WO2008007190A2 - Wear resistant high temperature alloy - Google Patents

Wear resistant high temperature alloy Download PDF

Info

Publication number
WO2008007190A2
WO2008007190A2 PCT/IB2007/001860 IB2007001860W WO2008007190A2 WO 2008007190 A2 WO2008007190 A2 WO 2008007190A2 IB 2007001860 W IB2007001860 W IB 2007001860W WO 2008007190 A2 WO2008007190 A2 WO 2008007190A2
Authority
WO
WIPO (PCT)
Prior art keywords
alloy
weight
alloys
elements
present
Prior art date
Application number
PCT/IB2007/001860
Other languages
French (fr)
Other versions
WO2008007190A3 (en
Inventor
Maria K. Sawford
Shubhayu Sinharoy
Sundaram Narasimhan
Alojz Kajinic
Andrzej L. Wojcieszynski
Jeryl K. Wright
Original Assignee
Eaton Corporation
Crucible Materials Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eaton Corporation, Crucible Materials Corporation filed Critical Eaton Corporation
Priority to CA2658234A priority Critical patent/CA2658234C/en
Priority to EP07804566.3A priority patent/EP2038444B1/en
Priority to BRPI0713237A priority patent/BRPI0713237B1/en
Priority to CN2007800257108A priority patent/CN101484597B/en
Priority to JP2009518991A priority patent/JP5302192B2/en
Publication of WO2008007190A2 publication Critical patent/WO2008007190A2/en
Publication of WO2008007190A3 publication Critical patent/WO2008007190A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01LCYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00Lift-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
    • F01L3/02Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01LCYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2301/00Using particular materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01LCYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2303/00Manufacturing of components used in valve arrangements

Definitions

  • the present invention relates to a Fe-Ni-based alloy that has improved wear resistance at high temperature over Ni-based superalloys.
  • the alloy is particularly useful for manufacturing engine exhaust valves and other high temperature engine components.
  • High temperature strength, abrasion resistance and corrosion/oxidation resistance are required for materials of exhaust valves, which are generally subjected to temperatures exceeding 800 0 C.
  • the exhaust valves used in most reciprocating engines can generally be divided into three sections; the head, stem and stem tip.
  • the head and a portion of the head leading from the stem consist of a high temperature, high strength and corrosion resistant alloy such as an austenitic stainless steel or a superalloy.
  • the sealing surface of the valve often includes a weld overlay material, such as a cobalt based, high temperature alloy.
  • the remainder of the stem often is made of a hardenable martensitic steel welded to the high-temperature heat-resistant alloy of the valve head end.
  • Austenitic stainless steels such as 21-2N, 21-4N-Nb-W and 23-8N have been used for the manufacture of engine valves for many decades. However, due to mechanical property limitations, these alloys are not suitable at operating temperatures above 1472°F (800 0 C) for current durability expectations.
  • Superalloys including Fe-Ni-based and Ni-based alloys, have been used for exhaust valve applications typically when the less expensive iron- based stainless valve steel would not provide sufficient high-temperature strength or corrosion resistance, or both, for a given application.
  • Some of the higher nickel alloys used for valve applications include Alloy 751 , Alloy 8OA, Pyromet 31 and Ni30, for example. Alloys 751, 8OA and Pyromet 31 contain high amounts of Ni and are therefore expensive. Valves manufactured from these higher content Ni alloys are susceptible to abrasive and adhesive wear on the seat face due to the lack of wear resistance. Therefore, valves manufactured from some of the higher Ni alloys must be hard faced with a Co-based alloy on the seat face to improve wear resistance.
  • a wear resistant alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1% Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1% to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities; wherein Mo +0.5W ⁇ 0.75%; Ti+Nb > 4.5% and 13 ⁇ (Ti + Nb)/C ⁇ 50, also on a weight percentage basis.
  • an engine valve for a motor vehicle that comprises an alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1 % Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1% to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities; wherein Mo +0.5W ⁇ 0.75%; Ti+Nb > 4.5% and 13 ⁇ (Ti + Nb)/C ⁇ 50, on a weight percentage basis.
