EP2582854B1 - Alliage à base de nickel - Google Patents

Alliage à base de nickel Download PDF

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Publication number
EP2582854B1
EP2582854B1 EP11755241.4A EP11755241A EP2582854B1 EP 2582854 B1 EP2582854 B1 EP 2582854B1 EP 11755241 A EP11755241 A EP 11755241A EP 2582854 B1 EP2582854 B1 EP 2582854B1
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max
content
mass
alloy
alloy according
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German (de)
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EP2582854A2 (fr
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Heike Hattendorf
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VDM Metals GmbH
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VDM Metals 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
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • 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
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W

Definitions

  • the invention relates to a nickel-based alloy.
  • Nickel-base alloys are used inter alia to produce electrodes of ignition elements for internal combustion engines. These electrons are exposed to temperatures between 400 ° C and 950 ° C. In addition, the atmosphere changes between reducing and oxidizing conditions. This produces a material destruction or loss due to high-temperature corrosion in the surface region of the electrodes. The generation of the spark leads to a further load (spark erosion). Temperatures of several 1000 ° C occur at the base of the spark, and currents of up to 100 A flow in the first nanoseconds during a breakthrough. With each flashover, a limited volume of material in the electrodes is melted and partially vaporized, producing a loss of material.
  • nickel alloys have a good potential to fulfill this property spectrum. They are inexpensive compared to precious metals, show no phase transformations to the melting point, such as cobalt or iron, are relatively insensitive to carburizing and Nitriding, have good heat resistance, good corrosion resistance and are easy to form and weld.
  • Wear by high temperature corrosion can be determined by mass change measurements as well as by metallographic analysis after aging at given test temperatures.
  • a generic nickel alloy consisting of about 0.2 to 3% Si, about 0.5% or less Mn, at least two metals selected from the group consisting of about 0.2 to 3% Cr, about 0.2 up to 3% Al and about 0.01 to 1% Y, balance nickel.
  • a nickel-based alloy which comprises 1.8 to 2.2% silicon, 0.05 to 0.1% yttrium and / or hafnium and / or zirconium, 2 to 2.4% aluminum, balance nickel.
  • Such alloys can be processed only in difficult conditions with respect to the high aluminum and silicon contents and are therefore not very suitable for large-scale industrial use.
  • a nickel-base alloy comprising 1.5 to 2.5% silicon, 1.5 to 3% aluminum, 0 to 0.5% manganese, 0.5 to 0.2% titanium is proposed in combination with 0.1 to 0.3% zirconium, wherein the zirconium can be replaced in whole or in part by the double mass hafnium.
  • a nickel-base alloy comprising 1.2 to 2.0% aluminum, 1.2 to 1.8% silicon, 0.001 to 0.1% carbon, 0.001 to 0.1% sulfur, and 0.1% or less chromium , maximum 0.01% manganese, maximum 0.1% Cu, maximum 0.2% iron, 0.005 to 0.06% magnesium, maximum 0.005% lead 0.05 to 0.15% Y and 0.05 to 0, 10% hafnium or lanthanum or 0.05 to 0.10% each hafnium and lanthanum, balance nickel and manufacturing-related impurities.
  • T1 has a negative mass change from the beginning. Ie. Parts of the oxide that formed during the oxidation have flaked off the sample, so that the mass loss due to oxide spalling is greater than the mass increase due to oxidation. This is unfavorable since the protective layer formation at the chipped areas must always start again. The behavior of T1 is more favorable. There, the first 192 hours outweigh the mass increase by oxidation. Only then is the mass increase due to spalling greater than the mass increase due to oxidation, with the mass loss of T2 being significantly lower than that of T1. Ie.
  • the aim of the subject invention is to provide a nickel-based alloy, which leads to an increase in the life of components made therefrom, which by raising the spark erosion and corrosion resistance at the same time good formability and weldability (workability) can be brought.
  • the alloy may further include calcium at levels between 0.0002 and 0.06%.
  • the alloy may be added zirconium at a content of 0.03 to 0.15.
  • cerium with a content of 0.03 to 0.15 is possible.
  • lanthanum may be added at a level of 0.03 to 0.15%.
  • the alloy can contain Ti up to max. 0.15% included.
  • the copper content is limited to max. 0.50% limited, preferably it is max. 0.20%
  • the nickel-based alloy according to the invention is preferably usable as a material for electrodes of ignition elements of internal combustion engines, in particular of spark plugs for gasoline engines.
  • Table 1 shows alloy compositions belonging to the prior art.
  • Table 2 shows examples of non-inventive nickel alloys with 1% aluminum and various oxygen-affinity elements: L1 contains 0.13% Y, L2 0.18% Hf, L3 0.12% Y and 0.20 Hf, L4 0 , 13% Zr, L5 0.043% Mg and L6 0.12% Sc. In addition, these batches contain different oxygen contents in the range of 0.001% to 0.004% and Si contents ⁇ 0.01%.
