US20100003163A1 - Nickel-Based Alloy - Google Patents

Nickel-Based Alloy Download PDF

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Publication number
US20100003163A1
US20100003163A1 US12/309,775 US30977507A US2010003163A1 US 20100003163 A1 US20100003163 A1 US 20100003163A1 US 30977507 A US30977507 A US 30977507A US 2010003163 A1 US2010003163 A1 US 2010003163A1
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Prior art keywords
nickel
based alloy
weight
max
accordance
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US12/309,775
Inventor
Jutta Kloewer
Frank Scheide
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VDM Metals GmbH
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ThyssenKrupp VDM GmbH
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Assigned to THYSSENKRUPP VDM GMBH reassignment THYSSENKRUPP VDM GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHEIDE, FRANK, KLOEWER, JUTTA
Publication of US20100003163A1 publication Critical patent/US20100003163A1/en
Assigned to OUTOKUMPU VDM GMBH reassignment OUTOKUMPU VDM GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: THYSSENKRUPP VDM GMBH
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    • 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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W

Definitions

  • the invention relates to a nickel-based alloy having silicon, aluminum, and reactive elements as alloy components.
  • Nickel-based alloys are used inter alia for producing electrodes for ignition elements in internal combustion engines. Two damaging mechanisms affect the wear of such electrodes, specifically high temperature corrosion and spark erosion.
  • Wear from high temperature corrosion can be determined by measuring losses in weight and using metallographic examinations after exposure to pre-specified testing temperatures.
  • Spark erosion is combustion of material that is caused by ignition sparks. With each flashover, a limited volume of electrode material is melted and in part evaporated.
  • the type of oxide layer formation is particularly significant for both damaging mechanisms.
  • Different alloy elements for nickel-based alloys are known for attaining optimum oxide layer formation for the specific application.
  • aluminum has a positive effect on oxide layer formation.
  • reactive elements can improve the adhesion of the oxide layer that forms and can increase life cycle.
  • GB-A 2031950 is a nickel alloy comprising (in % by weight) about 0.2 to 3% Si, about 0.5% or less Mn, at least two metals selected from the group comprising about 0.2 to 3% Cr, about 0.2 to 3% Al, and about 0.01 to 1% Y, and the remainder nickel.
  • DE-A 102 24 891 suggests an alloy that is based on nickel and that has (in % by weight) 1.8 to 2.2% silicon, 0.05 to 0.1% yttrium and/or hafnium and/or zirconium, 2 to 2.4% aluminum, and the remainder nickel. It is very difficult to process such alloys given the high aluminum and silicon content and they are thus not well suited for use on an industrial scale.
  • the object of the inventive subject-matter is to provide a nickel-based alloy that can be used to increase the life cycle of components produced therefrom by increasing resistance to spark erosion and oxidation while simultaneously providing good formability and weldability.
  • Nickel-based alloy having (in % by weight):
  • Nickel-based alloy having (in % by weight):
  • Nickel-based alloy having (in % by weight):
  • the inventive nickel-based alloy can preferably be used as a material for electrodes for spark plugs in gasoline engines.
  • the element Mg is particularly important in terms of binding sulfur so that in this case it is possible to selectively adjust low sulfur content in the inventive nickel-based alloy.
  • Preferred aluminum content (in % by weight) ranges from 1.2-1.5%.
  • Preferred silicon content (in % by weight) ranges from between 1.2 and 1.8%, in particular 1.2 and 1.5%, while the preferred Mg content (in % by weight) is adjusted between 0.008 and 0.05%.
  • FIGS. 1 and 2 are plots of the results of laboratory tests.
  • the table compares five inventive laboratory batches to two industrial batches belonging to the prior art.
  • Laboratory batch 1132 is an example in which the reactive elements Y+Hf are provided in the inventive nickel-based alloy.
  • Laboratory batch 1140 is an example in which the reactive elements Y+La are present in the inventive alloy.
  • Laboratory batches 1141 and 1142 disclose examples in which Y+La+Hf were adjusted as reactive elements in the inventive nickel-based alloy.
  • FIGS. 1 and 2 depict weight loss examinations for the alloys in accordance with the table at temperatures of 900° C. and 1000° C.
  • the two comparison alloys exhibit flaking of the previously constructed oxide layer. Although this also occurs with the inventive alloys at 1000° C., it does not occur to the same extent as in the comparison alloys.

