EP2430204B1 - Legierung auf nickelbasis für ventilsitzeinsätze - Google Patents

Legierung auf nickelbasis für ventilsitzeinsätze Download PDF

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Publication number
EP2430204B1
EP2430204B1 EP10767419.4A EP10767419A EP2430204B1 EP 2430204 B1 EP2430204 B1 EP 2430204B1 EP 10767419 A EP10767419 A EP 10767419A EP 2430204 B1 EP2430204 B1 EP 2430204B1
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EP
European Patent Office
Prior art keywords
alloy
weight percent
valve seat
seat insert
nickel
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Application number
EP10767419.4A
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English (en)
French (fr)
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EP2430204A4 (de
EP2430204A2 (de
Inventor
Cong Yue Qiao
Daniel W. Bancroft
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LE Jones Co
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LE Jones Co
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Publication of EP2430204A4 publication Critical patent/EP2430204A4/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
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • 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
    • C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2301/00—Using particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2820/00—Details on specific features characterising valve gear arrangements
    • F01L2820/01—Absolute values

Definitions

  • the invention relates to nickel based alloys having high hardness and compressive yield strength. Such alloys are especially useful for engine parts such as valve seat inserts.
  • Nickel based valve seat insert alloys generally have wear resistance, heat resistance, and corrosion resistance superior to those of high alloy steels, and are therefore often used as materials for structural members serving under severe conditions, such as valve seat inserts.
  • Known nickel based alloys used for exhaust valve seat inserts such as an alloy identified as J96 and marketed by L. E. Jones Company, have relatively good characteristics, including good hardness and compressive yield strengths.
  • Another alloy marketed by L. E. Jones is J89, details of which are provided in U.S. Patent No. 6,482,275 .
  • the J89 alloy includes, in weight percent (as used herein "percent” and “%” refer to percent by weight unless otherwise indicated), 2.25 to 2.6 % C, up to 0.5 % Mn, up to 0.6 % Si, 34.5 to 36.5 % Cr, 4.00 to 4.95 % Mo, 14.5 to 15.5 % W, 5.25 to 6.25 % Fe, balance Ni plus incidental impurities.
  • a nickel based alloy comprising, in weight percentage: carbon from 0.5 to 1.5; chromium from 25 to 35; tungsten from 12 to 18; iron from 3.5 to 8.5; molybdenum from 1 to 8; manganese up to 0.50; silicon up to 1.0; up to a total of 1.5% Co, vanadium, titanium, niobium, hafnium, zirconium, tantalum, rare earth, yttrium, copper, sulphur, phosphorous, nitrogen and the balance nickel and incidental impurities.
  • the alloy is suitable for valve seat insert applications in internal combustion engines.
  • the nickel based alloy described herein (referred to as “the J91 alloy”) has been designated to promote machinability while maintaining desired hardness and wear resistance at elevated temperatures. Through adjustments in carbon, chromium, nickel and tungsten contents, it is possible to provide a matrix material which is free of coarse primary carbides yet exhibits desired wear resistance properties.
  • the microstructure of the J91 alloy can be characterized as spheroidal or egg-shaped eutectic domains interspersed with a Ni-rich FCC phase and thus provide desired wear resistance properties without reliance on coarse primary carbides.
  • the J91 alloy can exhibit high compressive yield strength, good corrosion resistance and good oxidation resistance.
  • J91 alloy is not limited in its application to the details of the composition and concentrations of components set forth in the following description.
  • the J91 alloy is capable of other embodiments and of being practiced or being carried out in various ways. Also, it is understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
  • the J91 alloy is designed particularly for use in internal combustion engine valve seat inserts, other applications are feasible.
  • the J91 alloy is based on experimental findings that hardness and compressive yield strength of the nickel based alloys can be obtained by removal of coarse primary carbides and creating an evenly distributed face centered cubic (FCC) nickel-solid solution phase in eutectic reaction phases matrix in which additional strengthening solutes can be introduced.
  • FCC face centered cubic
  • Carbon (C) is present in the J91 alloy in an amount ranging from 0.5 to 1.5 weight percent of the total alloy; preferably, about 0.95 to about 1.3 weight percent.
  • the J91 alloy surprisingly exhibits wear resistance properties equivalent to that of the J89 alloy but with a much lower carbon content. Whereas the J89 alloy relies on the presence of coarse primary carbides to achieve wear resistance, the J91 alloy which is preferably free of coarse primary carbides can achieve desired wear resistance in an as-cast condition through an improved wear resistant matrix microstructures.
  • Ni, Cr and W contents it is possible to increase the amount of eutectic structure through ternary eutectic reactions which produce spheroidal or egg-shaped eutectic domains interspersed with a Ni-rich FCC phase.
  • Chromium (Cr) is present in the alloy in an amount ranging from 25 to 35 weight percent of the total alloy, preferably 27 to 33 weight percent, and more preferably 28.5 to 31.5 weight percent of the total alloy.
