EP2971204B1 - Nickelbasislegierung mit silizium, aluminium und chrom - Google Patents

Nickelbasislegierung mit silizium, aluminium und chrom Download PDF

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Publication number
EP2971204B1
EP2971204B1 EP14709528.5A EP14709528A EP2971204B1 EP 2971204 B1 EP2971204 B1 EP 2971204B1 EP 14709528 A EP14709528 A EP 14709528A EP 2971204 B1 EP2971204 B1 EP 2971204B1
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EP
European Patent Office
Prior art keywords
max
content
mass
comprised
alloy
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Application number
EP14709528.5A
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German (de)
English (en)
French (fr)
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EP2971204A1 (de
Inventor
Heike Hattendorf
Frank Scheide
Larry Paul
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VDM Metals International GmbH
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VDM Metals International GmbH
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Application filed by VDM Metals International GmbH filed Critical VDM Metals International GmbH
Priority to SI201430413T priority Critical patent/SI2971204T1/sl
Publication of EP2971204A1 publication Critical patent/EP2971204A1/de
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Classifications

    • 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
    • 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

Definitions

  • the invention relates to a nickel-based alloy with silicon, aluminum, chromium and reactive elements as alloying constituents.
  • Nickel-base alloys are used inter alia to produce electrodes of ignition elements for internal combustion engines. These electrodes 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 nanosecond 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 comparatively insensitive to carburizing and nitriding, have good heat resistance, good corrosion resistance, and are readily formable and weldable.
  • a nickel alloy has been disclosed 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 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.
  • EP 1 867 739 A1 For example, there is proposed a nickel base alloy containing 1.5 to 2.5% silicon, 1.5 to 3% aluminum, 0 to 0.5% manganese, 0.05 to 0.2% titanium in combination with 0.1 to 0.3% zirconium, wherein Zr can be replaced wholly or partially 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 in each case 0.05 to 0.10% hafnium and lanthanum, balance nickel and manufacturing-related impurities.
  • the aim of the subject invention is to provide a nickel-based alloy by which it comes to an increase in the life of components made therefrom, which by raising the spark erosion and corrosion resistance at the same time sufficient formability and weldability (workability) can be brought.
  • the alloy should in particular have a high corrosion resistance and even with very corrosive acting fuels such. B. with a proportion of ethanol, have a sufficiently high corrosion resistance.
  • the goal is achieved by a nickel base alloy consisting of (in mass%) Si 1.5 - 3.0% al 1.5 - 3.0% Cr > 0.1 - 3.0%, where 4.0 ⁇ ⁇ Al + Si + Cr ⁇ ⁇ 8.0 is satisfied with the contents of Si, Al and Cr in%, Fe 0.005 to 0.20%, Y 0.012-0.20%, ⁇ 0.001-0.20% of one or more of Hf, Zr, La, Ce, Ti, where 0.02 ⁇ ⁇ Y + 0.5 * Hf + Zr + 1.8 * Ti + 0 , 6 * (La + Ce) ⁇ ⁇ 0.30 is satisfied with the contents of Y, Hf, Zr, La, Ce, Ti in%.
  • the alloy yttrium with a content of 0.01% to 0.20% and 0.001 to 0.20% of one or more of the elements Hf, Zr, La, Ce, Ti, where 0.02 ⁇ Y + 0.5 * Hf + Zr + 1.8 * Ti + 0.6 * (La + Ce) ⁇ 0.30 with the contents of Y, Hf, Zr, La, Ce, Ti in% is satisfied.
  • Preferred ranges are given as follows: Y 0.01 to 0.15% Y 0.02 to 0.10% Hf, Zr, La, Ce, Ti 0.001 to 0.15%, respectively with 0.02 ⁇ Y + 0.5 * Hf + Zr + 1.8 * Ti + 0.6 * (La + Ce) ⁇ 0.25 Hf, Zr, La, Ce, Ti 0.001 to 0.10% each with 0.02 ⁇ Y + 0.5 * Hf + Zr + 1.8 * Ti + 0.6 * (La + Ce) ⁇ 0.20 Hf, Zr, Ti in each case 0.01 to 0.05% or La, Ce in each case 0.001 to 0.10% with 0.02 ⁇ Y + 0.5 * Hf + Zr + 1.8 * Ti + 0.6 * (La + Ce) ⁇ 0.20
  • the element Mn may be given in the alloy as follows: Mn 0.001 to 0.20% preferably the following ranges are given: Mn 0.001 to 0.10% Mn 0.001 to 0.08%
  • the alloy may further include calcium in amounts between 0.0001 and 0.06%, as needed.
  • the sulfur content is limited to max. 0.015% limited. Preferred contents can be given as follows: S Max. 0.010%
  • the copper content is limited to max. 0.80% limited. Preferably, a restriction occurs Max. 0.50% Max. 0.20%
  • impurities may still have the following elements: Co max.0,50% W Max. 0.02% (maximum 0.10%) Not a word Max. 0.02% (maximum 0.10%) Nb Max. 0.02% (maximum 0.10%) V Max. 0.02% (maximum 0.10%) Ta Max. 0.02% (maximum 0.10%) pb Max. 0.005% Zn Max. 0.005% sn Max. 0.005% Bi Max. 0.005% P Max. 0.050% (max 0.020%) B Max. 0.020% (max 0.010%)
