting of: Y, Hf, Ce, La, Zr, Ta and Yb, and
    d) at least one further element selected from the group consisting of: V, Zn and Ti, wherein
    the total content of element b) in relation to the total weight of the electrode material is ≤ 0.3% by weight, and wherein
    the total content of element d) in relation to the total weight of the electrode material is 1.5 to 18% by weight and preferably 2 to 15% by weight and wherein the electrode material has an oxygen content of at most 0.003% by weight and in particular 0.002% by weight, in relation to the total weight of the electrode material.
  5. Spark plug electrode according to Claim 1, characterized in that the total proportion of oxidized element b) in the electrode material in relation to the total weight of the electrode material is less than 15 mol% and preferably less than 10 mol%.
  6. Spark plug electrode according to one of the preceding claims, characterized in that the proportion of intermetallic phases in the electrode material in relation to the overall composition of the electrode material is less than 15 mol% and preferably less than 10 mol%.
  7. Spark plug electrode according to one of the preceding claims, characterized in that the electrode material contains essentially no intermetallic phases.
  8. Spark plug, comprising at least one spark plug electrode according to one of the preceding claims.
EP10752780.6A 2009-10-26 2010-09-06 Spark plug electrode produced from improved electrode material Active EP2514052B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009046005A DE102009046005A1 (en) 2009-10-26 2009-10-26 Spark plug electrode made of improved electrode material
PCT/EP2010/063021 WO2011054561A1 (en) 2009-10-26 2010-09-06 Spark plug electrode produced from improved electrode material

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

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JP (1) JP5826182B2 (en)
CN (1) CN102598443B (en)
BR (1) BR112012010819A2 (en)
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WO (1) WO2011054561A1 (en)

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Publication number Priority date Publication date Assignee Title
DE102011007532A1 (en) * 2011-04-15 2012-10-18 Robert Bosch Gmbh A spark plug electrode material and spark plug, and a method of manufacturing the spark plug electrode material
DE102011007496A1 (en) * 2011-04-15 2012-10-18 Robert Bosch Gmbh A spark plug electrode material and spark plug, and a method of manufacturing the spark plug electrode material and an electrode for the spark plug
JP6065580B2 (en) 2012-12-25 2017-01-25 住友電気工業株式会社 Evaluation test method for internal combustion engine materials
JP6438249B2 (en) * 2014-09-16 2018-12-12 株式会社東芝 Electrode material, electrode layer using the same, battery, and electrochromic device
JP6312723B2 (en) 2016-01-18 2018-04-18 日本特殊陶業株式会社 Spark plug

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EP1065290A1 (en) † 1999-06-30 2001-01-03 Sumitomo Metal Industries, Ltd. Heat resistant nickel base alloy
JP2007092139A (en) † 2005-09-29 2007-04-12 Hitachi Metals Ltd Electrode material for spark plug
US20080050264A1 (en) † 2006-08-28 2008-02-28 Federal-Mogul World Wide, Inc. Ignition Device Electrode Composition
JP2009245640A (en) † 2008-03-28 2009-10-22 Ngk Spark Plug Co Ltd Spark plug

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JPS5185052A (en) * 1975-01-08 1976-07-26 Hitachi Ltd TENKAPURAGUDENKYOKUYONITSUKERUGOKIN
US7323811B2 (en) * 2001-08-23 2008-01-29 Federal-Mogul Ignition (U.K.) Limited Noble metal tip for spark plug electrode and method of making same
DE10224891A1 (en) * 2002-06-04 2003-12-18 Bosch Gmbh Robert Nickel alloy suitable for internal combustion engine spark plug electrodes, contains silicon and aluminum with yttrium, hafnium or zirconium
JP4699867B2 (en) * 2004-11-04 2011-06-15 日立金属株式会社 Spark plug electrode material
WO2008013159A1 (en) * 2006-07-25 2008-01-31 Tanaka Kikinzoku Kogyo K.K. Noble metal alloy for spark plug and method for producing and processing the same
JP4413951B2 (en) * 2007-07-06 2010-02-10 日本特殊陶業株式会社 Spark plug

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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 (en) † 1998-01-28 1999-08-04 Ngk Spark Plug Co., Ltd Spark plug with built-in resistor
EP1065290A1 (en) † 1999-06-30 2001-01-03 Sumitomo Metal Industries, Ltd. Heat resistant nickel base alloy
JP2007092139A (en) † 2005-09-29 2007-04-12 Hitachi Metals Ltd Electrode material for spark plug
US20080050264A1 (en) † 2006-08-28 2008-02-28 Federal-Mogul World Wide, Inc. Ignition Device Electrode Composition
JP2009245640A (en) † 2008-03-28 2009-10-22 Ngk Spark Plug Co Ltd Spark plug

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JP2013508557A (en) 2013-03-07
CN102598443A (en) 2012-07-18
EP2514052B1 (en) 2015-02-25
BR112012010819A2 (en) 2017-12-19
DE102009046005A1 (en) 2011-04-28
JP5826182B2 (en) 2015-12-02
EP2514052A1 (en) 2012-10-24
WO2011054561A1 (en) 2011-05-12
CN102598443B (en) 2015-05-06

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