  • the chromium content can be selected such that the relative amounts of Cr, Ni and W move the J91 alloy closer to the center of the eutectic center point of the Ni-W-Cr ternary phase diagram so as to promote the tendency for intermetallic phase(s) formation between W and Ni.
  • Tungsten (W) is present in the alloy in an amount ranging from 12 to 18 weight percent of the total alloy.
  • the tungsten content is at least 14 weight percent and at most 16 weight percent.
  • a more preferred W content is about 14.5 to about 15.5 %.
  • Iron (Fe) is present in the alloy in an amount ranging from 3.5 to 8.5 weight percent of the total alloy; preferably, at least 5 weight percent and at most 7 weight percent.
  • a preferred Fe content is 5.25 % to about 8.25%.
  • Molybdenum is present in the alloy in an amount ranging from 1 to 8 weight percent of the total alloy. Generally, greater molybdenum increases alloy hardness and decreases carbide size; however, too much molybdenum may result in a brittle product.
  • the weight percent molybdenum is preferably at least 2 weight percent and at most 6.25 weight percent. More preferably, the alloy contains about 4 to 5 weight percent Mo, most preferably the Mo content is 4.35 % to 4.95 %.
  • Manganese (Mn) can be added or present in an amount of up to about 0.5 weight percent of the total alloy.
  • a preferred Mn content is about 0.25 % to about 0.5 %.
  • Silicon (Si) may be added to or present in the alloy at levels up to 1.0 weight percent of the total alloy.
  • a preferred Si content is 0.15 % to 0.60 %.
  • the alloy may contain other intentionally added elements up to a total of 1.5 weight percent. These elements are cobalt (Co), vanadium (V), titanium (Ti), niobium (Nb), hafnium (Hf), zirconium (Zr), tantalum (Ta), rare earth, yttria (Y), copper (Cu), sulfur (S), phosphorus (P), nitrogen (N) or other elements.
  • the alloy may include up to 0.5% V, up to 0.5% Co, up to 0.03% P, up to 0.03% S.
  • the balance of the alloy is nickel (Ni) and incidental impurities. Generally, the alloy contains at least 30 weight percent nickel. A preferred Ni content is 35 to 45 %. Thus, the alloy preferably consists essentially of C, Cr, W, Mo, Fe, Ni, Mn and Si. As used herein "consisting essentially of' excludes additions which adversely affect machinability and wear properties of the alloy.
  • the matrix material between the carbides preferably contains a three-phase eutectic composition of the elements Cr--Ni--W, which provides increased strength.
  • the relative concentration of Cr--Ni--W necessary to form a three-phase eutectic composition may be determined by reference to a Cr--Ni--W ternary component phase diagram. Such phase diagrams are shown, for example, on page 3-48 of the ASM Handbook, Copyright 1992, Volume 3 , which is herein incorporated by reference.
  • the alloy comprises: Element Weight Percent Range C 0.95-1.3 Cr 28.5-31.5 Mo 4.35-4.95 W 14.5-15.5 Fe 5.25-8.25 Si 0.15-0.6 Mn 0.25-0.50 V up to 0.5 Co up to 0.5 S up to 0.03 P up to 0.03 Ni balance other elements up to 1.5
  • Metal parts can be made from the alloy by casting or forming from a powder and sintering, or the alloy can be used as a coating to hardface parts.
  • the alloy is manufactured by casting. Casting is a conventional process in which raw materials are added together and melted to liquid state, and then poured into a cast mold.
  • the metal parts are valve seat inserts made by casting or powder metallurgy for use in internal combustion engines.
  • the thermal expansion coefficient of the alloy tends to be closer to that of iron than nickel.
  • the thermal expansion coefficient of cast iron is approximately 11.5 x 10 -6 mm/mm °C. at a temperature of 25-600°C.
  • the J91 alloy has good high temperature compressive yield strength which increases wear resistance and decreases material yielding during operation. Decreased yielding serves to improve insert retention.
  • the alloy has a compressive yield strength of at least about 110 thousand pounds per square inch (KSI) at room temperature; more preferably, at least about 130 KSI at room temperature.
  • KSI thousand pounds per square inch
  • Increased hot hardness contributes to improved wear resistance and provides a safety factor for inserts which run beyond the normal operating temperature.
  • the J91 alloy possesses a matrix composed of eutectic reaction phases along with a small amount of randomly distributed FCC nickel solid solution phase.
  • the nickel solid solution phase is distributed along the grain boundaries of eutectic phases.
  • An optical light microscope (OLM) photomicrograph and a scanning electron microscope (SEM) photomicrograph exhibiting typical J91 microstructures are depictured in Figures 1 and 2 , respectively.
  • a heat of J89 (Heat No. 7K17K) and a heat of J91 (Heat No. 8L15XA) were employed for the optical light microscopic microstructural characterization.
  • a heat of J91 Heat No.
  • Typical bulk hardness of alloy J91 is Rockwell C (HRC) of 48 to 52, preferably about 49 to 51. Thus, alloy J91 possesses a bulk hardness in between that for J96 (HRC 40) and J89 (HRC 55).
  • the wear resistance of alloy J91 under engine wear conditions is expected to be similar to J89.
  • a comparison of wear resistance as a function of test temperature for J91, J3, J130, and J160 vs Pyromet 31 V valve material is exhibited in Figure 3 and Table 8, respectively.
  • J91 exhibited overall the least total materials wear among the four materials pairs evaluated. Within the lower test temperature range (ambient to 250°C), J91 showed a similar wear resistance to alloys J130 and J160 when paired with Pyromet 31 V valve material. Table 8. Summary of the Plint wear test results.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Powder Metallurgy (AREA)
  • Lift Valve (AREA)