  • the alloy of the invention is preferably melted open, followed by treatment in a VOD or VLF plant. But also a melting and pouring in a vacuum is possible. Thereafter, the alloy is poured in blocks or as a continuous casting. If necessary, the block / continuous casting is then annealed at temperatures between 800 ° C and 1270 ° C for 0.1 h to 70 h. Furthermore, it is possible to remelt the alloy additionally with ESU and / or VAR. Thereafter, the alloy is brought into the desired semifinished product.
  • annealed at temperatures between 700 ° C and 1270 ° C for 0.1 h to 70 h then hot formed, possibly with intermediate anneals between 700 ° C and 1270 ° C for 0.05 h to 70 h.
  • the surface of the material can optionally (also several times) be removed chemically and / or mechanically in between and / or after the hot forming for cleaning.
  • one or more cold forming with degrees of deformation up to 99% in the desired semi-finished mold optionally with intermediate anneals between 700 ° C and 1250 ° C for 0.1 to 70 h, if necessary under inert gas such.
  • the alloy according to the invention can be well in the product forms band, in particular in thicknesses of 100 microns to 4 mm, sheet, in particular in thicknesses of 1 mm to 70 mm, rod, in particular in thicknesses of 10 mm to 500 mm, and wire in particular in thicknesses from 0.1 mm to 15 mm, manufacture and use pipes, in particular in wall thicknesses of 0.10 mm to 70 mm and diameters of 0.2 mm to 3000 mm.
  • These product forms are produced with a mean particle size of 4 ⁇ m to 600 ⁇ m.
  • the preferred range is between 10 ⁇ m and 200 ⁇ m.
  • the nickel-based alloy according to the invention is preferably usable as a material for electrodes of spark plugs for gasoline engines.
  • an aluminum content of at least 1.5% further increases the oxidation resistance.
  • the upper limit is therefore set to 3.0 wt% Si.
  • a chromium content of at least 0.1% further increases the oxidation resistance.
  • the upper limit is therefore set to 3.0 wt% Cr.
  • Iron is limited to 0.20% because this element reduces the oxidation resistance. Too low an Fe content increases the cost of producing the alloy. The Fe content is therefore greater than or equal to 0.005%.
  • a minimum content of 0.01% Y is necessary to obtain the oxidation resistance-enhancing effect of Y.
  • the upper limit is set at 0.20% for cost reasons.
  • Oxidation resistance further increases with the addition of at least 0.001% of one or more of the elements Hf, Zr, La, Ce, Ti, where Y + 0.5 * Hf + Zr + 1.8 * Ti + 0.6 * (La + Ce) must be greater than or equal to 0.02 in order to obtain the desired oxidation resistance.
  • the addition of at least one or more of the elements Hf, Zr, La, Ce, Ti, greater than 0.20% increases the cost, where Y + 0.5 * Hf + Zr + 1.8 * Ti + 0.6 * ( La + Ce) is additionally restricted to less than or equal to 0.30 (with the contents of Y, Hf, Zr, La, Ce, Ti in%).
  • 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% because this element reduces 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%.
  • Manganese is limited to 0.20% because this element reduces oxidation resistance. Too small Mn contents cause increased costs in the production of the alloy. The manganese content should therefore be greater than 0.001%
  • Mg manganese-based nickel-semiconductor
  • 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% by weight.
  • 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%.
  • the levels of sulfur should be kept as low as possible, since this surfactant affects the oxidation resistance. It will therefore max. 0.015% S set.
  • Copper is limited to 0.80% as this element reduces the oxidation resistance.
  • Cobalt is reduced to max. 0.50% because this element reduces the oxidation resistance.
  • Molybdenum is reduced to max. 0.20% limited because this element reduces the oxidation resistance. The same applies to tungsten, niobium and vanadium.
  • the content of phosphorus should be less than 0.050%, 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. 0.020% B is set.
  • Pb is set to max. 0.005% limited because this element reduces the oxidation resistance.
  • Zn, Sn and Bi The same applies to Zn, Sn and Bi.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Spark Plugs (AREA)
  • Conductive Materials (AREA)
  • Soft Magnetic Materials (AREA)
  • Fuel Cell (AREA)
EP14709528.5A 2013-03-14 2014-01-28 Nickelbasislegierung mit silizium, aluminium und chrom Active EP2971204B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI201430413T SI2971204T1 (sl) 2013-03-14 2014-01-28 Zlitina na osnovi niklja s silicijem, aluminijem in kromom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013004365.4A DE102013004365B4 (de) 2013-03-14 2013-03-14 Nickelbasislegierung mit Silizium, Aluminium und Chrom
PCT/DE2014/000034 WO2014139490A1 (de) 2013-03-14 2014-01-28 Nickelbasislegierung mit silizium, aluminium und chrom