  • Table 3 shows examples of nickel alloys according to the invention with about 1% silicon and different oxygen-affine elements: E1 and E2 each contain about 0.1% Y, E3, E4 and E5 each contain about 0.20% Hf, E6 and E7 each contain about 0.12% Y and 0.14 and 0.22 Hf respectively, E8 and E9 each contain about 0.10% Zr, E10 0.037% Mg, E11 contains 0.18% Hf and 0.055% Mg, E12 contains 0.1% Y and 0.065% Mg and E13 0.11% Y and 0.19% Hf and 0.059% Mg. In addition, these lots contain varying levels of oxygen in the range of 0.002% to 0.007% and Al -Contained between 0.003 and 0.035%.
  • Figure 3 shows that the 1% Al-containing alloys all have a greater mass increase by oxidation than the 1% Si-containing alloys from Table 3. Therefore, the aluminum content is inventively limited to max. 0.10% limited. Too low an Al content increases costs. The Al content is therefore greater than or equal to 0.001%.
  • the NiSi alloys with Mg show a particularly low mass increase, ie a particularly good one Oxidation resistance.
  • Mg improves the oxidation resistance of the Si-containing melts.
  • none of the Si-containing alloys in Figure 3 show flaking.
  • Y, Hf and Zr if added in sufficient amounts, also improve the oxidation resistance, albeit in part with a slightly higher oxidation rate compared to Mg.
  • the Al-containing alloys also show Y, Hf and / or Zr additions to the Sc-containing alloy LB2174 no flaking, but only an increased oxidation rate compared to the Si-containing alloys.
  • Aluminum deteriorates the oxidation resistance when added in the range of 1%. Therefore the aluminum content is reduced to max. 0.10% limited. Too low an Al content increases costs. The Al content is therefore set equal to or greater than 0.001%.
  • Iron is limited to 0.20% because this element reduces the oxidation resistance. Too little Fe content increases the cost of producing the alloy. The Fe content is therefore greater than or equal to 0.01%.
  • the carbon content should be less than 0.10% to ensure processability. Too small C contents cause increased costs in the production of the alloy. The carbon content should therefore be greater than 0.001%.
  • Nitrogen is limited to 0.10% as this element reduces the oxidation resistance. Too small N contents cause increased costs in the production of the alloy. The nitrogen content should therefore be greater than 0.0005%.
  • the NiSi alloy with Mg (E10) has a particularly small increase in mass, i. a particularly good oxidation resistance, so that a Mg content is favorable. Even very low Mg contents improve the processing, by the setting of sulfur, whereby the occurrence of low-melting NiS eutectics is avoided. For Mg, therefore, a minimum content of 0.0001% is required. Excessively high levels can lead to intermetallic Ni-Mg phases, which significantly impair processability. The Mg content is therefore limited to 0.08%.
  • the oxygen content must be less than 0.010% to ensure the manufacturability of the alloy. Too small oxygen levels cause increased costs. The oxygen content should therefore be greater than 0.0001%.
  • Manganese is limited to 0.1% as this element reduces oxidation resistance.
  • Chromium is limited to 0.10% because this element, as the example of T1 in Figure 1 shows, is not beneficial.
  • Copper is limited to 0.50% because this element reduces oxidation resistance.
  • the levels of sulfur should be kept as low as possible, since this surfactant affects the oxidation resistance. It will therefore max. 0.008% S set.
  • a minimum content of 0.03% Y is necessary to obtain the oxidation resistance enhancing effect of Y.
  • the upper limit is set at 0.20% for cost reasons.
  • a minimum content of 0.03% Hf is required to obtain the oxidation resistance enhancing effect of Hf.
  • the upper limit is set at 0.25% Hf for cost reasons.
  • a minimum content of 0.03% Zr is necessary to obtain the oxidation resistance enhancing effect of Zr.
  • the upper limit is set at 0.15% Zr for cost reasons.
  • the alloy can contain up to 0.15% Ti without degrading its properties.
  • Cobalt is reduced to max. 0.50% because this element reduces the oxidation resistance.
  • Molybdenum is reduced to max. 0.10% limited because this element reduces the oxidation resistance. The same applies to tungsten and vanadium.
  • the content of phosphorus should be less than 0.020%, since this surfactant affects the oxidation resistance.
  • the content of boron should be kept as low as possible because this surfactant affects the oxidation resistance. It will therefore max. 0.005% B is set.
  • Pb is set to max. 0.005% limited because this element reduces the oxidation resistance.
  • Table 1 Composition of prior art alloys NiCr2MnSi - 2.4146 DE 2936312 charge T1 T2 element Ni rest rest Si 0.5 1.0 al - 1.0 Y - 0.17 Ti 12:01 - C 0,003 - Co 0.04 - Cu 0.01 0.01 Cr 1.6 0.01 Mn 1.5 0.02 Fe 0.08 0.13 material NiAlY NiAlHf NiAlYHf NiAlZr NiAlMg NiAlSc charge L1 L2 L3 L4 L5 L6 C 0,003 0,002 0,002 0,002 0,002 0,003 S ⁇ 0.0006 ⁇ 0.0005 0.0005 0.0005 0.0009 0.0005 N 0,002 0,002 ⁇ 0.001 0,003 ⁇ 0.001 ⁇ 0.002 Cr 12:01 12:01 0.01 0.01 ⁇ 00:01 0.01 Ni (remainder) 98.5 98.6