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Contacts (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Continuous Casting (AREA)
  • Fuel Cell (AREA)

Abstract

Nickel-based alloy, consisting of (in % by mass) Al 1.2-<2.0% Si 1.2-<1.8% C 0.001-0.1% S 0.001-0.1% Cr 0.03-0.1% Mn 0.03-0.1% Cu max. 0.1% Fe 0.02-0.2% Mg 0.005-0.06% Pb max. 0.005% Y 0.05-0.15% and Hf 0.05-0.10% or Y 0.05-0.15% and La 0.05-0.10% or Y 0.05-0.15% and Hf 0.05-0.10% and La 0.05-0.10% Ni remainder together with manufacturing-related impurities.

Description

    BACKGROUND OF THE INVENTION
  • The invention relates to a nickel-based alloy having silicon, aluminum, and reactive elements as alloy components.
  • Nickel-based alloys are used inter alia for producing electrodes for ignition elements in internal combustion engines. Two damaging mechanisms affect the wear of such electrodes, specifically high temperature corrosion and spark erosion.
  • Wear from high temperature corrosion can be determined by measuring losses in weight and using metallographic examinations after exposure to pre-specified testing temperatures.
  • Spark erosion is combustion of material that is caused by ignition sparks. With each flashover, a limited volume of electrode material is melted and in part evaporated.
  • The type of oxide layer formation is particularly significant for both damaging mechanisms.
  • Different alloy elements for nickel-based alloys are known for attaining optimum oxide layer formation for the specific application. Thus, for instance, aluminum has a positive effect on oxide layer formation. It is also known that reactive elements can improve the adhesion of the oxide layer that forms and can increase life cycle.
  • Known from GB-A 2031950 is a nickel alloy comprising (in % by weight) about 0.2 to 3% Si, about 0.5% or less Mn, at least two metals selected from the group comprising about 0.2 to 3% Cr, about 0.2 to 3% Al, and about 0.01 to 1% Y, and the remainder nickel.
  • DE-A 102 24 891 suggests an alloy that is based on nickel and that has (in % by weight) 1.8 to 2.2% silicon, 0.05 to 0.1% yttrium and/or hafnium and/or zirconium, 2 to 2.4% aluminum, and the remainder nickel. It is very difficult to process such alloys given the high aluminum and silicon content and they are thus not well suited for use on an industrial scale.
    • SUMMARY OF THE INVENTION
  • The object of the inventive subject-matter is to provide a nickel-based alloy that can be used to increase the life cycle of components produced therefrom by increasing resistance to spark erosion and oxidation while simultaneously providing good formability and weldability.
  • This object is attained using a nickel-based alloy that contains (in % by weight):
      • Al 1.2-<2.0%
      • Si 1.2-<1.8
      • C 0.001-0.1%
      • S 0.001-0.1%
      • Cr 0.03-0.1%
      • Mn 0.03-0.1%
      • Cu max. 0.1%
      • Fe 0.02-0.2%
      • Mg 0.005-0.06%
      • Pb max. 0.005%
      • Y 0.05-0.15% and Hf 0.05-0.10% or
      • Y 0.05-0.15% and La 0.05-0.10% or
      • Y 0.05-0.15% and Hf 0.05-0.10% and La 0.05-0.10%
      • Ni remainder and production-related impurities
  • Preferred alternative embodiments of the inventive subject-matter are as follows.
  • Nickel-based alloy having (in % by weight):
      • Al 1.2-<2.0%
      • Si 1.2-<1.8
      • C 0.001-0.05%
      • S 0.001-0.05%
      • Cr 0.03-0.1%
      • Mn 0.03-0.1%
      • Cu max. 0.1%
      • Fe 0.02-0.2%