Publications (2)

Publication Number Publication Date
EP2971204A1 EP2971204A1 (de) 2016-01-20
EP2971204B1 true EP2971204B1 (de) 2017-09-06

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EP14709528.5A Active EP2971204B1 (de) 2013-03-14 2014-01-28 Nickelbasislegierung mit silizium, aluminium und chrom

Country Status (11)

Country Link
US (1) US9932656B2 (pt)
EP (1) EP2971204B1 (pt)
JP (1) JP6150910B2 (pt)
KR (1) KR20150114543A (pt)
CN (1) CN105008562A (pt)
BR (1) BR112015018192B1 (pt)
DE (1) DE102013004365B4 (pt)
MX (1) MX358313B (pt)
RU (1) RU2610990C1 (pt)
SI (1) SI2971204T1 (pt)
WO (1) WO2014139490A1 (pt)

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WO2015120832A1 (de) * 2014-02-13 2015-08-20 VDM Metals GmbH Titanfreie legierung
JP6484160B2 (ja) * 2015-11-02 2019-03-13 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
CN105385897B (zh) * 2015-11-04 2018-06-19 重庆材料研究院有限公司 核反应堆堆芯测温用热电偶材料及制备方法
CN105296941B (zh) * 2015-11-23 2017-12-19 沈阳黎明航空发动机(集团)有限责任公司 一种镍基管状阴极靶材的制备及在真空电弧镀涂镀的应用
CN108699634B (zh) * 2015-12-23 2021-03-19 美题隆公司 用于生物传感器的镍合金
CN105587771B (zh) * 2016-02-23 2019-03-26 安徽省宁国顺昌机械有限公司 一种使用寿命长轴承
CN105673706B (zh) * 2016-02-23 2018-07-06 安徽省宁国顺昌机械有限公司 一种耐磨耐腐蚀轴承
CN105757124B (zh) * 2016-02-23 2018-07-06 安徽省宁国顺昌机械有限公司 一种高韧性高硬度滚动轴承
CN105587773B (zh) * 2016-02-23 2019-03-12 安徽省宁国顺昌机械有限公司 一种高硬度轴承
CN105626697B (zh) * 2016-02-23 2018-07-06 安徽省宁国顺昌机械有限公司 一种接触疲劳性好的滚动轴承
TWI791611B (zh) * 2017-09-14 2023-02-11 美商博隆能源股份有限公司 使用火花點火器起動之用於固體氧化物燃料電池系統的內部點火機制
DE102017218032A1 (de) * 2017-10-10 2019-04-11 Robert Bosch Gmbh Zündkerzen-Widerstandselement mit erhöhtem ZrSiO4-Phasenanteil
CN108048692A (zh) * 2017-11-15 2018-05-18 重庆嘉萌鸿业科技有限公司 一种铝合金齿轮箱及其制备工艺
KR102399595B1 (ko) * 2017-11-21 2022-05-19 엘지이노텍 주식회사 금속판 및 이를 이용한 증착용 마스크
CN108220689B (zh) * 2017-11-29 2020-05-12 重庆材料研究院有限公司 高温长时间稳定测温k型热电偶正极材料及制备方法
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
CN108411161B (zh) * 2018-04-25 2020-07-17 常州市潞城慧热电子厂 一种k型热电偶的负极合金丝及其制备工艺
CN109136696B (zh) * 2018-08-08 2023-11-03 倧奇健康科技有限公司 一种红外辐射材料及其制备方法以及红外发射基材
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
CN110055440A (zh) * 2019-05-29 2019-07-26 南京达迈科技实业有限公司 一种用于火花塞的多元合金丝及其制备方法
DE102020116858A1 (de) * 2019-07-05 2021-01-07 Vdm Metals International Gmbh Nickel-Basislegierung für Pulver und Verfahren zur Herstellung eines Pulvers
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Also Published As

Publication number Publication date
DE102013004365A1 (de) 2014-09-18
DE102013004365B4 (de) 2015-09-24
CN105008562A (zh) 2015-10-28
WO2014139490A1 (de) 2014-09-18
JP6150910B2 (ja) 2017-06-21
MX2015010814A (es) 2015-11-26
SI2971204T1 (sl) 2017-11-30
MX358313B (es) 2018-08-14
US20160032425A1 (en) 2016-02-04
US9932656B2 (en) 2018-04-03
KR20150114543A (ko) 2015-10-12
BR112015018192B1 (pt) 2021-01-26
EP2971204A1 (de) 2016-01-20
BR112015018192A2 (pt) 2017-07-18
JP2016516127A (ja) 2016-06-02
RU2610990C1 (ru) 2017-02-17

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