  • FIG. 1A and FIG. 1B are optical photomicrographs of the alloy of Example 4 of the present invention and a comparative alloy, respectively.
  • FIG. 2 is a bar graph of the relative wear depths of an embodiment of an exhaust valve the present invention and comparative alloy exhaust valves.
  • FIG. 3 is a graph of the hot hardness versus temperature for an embodiment of the alloy of the present invention and several comparative alloys.
  • FIG. 4 is a bar graph of the fatigue endurance limit determined using a standard RR Moore type rotating beam test at 816°C at 10 8 cycles for an embodiment of the present invention and several comparative alloys.
  • FIG. 5 is a bar graph of the fatigue endurance limit determined using a standard RR Moore type rotating beam test at 871 0 C at 10 8 cycles for an embodiment of the present invention and several comparative alloys.
  • the present invention relates to an iron-nickel-based alloy.
  • the hot hardness, high temperature strength, fatigue strength and wear resistance of the alloy make it useful in a variety of high temperature applications.
  • the alloy is particularly useful in internal combustion engines as cylinder head intake valves, exhaust valves and exhaust gas recirculation valves.
  • Other applications of the alloy include turbine applications, fasteners, afterburner parts, combustion chamber parts, shields for exhaust system oxygen sensors and other parts exposed to elevated temperature and exhaust gas and condensate environments.
  • Iron-based alloys achieve high temperature mechanical properties through precipitation hardening and solid solution strengthening.
  • the desired properties of iron-based alloys are developed by heat treatment sequences usually involving solution treatment to dissolve strengthening constituents, followed by aging heat treatments to precipitate phases in morphologies and distributions that will produce the desired mechanical properties.
  • the precipitation of a finely dispersed, stable and ordered intermetallic phase, (Fe,Ni) 3 (AI, Ti 1 Nb), commonly referred to as gamma prime ( ⁇ ! ) contributes to the high temperature strength of the alloy.
  • the alloy contains primary carbides and carbonitrides for enhanced wear resistance.
  • the alloy in one embodiment, comprises in weight percent, 0.15% up to 0.35% C; up to 1% Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1 % to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities.
  • Carbon may be present in the alloy in an amount ranging from 0.15% to about 0.35% by weight. In one embodiment, carbon is present in an amount of greater than 0.15% to about 0.3%, or from about 0.16% to about 0.3% by weight. Improved wear resistance properties are attributed, at least in part, to the microstructure and hardness of the alloy. Carbon is added to the alloy to promote the formation of niobium-titanium rich primary carbides during ingot solidification. In one embodiment of the invention, the total primary carbide volume fraction of the alloy is greater than 1 % and up to 4%. These primary carbides positively influence the adhesive and abrasion wear resistance of the alloy, particularly at elevated temperatures.
  • Chromium may be present in the alloy in an amount of 15 to about 25 weight percent. In one embodiment, chromium is present in an amount between about 15 to about 20 weight percent. Chromium provides a desirable combination of corrosion resistance such as resistance to acid attack, wear resistance and oxidation resistance. The chromium in the alloy is believed to form a tenacious chromium oxide scale on the surface of the alloy that inhibits progressive high temperature oxidation formation and minimizes oxidation, corrosion and wear rates.
  • Nickel is added to stabilize the austenitic matrix and to promote the formation of the y' phase, which improves the high temperature strength of the alloy.
  • Nickel can also advantageously increase resistance to attack from acids formed from exhaust condensates, resistance to oxidation and lead (Pb) corrosion and can also increase the hardness.
  • Pb oxidation and lead
  • nickel can increase low temperature wear rates and add to the cost of the alloy.
  • the nickel content is within the range of greater than 25% to less than 40% by weight. In one embodiment, the Ni content is greater than 25% to about 35% by weight, or about 29% to about 35% by weight, or about 30% to about 35%. Higher levels of nickel have also been shown to cause significant sulfidation attack due to the high affinity of nickel to sulfur based constituents present in the engine oil or certain fuels.