      • Mg 0.005-0.06%
      • Pb max. 0.005%
      • Y 0.10-0.15% and Hf 0.05-0.10%
      • Ni remainder and production-related impurities
  • Nickel-based alloy having (in % by weight):
      • Al 1.2-<2.0%
      • Si 1.2-<1.8
      • C 0.001-0.05%
      • S 0.001-0.05%
      • Cr 0.03-0.1%
      • Mn 0.03-0.1%
      • Cu max. 0.1%
      • Fe 0.02-0.2%
      • Mg 0.005-0.06%
      • Pb max. 0.005%
      • Y 0.10-0.15% and La 0.05 to 0.10%
      • Ni remainder and production-related impurities
  • Nickel-based alloy having (in % by weight):
      • Al 1.2-<2.0%
      • Si 1.2-<1.8
      • C 0.001-0.05%
      • S 0.001-0.05%
      • Cr 0.03-0.1%
      • Mn 0.03-0.1%
      • Cu max. 0.1%
      • Fe 0.02-0.2%
      • Mg 0.005-0.06%
      • Pb max. 0.005%
      • Y 0.10-0.15% and Hf 0.05-0.10% and La 0.05-0.10%
  • Thus, there are three conceivable variants in terms of the reactive elements, specifically:
      • Y+Hf
      • Y+La and
      • Y+Hf+La
  • The inventive nickel-based alloy can preferably be used as a material for electrodes for spark plugs in gasoline engines.
  • Selectively adjusting the elements Al, Si, Cr, Mn, and Mg, as well as the reactive elements Y, Hf, La in their respective combinations can bring about an increased life cycle for electrode materials by increasing the spark erosion resistance and oxidation resistance while simultaneously promoting formability and weldability.
  • The element Mg is particularly important in terms of binding sulfur so that in this case it is possible to selectively adjust low sulfur content in the inventive nickel-based alloy.
  • Preferred aluminum content (in % by weight) ranges from 1.2-1.5%.
  • Preferred silicon content (in % by weight) ranges from between 1.2 and 1.8%, in particular 1.2 and 1.5%, while the preferred Mg content (in % by weight) is adjusted between 0.008 and 0.05%.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIGS. 1 and 2 are plots of the results of laboratory tests.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • The table compares five inventive laboratory batches to two industrial batches belonging to the prior art.
  • Laboratory batch 1132 is an example in which the reactive elements Y+Hf are provided in the inventive nickel-based alloy.
  • Laboratory batch 1140 is an example in which the reactive elements Y+La are present in the inventive alloy.
  • Laboratory batches 1141 and 1142 disclose examples in which Y+La+Hf were adjusted as reactive elements in the inventive nickel-based alloy.
  • Ele- LB LB LB LB
    ment 1132 1140 1141 1142 NiCr2MnSi NiAl1Si1Y
    Ni 96.83 96.91 96.89 96.79 96.24 97.56
    Si 1.47 1.36 1.36 1.42 0.49 0.96
    Al 1.38 1.43 1.44 1.40 0.02 0.98
    Zr
    Y 0.15 0.12 0.14 0.13 0.17
    Hf 0.08 0.078 0.073
    La 0.09 0.096 0.096
    Ti 0.1 0.01 0.01
    C 0.002 0.006 0.004 0.003 0.003 0.03
    S 0.002 0.002 0.002 0.002 0.002 0.002
    Co 0.04 0.05
    Cu 0.01 0.01
    Cr 0.04 0.03 0.06 0.04 1.57 0.01
    Zr 0.01
    Mg 0.02 0.03 0.01 0.03 0.02 0.04
    Mn 0.06 0.03 0.03 0.06 1.48 0.02
    Fe 0.03 0.03 0.03 0.04 0.08 0.13
    Pb 0.001 0.001
  • FIGS. 1 and 2 depict weight loss examinations for the alloys in accordance with the table at temperatures of 900° C. and 1000° C.
  • At just 900° C. the two comparison alloys exhibit flaking of the previously constructed oxide layer. Although this also occurs with the inventive alloys at 1000° C., it does not occur to the same extent as in the comparison alloys.