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Spark Plugs (AREA)
  • Soft Magnetic Materials (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Electrodes For Cathode-Ray Tubes (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Claims (15)

  1. Alliage à base de nickel, composé de (en % en poids)
    Si 0,8 - 2,0 %
    Al 0,001 à 0,1 %
    Fe 0,01 à 0,2 %
    C 0, 001 - 0,10 %
    N 0,0005 - 0,10 %
    Mg 0,0001 - 0,08 %
    O 0,0001 à 0,010 %
    Mn max. 0,10 %
    Cr max. 0,10 %
    Cu max. 0,50 %
    S max. 0,008 %
    comprenant sélectivement les éléments suivants :
    Ca 0,0002 - 0,06 %
    Y 0,03 - 0,20 %
    Hf 0,03 - 0,25 %
    Zr 0,03 - 0,15 %
    Ce 0,03 - 0,15 %
    La 0,03 - 0,15 %
    Ti max. 0,15 %
    Co max. 0,50 %
    W max. 0,10 %
    Mo max. 0,10 %
    V max. 0,10 %
    P max. 0,020 %
    B max. 0,005 %
    Pb max. 0,005 %
    Zn max. 0,005 %
    Ni le reste et les impuretés usuelles résultant de l'élaboration.
  2. Alliage selon la revendication 1, comprenant une teneur en Si (en % en poids) de 0,8 à 1,5 %.
  3. Alliage selon la revendication 1 ou la revendication 2, comprenant une teneur en Si (en % en poids) de 0,8 à 1,2 %.
  4. Alliage selon l'une ou plusieurs des revendications 1 à 3, comprenant une teneur en Al (en % en poids) de 0,001 à 0,05 %.
  5. Alliage selon l'une ou plusieurs des revendications 1 à 4, comprenant une teneur en Fe (en % en poids) de 0,01 à 0,10 %.
  6. Alliage selon l'une ou plusieurs des revendications 1 à 5, comprenant une teneur en Fe (en % en poids) de 0,01 à 0,05 %
  7. Alliage selon l'une ou plusieurs des revendications 1 à 6, comprenant une teneur en C (en % en poids) de 0,001 à 0,5 % et une teneur en N (en % en poids) de 0,001 à 0,05 %.
  8. Alliage selon l'une ou plusieurs des revendications 1 à 7, comprenant une teneur en Mg (en % en poids) de 0,005 à 0,08 %.
  9. Alliage selon l'une ou plusieurs des revendications 1 à 8, comprenant une teneur en O (en % en poids) de 0,0001 à 0,008 %.
  10. Alliage selon l'une ou plusieurs des revendications 1 à 9, comprenant une teneur en Mn (en % en poids) de max. 0,05 % et une teneur en Cr (en % en poids) de max. 0,05 %.
  11. Alliage selon l'une ou plusieurs des revendications 1 à 10, comprenant une teneur en Y (en % en poids) de 0,05 à 0,15 %.
  12. Alliage selon l'une ou plusieurs des revendications 1 à 11, comprenant une teneur en Hf (en % en poids) de 0,03 à 0,15 %.
  13. Alliage selon l'une ou plusieurs des revendications 1 à 12, comprenant une teneur en Cu (en % en poids) de max. 0,20 %.
  14. Utilisation d'un alliage à base de nickel selon l'une ou plusieurs des revendications 1 à 13, en tant que matière d'électrode pour des éléments d'allumage des moteurs à combustion interne.
  15. Utilisation selon la revendication 14, en tant que matière d'électrode pour des bougies d'allumage des moteurs à essence.
EP11755241.4A 2010-06-21 2011-06-08 Alliage à base de nickel Active EP2582854B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201010024488 DE102010024488B4 (de) 2010-06-21 2010-06-21 Nickelbasislegierung
PCT/DE2011/001174 WO2011160617A2 (fr) 2010-06-21 2011-06-08 Alliage à base de nickel