  • Aluminum may be present in the alloy in an amount greater than 1.6% by weight and up to 3% by weight. Aluminum enhances the high temperature strength of the alloy by combining with Ni to precipitate the y' phase. When the aluminum content is lower than 1.6%, the ⁇ J phase becomes unstable and can transform to the ⁇ [(Fe,Ni) 3 (Ti, Al)] phase which degrades the mechanical properties of the alloy. In one embodiment, the Al content is between 1.63 % to about 2.3% by weight.
  • the titanium content of the alloy is about 1% to about 3.5% by weight. In one embodiment, the Ti content is about 2.0% to about 3.5% by weight.
  • the high temperature strength of the alloy of the invention is enhanced by the precipitation of the ⁇ ! phase, which includes titanium, aluminum, iron and nickel. If the titanium content is too high, the workability of the alloy may decrease and the high temperature strength and toughness deteriorate because the deleterious ⁇ phase is liable to precipitate. In addition, the titanium combines with carbon and niobium to precipitate the primary carbides that are necessary for wear resistance.
  • Niobium may be present in the alloy in an amount greater than 1.1% up to about 3.0% by weight. In one embodiment, Nb is present in an amount ranging from about 1.8% to about 2.5% by weight. Niobium partitions to both the Y' phase and the primary carbides. The primary carbides impart wear resistance to the alloy. Due to the chemical similarity between Nb and Ta, Ta can replace some of the Nb. However, the cost of Ta is high, so that a large amount of Ta may be prohibitive. The amount of Nb and Ta together may be 1.1% to about 3.0% by weight, or about 1.8% to about 2.5% by weight.
  • the alloy should contain a minimum amount of the carbide forming elements Ti and Nb.
  • the elements of the alloy satisfy the equation: Ti + Nb ⁇ 4.5, based on weight percent of the elements in the alloy.
  • the amount of carbide forming elements must be balanced with the carbon content to achieve the desired wear resistance through the precipitation of primary carbides.
  • the ratio of carbide forming elements to carbon content in one embodiment, is generally in the range of 13 ⁇ (Ti + Nb)/C ⁇ 50, based on the weight percent of the elements in the alloy. In one embodiment, the ratio is within the range 15 ⁇ (Ti + Nb)/C ⁇ 35, or within the range 17 ⁇ (Ti + Nb)/C ⁇ 30.
  • the boron content in the alloy may be up to about 0.015% by weight. In one embodiment, the boron content is between from about 0.010% to 0.015% by weight.
  • Molybdenum may be present in the alloy in an amount up to about 0.5% by weight. In one embodiment, the amount of Mo is from about 0.05% to about 0.5% by weight. In one embodiment, molybdenum is not intentionally added to the alloy, but may be present as an inevitable impurity. Molybdenum may be added in an amount effective to promote solid solution hardening of the alloy and provide resistance to creep of the alloy when exposed to elevated temperatures. Molybdenum can also combine with carbon to form primary carbides.
  • Tungsten may be present in the alloy in an amount up to about 0.5% by weight. In one embodiment, the amount of W is from between about 0.05 to about 0.25% by weight. In one embodiment, tungsten is not intentionally added to the alloy, but may be present as an inevitable impurity. Like molybdenum, tungsten may be added to the alloy to promote solid solution hardening of the alloy and provide resistance to creep of the alloy when exposed to elevated temperatures. In one embodiment, the amount (by weight percent) of molybdenum and tungsten in the alloy satisfies the equation: Mo + 0.5W ⁇ 0.75%.
  • silicon may be present in an amount up to about 1.0 weight percent.
  • Manganese may be present in an amount up to about 1.0 weight percent. Silicon and manganese can form a solid solution with iron and increase the strength of the alloy through solid solution strengthening as well as increase the resistance to oxidation. When the alloy is formed into parts by casting, the addition of silicon and manganese can contribute to de- oxidation and/or degassing of the alloy. Silicon can also improve the castability of the material. In the case where the part is not cast, silicon and manganese can be reduced or omitted from the alloy.
  • the balance of the alloy is preferably iron (Fe) and incidental impurities.