Claims (11)

1. Nickel-based alloy comprising, in % by weight:
Al 1.2-<2.0%
Si 1.2-<1.8
C 0.001-0.1%
S 0.001-0.1%
Cr 0.03-0.1%
Mn 0.03-0.1%
Cu max. 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb max. 0.005%
Y 0.05-0.15% and Hf 0.05-0.10% or
Y 0.05-0.15% and La 0.05-0.10% or
Y 0.05-0.15% and Hf 0.05-0.10% and La 0.05-0.10%
Ni remainder and production-related impurities
2. Nickel-based alloy in accordance with claim 1, comprising, in % by weight:
Al 1.2-<2.0%
Si 1.2-<1.8
C 0.001-0.05%
S 0.001-0.05%
Cr 0.03-0.1%
Mn 0.03-0.1%
Cu max. 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb max. 0.005%
Y 0.10-0.15% and Hf 0.05-0.10%
Ni remainder and production-related impurities
3. Nickel-based alloy in accordance with claim 1, comprising, in % by weight:
Al 1.2-<2.0%
Si 1.2-<1.8
C 0.001-0.05%
S 0.001-0.05%
Cr 0.03-0.1%
Mn 0.03-0.1%
Cu max. 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb max. 0.005%
Y 0.10-0.15% and La 0.05to 0.10%
Ni remainder and production-related impurities
4. Nickel-based alloy in accordance with claim 1, further comprising, in % by weight:
Al 1.2-<2.0%
Si 1.2-<1.8
C 0.001-0.05%
S 0.001-0.05%
Cr 0.03-0.1%
Mn 0.03-0.1%
Cu max. 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb max. 0.005%
Y 0.10-0.15% and Hf 0.05-0.10% and La 0.05-0.10%
Ni remainder and production-related impurities
5. Nickel-based alloy in accordance with any of claims 1 through 4, further comprising, in % by weight:
Al 1.2-1.5%
Si 1.2-1.5%
6. Nickel-based alloy in accordance with any of claims 1 through 4, further comprising, in % by weight:
Mg 0.008-0.05%
7. Nickel-based alloy in accordance with any of claims 1 through 4, further comprising, in % by weight:
Y+Hf 0.11-0.18%
8. Nickel-based alloy in accordance with any of claims 1 through 4, further comprising, in % by weight:
Y+La 0.11-0.18%
9. Nickel-based alloy in accordance with any of claims 1 through 4, further comprising, in % by weight:
Y+Hf+La 0.18-0.22%
10. Nickel-based alloy in accordance with any of claims 1 through, further comprising, in % by weight:
Y+Mg 0.11-0.13%
11. A spark plug electrode comprising the nickel-based alloy in accordance with any of claims 1 through 4.
US12/309,775 2006-07-29 2007-07-06 Nickel-Based Alloy Abandoned US20100003163A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102006035111A DE102006035111B4 (en) 2006-07-29 2006-07-29 Nickel-based alloy
DE102006035111.8 2006-07-29
PCT/DE2007/001203 WO2008014741A1 (en) 2006-07-29 2007-07-06 Nickel-based alloy

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EP (1) EP2047004B1 (en)
JP (1) JP5273620B2 (en)
AT (1) ATE510034T1 (en)
BR (1) BRPI0715515B1 (en)
DE (1) DE102006035111B4 (en)
MX (1) MX2009000987A (en)
PL (1) PL2047004T3 (en)
RU (1) RU2399690C1 (en)
WO (1) WO2008014741A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011123322A1 (en) * 2010-03-31 2011-10-06 Verizon Patent And Licensing Inc. Resolution-based recording instructions for scheduled recording of media
CN102651538A (en) * 2011-02-25 2012-08-29 株式会社电装 Electrode material for electrode of spark plug
US20120256530A1 (en) * 2010-10-26 2012-10-11 Ngk Spark Plug Co., Ltd. Spark plug
US20130078136A1 (en) * 2010-06-21 2013-03-28 Thyssenkrupp Vdm Gmbh Nickel-based alloy
US9360051B2 (en) 2013-04-03 2016-06-07 Nidec Gpm Gmbh Shaft bearing with a shaft seal
US20170009704A1 (en) * 2015-07-06 2017-01-12 Rohr, Inc. Thrust reverser staggered translating sleeve
US9932656B2 (en) 2013-03-14 2018-04-03 Vdm Metals International Gmbh Nickel-based alloy with silicon, aluminum, and chromium

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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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
EP2698439B1 (en) * 2012-08-17 2014-10-01 Alstom Technology Ltd Oxidation resistant nickel alloy