Claims (15)

  1. Eine Legierung auf Nickelbasis, bestehend aus, in Gewichtsprozent: 0,5 bis 1,5 Kohlenstoff, 25 bis 35 Chrom, 12 bis 18 Wolfram, 3,5 bis 8,5 Eisen, 1 bis 8 Molybdän, bis zu etwa 0,50 Mangan, bis zu etwa 1,0 Silicium, insgesamt bis zu 1,5 Cobalt, Vanadium, Titan, Niob, Hafnium, Zirconium, Tantal, Seltenerden, Yttrium, Kupfer, Schwefel, Phosphor oder Stickstoff, und als Rest 30 bis 45 Nickel und zufällige Verunreinigungen.
  2. Die Legierung nach Anspruch 1, wobei die Legierung 0,95 bis 1,30 Gew.-% Kohlenstoff umfasst.
  3. Die Legierung nach Anspruch 1, wobei die Legierung 28,5 bis 30,5 Gew.-% Chrom umfasst.
  4. Die Legierung nach Anspruch 1, wobei die Legierung wenigstens 14,0 Gew.-% Wolfram umfasst.
  5. Die Legierung nach Anspruch 1, wobei die Legierung wenigstens 5,0 Gew.-% Eisen und höchstens 7,0 Gew.-% Eisen umfasst.
  6. Die Legierung nach Anspruch 1, wobei die Legierung 4,35 bis 4,95 Gew.-% Molybdän umfasst.
  7. Die Legierung nach Anspruch 1, wobei die Legierung höchstens 1,3 Gew.-% Kohlenstoff umfasst, oder wobei die Legierung höchstens 32,0 Gew.-% Chrom umfasst, oder wobei die Legierung höchstens 16,0 Gew.-% Wolfram umfasst.
  8. Die Legierung nach Anspruch 1, wobei die Legierung 40 bis 42 Gew.-% Nickel umfasst, oder wobei die relative Konzentration von Cr, Ni und W derart ist, dass sich bei einer Temperatur von etwa 800°C eine dreiphasige eutektische Zusammensetzung bildet.
  9. Die Legierung nach Anspruch 1, wobei die Legierung im Wesentlichen besteht aus, in Gewichtsprozent: 0,95 bis 1,3 Kohlenstoff, 28,5 bis 31,5 Chrom, 14,5 bis 15,5 Wolfram, 5,25 bis 8,25 Eisen, 4,35 bis 4,95 Molybdän, 0,25 bis 0,5 Mangan, 0,15 bis 0,6 Silicium, bis zu etwa 0,5 Vanadium, bis zu etwa 0,5 Cobalt, bis zu etwa 0,03 Schwefel, bis zu etwa 0,03 Phosphor, 38 bis 42 Nickel, und zufällige Verunreinigungen.
  10. Die Legierung nach Anspruch 1 oder Anspruch 9, wobei die Legierung ein Guss ist.
  11. Die Legierung nach Anspruch 1, wobei die Legierung ein Ventilsitzring für einen Verbrennungsmotor ist, oder wobei die Legierung eine Mikrostruktur im Gusszustand besitzt, die eine verschleißfeste Matrix aus sphäroidischen eutektischen Domänen, frei von groben primären Carbiden, umfasst.
  12. Ein Ventilsitzring zur Verwendung in einem Verbrennungsmotor, wobei der Ventilsitzring aus der Legierung nach Anspruch 1 hergestellt ist.
  13. Der Ventilsitzring nach Anspruch 12, wobei der Ventilsitzring ein Guss ist.
  14. Der Ventilsitzring nach Anspruch 12, wobei die Legierung besteht aus, in Gewichtsprozent: 0,95 bis 1,3 Kohlenstoff, 28,5 bis 31,5 Chrom, 14,5 bis 15,5 Wolfram, 5,25 bis 8,25 Eisen, 4,35 bis 4,95 Molybdän, 0,25 bis 0,5 Mangan, 0,15 bis 0,6 Silicium, insgesamt nicht mehr als 0,5 Vanadium und Cobalt, nicht mehr als 0,03 Schwefel, nicht mehr als 0,03 Phosphor, und als Rest Nickel und zufällige Verunreinigungen.
  15. Der Ventilsitzring nach Anspruch 12, der eine Rockwell-C-Härte von 48 bis 52 besitzt.
EP10767419.4A 2009-04-24 2010-04-21 Legierung auf nickelbasis für ventilsitzeinsätze Active EP2430204B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/429,837 US20100272597A1 (en) 2009-04-24 2009-04-24 Nickel based alloy useful for valve seat inserts
PCT/US2010/001177 WO2010123552A2 (en) 2009-04-24 2010-04-21 Nickel based alloy useful for valve seat inserts