Publications (2)

Publication Number Publication Date
EP2582854A2 EP2582854A2 (fr) 2013-04-24
EP2582854B1 true EP2582854B1 (fr) 2014-08-06

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EP11755241.4A Active EP2582854B1 (fr) 2010-06-21 2011-06-08 Alliage à base de nickel

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US (1) US8784730B2 (fr)
EP (1) EP2582854B1 (fr)
JP (1) JP5680192B2 (fr)
CN (1) CN102947474B (fr)
BR (1) BR112012032829B1 (fr)
DE (1) DE102010024488B4 (fr)
MX (1) MX2012013578A (fr)
RU (1) RU2518814C1 (fr)
WO (1) WO2011160617A2 (fr)

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JP5697484B2 (ja) * 2011-02-25 2015-04-08 株式会社デンソー 点火プラグ用電極材料
DE102011007532A1 (de) * 2011-04-15 2012-10-18 Robert Bosch Gmbh Zündkerzenelektrodenmaterial und Zündkerze, sowie Verfahren zur Herstellung des Zündkerzenelektrodenmaterials
JP6155575B2 (ja) * 2012-02-03 2017-07-05 住友電気工業株式会社 電極材料及び点火プラグ用電極、並びに点火プラグ
DE102013004365B4 (de) * 2013-03-14 2015-09-24 VDM Metals GmbH Nickelbasislegierung mit Silizium, Aluminium und Chrom
CN104404309A (zh) * 2014-12-02 2015-03-11 常熟市良益金属材料有限公司 一种耐高温镍合金
CN104532064A (zh) * 2014-12-25 2015-04-22 春焱电子科技（苏州）有限公司 一种电子材料用合金
TWI518183B (zh) * 2015-02-04 2016-01-21 China Steel Corp Corrosion resistant high nickel alloy and its manufacturing method
CN105950917A (zh) * 2016-05-26 2016-09-21 张日龙 一种耐热合金及其制备方法
WO2018066709A1 (fr) 2016-10-07 2018-04-12 新日鐵住金株式会社 Matériau nickel et procédé de production de matériau nickel
CN108220688B (zh) * 2017-11-29 2020-05-12 重庆材料研究院有限公司 高抗核辐射的核场测温用热电偶负极材料及制备方法
CN108486418B (zh) * 2018-04-25 2020-08-11 常州市潞城慧热电子厂 一种用于温差发电器的合金丝及其制备工艺
JP6944429B2 (ja) * 2018-11-09 2021-10-06 日本特殊陶業株式会社 スパークプラグ
CN111719057A (zh) * 2019-03-20 2020-09-29 沈阳人和机械制造有限公司 一种降膜管及其制造工艺
JP7448799B2 (ja) 2020-04-07 2024-03-13 日本製鉄株式会社 ニッケル材およびその製造方法

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Also Published As

Publication number Publication date
WO2011160617A2 (fr) 2011-12-29
MX2012013578A (es) 2013-01-24
EP2582854A2 (fr) 2013-04-24
BR112012032829B1 (pt) 2018-09-11
JP5680192B2 (ja) 2015-03-04
DE102010024488B4 (de) 2012-04-26
WO2011160617A3 (fr) 2012-04-05
US20130078136A1 (en) 2013-03-28
US8784730B2 (en) 2014-07-22
DE102010024488A1 (de) 2011-12-22
CN102947474A (zh) 2013-02-27
JP2013531132A (ja) 2013-08-01
BR112012032829A2 (pt) 2016-11-08
CN102947474B (zh) 2015-07-29
RU2518814C1 (ru) 2014-06-10

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