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US4013459A (en) * 1975-10-24 1977-03-22 Olin Corporation Oxidation resistant nickel base alloys
US4103459A (en) * 1975-12-19 1978-08-01 Draftex Development Ag Channel-shaped sealing strips
US4329174A (en) * 1978-09-07 1982-05-11 Ngk Spark Plug Co., Ltd. Nickel alloy for spark plug electrodes
US5204059A (en) * 1988-07-25 1993-04-20 Mitsubishi Metal Corporation Ni base alloy for spark plug electrodes of internal combustion engines
US20020192494A1 (en) * 2001-05-22 2002-12-19 Tzatzov Konstantin K. Protective system for high temperature metal alloy products
US20040013560A1 (en) * 2002-06-04 2004-01-22 Klaus Hrastnik Nickel-based alloy

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JP2550158B2 (en) * 1988-07-25 1996-11-06 三菱マテリアル株式会社 Spark plug electrode material for internal combustion engines
JPH0445239A (en) * 1990-06-08 1992-02-14 Toshiba Corp Alloy for spark plug
EP1090155A1 (en) * 1998-06-30 2001-04-11 Federal-Mogul Corporation Spark plug electrode alloy
JP4769070B2 (en) * 2005-01-31 2011-09-07 日本特殊陶業株式会社 Spark plug for internal combustion engine

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US4013459A (en) * 1975-10-24 1977-03-22 Olin Corporation Oxidation resistant nickel base alloys
US4103459A (en) * 1975-12-19 1978-08-01 Draftex Development Ag Channel-shaped sealing strips
US4329174A (en) * 1978-09-07 1982-05-11 Ngk Spark Plug Co., Ltd. Nickel alloy for spark plug electrodes
US5204059A (en) * 1988-07-25 1993-04-20 Mitsubishi Metal Corporation Ni base alloy for spark plug electrodes of internal combustion engines
US20020192494A1 (en) * 2001-05-22 2002-12-19 Tzatzov Konstantin K. Protective system for high temperature metal alloy products
US20040013560A1 (en) * 2002-06-04 2004-01-22 Klaus Hrastnik Nickel-based alloy

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011123322A1 (en) * 2010-03-31 2011-10-06 Verizon Patent And Licensing Inc. Resolution-based recording instructions for scheduled recording of media
US20130078136A1 (en) * 2010-06-21 2013-03-28 Thyssenkrupp Vdm Gmbh Nickel-based alloy
US8784730B2 (en) * 2010-06-21 2014-07-22 Outokumpu Vdm Gmbh Nickel-based alloy
US20120256530A1 (en) * 2010-10-26 2012-10-11 Ngk Spark Plug Co., Ltd. Spark plug
US8866370B2 (en) * 2010-10-26 2014-10-21 Ngk Spark Plug Co., Ltd. Spark plug
CN102651538A (en) * 2011-02-25 2012-08-29 株式会社电装 Electrode material for electrode of spark plug
US20120217433A1 (en) * 2011-02-25 2012-08-30 Hitachi Metals, Ltd. Electrode material for electrode of spark plug
US8915226B2 (en) * 2011-02-25 2014-12-23 Denso Corporation Electrode material for electrode of spark plug
US9932656B2 (en) 2013-03-14 2018-04-03 Vdm Metals International Gmbh Nickel-based alloy with silicon, aluminum, and chromium
US9360051B2 (en) 2013-04-03 2016-06-07 Nidec Gpm Gmbh Shaft bearing with a shaft seal
US20170009704A1 (en) * 2015-07-06 2017-01-12 Rohr, Inc. Thrust reverser staggered translating sleeve

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Publication number Publication date
DE102006035111A1 (en) 2008-02-07
JP2009544855A (en) 2009-12-17
JP5273620B2 (en) 2013-08-28
DE102006035111B4 (en) 2010-01-14
EP2047004A1 (en) 2009-04-15
RU2399690C1 (en) 2010-09-20
MX2009000987A (en) 2009-02-06
BRPI0715515B1 (en) 2015-08-04
WO2008014741A1 (en) 2008-02-07
EP2047004B1 (en) 2011-05-18
PL2047004T3 (en) 2011-10-31
ATE510034T1 (en) 2011-06-15
BRPI0715515A2 (en) 2013-03-05

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