Publications (3)

Publication Number Publication Date
EP2430204A2 EP2430204A2 (de) 2012-03-21
EP2430204A4 EP2430204A4 (de) 2015-09-02
EP2430204B1 true EP2430204B1 (de) 2018-07-04

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US (1) US20100272597A1 (de)
EP (1) EP2430204B1 (de)
CN (1) CN102439184B (de)
HK (1) HK1168391A1 (de)
WO (1) WO2010123552A2 (de)

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DK177487B1 (en) 2012-07-06 2013-07-15 Man Diesel & Turbo Deutschland An exhaust valve spindle for an exhaust valve in an internal combustion engine
JP6065580B2 (ja) 2012-12-25 2017-01-25 住友電気工業株式会社 内燃機関用材料の評価試験方法
US10519529B2 (en) 2013-11-20 2019-12-31 Questek Innovations Llc Nickel-based alloys
US9638075B2 (en) * 2013-12-02 2017-05-02 L.E. Jones Company High performance nickel-based alloy
CN103882265B (zh) * 2014-02-26 2016-05-25 蚌埠市英路光电有限公司 一种排气阀用镍基高温合金材料及其制备方法
US11353117B1 (en) 2020-01-17 2022-06-07 Vulcan Industrial Holdings, LLC Valve seat insert system and method
US11421680B1 (en) 2020-06-30 2022-08-23 Vulcan Industrial Holdings, LLC Packing bore wear sleeve retainer system
US11421679B1 (en) 2020-06-30 2022-08-23 Vulcan Industrial Holdings, LLC Packing assembly with threaded sleeve for interaction with an installation tool
US11384756B1 (en) 2020-08-19 2022-07-12 Vulcan Industrial Holdings, LLC Composite valve seat system and method
USD997992S1 (en) 2020-08-21 2023-09-05 Vulcan Industrial Holdings, LLC Fluid end for a pumping system
USD980876S1 (en) 2020-08-21 2023-03-14 Vulcan Industrial Holdings, LLC Fluid end for a pumping system
USD986928S1 (en) 2020-08-21 2023-05-23 Vulcan Industrial Holdings, LLC Fluid end for a pumping system
US11391374B1 (en) 2021-01-14 2022-07-19 Vulcan Industrial Holdings, LLC Dual ring stuffing box
US11434900B1 (en) 2022-04-25 2022-09-06 Vulcan Industrial Holdings, LLC Spring controlling valve
US11920684B1 (en) 2022-05-17 2024-03-05 Vulcan Industrial Holdings, LLC Mechanically or hybrid mounted valve seat

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Also Published As

Publication number Publication date
CN102439184B (zh) 2014-07-02
EP2430204A4 (de) 2015-09-02
US20100272597A1 (en) 2010-10-28
HK1168391A1 (en) 2012-12-28
WO2010123552A3 (en) 2011-01-27
WO2010123552A2 (en) 2010-10-28
EP2430204A2 (de) 2012-03-21
CN102439184A (zh) 2012-05-02

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