  • the alloy can contain trace amounts of sulphur, nitrogen, phosphorous and oxygen. Other alloy additions that do not adversely affect corrosion, wear and/or hardness properties of the alloy may be added to the alloy.
  • the alloy does not contain any intentionally added vanadium.
  • the presence of significant amounts of vanadium may adversely affect the desirable properties of the alloy due to the formation of the low melting temperature oxide, V 2 O 5 .
  • the alloy does not contain any intentionally added copper, which is generally added when the alloy will be cold worked into the desired geometry.
  • the alloy of the present invention has good pin abrasion wear resistance. In one embodiment, the alloy has a pin abrasion wear loss of less than 100 mg after solution treating and aging.
  • the alloy of the present invention can be prepared using conventional practices.
  • the elemental materials may be melted by vacuum induction melting, air induction melting, arc melting/AOD (argon-oxygen decarburization), ESR (electoslag remelting), or combinations thereof.
  • the melted materials are then cast into ingots.
  • Each of the resulting ingots is then subjected to a soaking treatment, and then scarfed, and further subjected to forging and rolling to form a bar.
  • Alloys of the invention shown in Table 1 are produced in the form of 50 Ib. (22.7kg) ingots by vacuum induction melting, and forged into octagonal bars 1 inch in diameter. Mechanical test specimens are cut from the bars and are solution treated at 1650 0 F (900 0 C) for 30 minutes, air or water cooled, and then aged at 1350°F (730°C) for 4 hours and air cooled. Examples 1-8 are embodiments of the present invention and Alloys A-G are comparative alloys. Comparative alloys A, C and D are commercially available superalloys and comparative alloys E-G are commercially available austenitic valve steels. Alloy B is a modification of Alloy A, wherein the amount of carbon is increased to show the effect of carbon on the mechanical properties of Alloy A.
  • the alloys of the present invention require solution treating at 1650°F (899°C) for 30 minutes and aging at 1350 0 F (732°C) for four hours to produce a hardness of 36/39 HRC.
  • the solution treating temperature is lower than that typically used to solution treat commercially available superalloys including the Alloys A, C and D. These superalloys are typically solution treated at 1950 0 F (1066 0 C) and above and generally require a two-step aging process to produce adequate hardness.
  • the alloys of the present invention can be aged in a single step at one temperature for adequate hardness response.
  • the etched microstructure of the alloy of Example 4 of the present invention that was solution treated at 1650 0 F (899 0 C) for 30 minutes and aged at 1350°F (732°C) for four hours is shown in FIG. 1A.
  • the etched microstructure of comparative Alloy A that was solution treated at 1950° (1066°C) for 30 minutes and aged at 1380 0 F (749°C) for four hours is shown in FlG. 1B.
  • These microstructures consist of primary carbides in an austenitic matrix. The primary carbides are those that precipitate during ingot solidification.
  • the primary carbides impart wear resistance to the alloy. As the volume fraction of primary carbides increase, the wear resistance of the alloy increases. The volume fraction of primary carbides in the alloys of Example 4 and comparative Alloy A are also shown in FIG. 1. The carbide volume fraction in the alloy of Example 4 is about 2.1%. The carbide volume fraction of comparative Alloy A is about 0.4%.
  • the abrasive wear resistance of the alloys was evaluated using a pin abrasive wear test according to ASTM G132. This test uses % inch diameter specimens that are heat treated to application hardness. A 15-Ib load is applied to the specimen as it rotates at 22 rpm. The specimen traverses 500 inches (12.7m) in a non-overlapping pattern on a 150 mesh garnet paper. The weight of the specimen before and after the test is used to determine the pin abrasion weight loss. The lower the weight loss, the more resistant the alloy is to abrasive wear. The data is given in Table 2. Example 4 has a weight loss of 93 mg, which is lower than that of the superalloys Alloys A through D.
  • the wear resistance is directly related to the amount of primary carbides (and, thus, the total titanium and niobium content) in an alloy.
  • Example 4 and Alloy A have a total carbide volume fraction of about 2.1% and 0.4%, respectively, and Example 4 has better wear resistance.
  • Increasing carbon content of Alloy A will not result in a sufficient increase in wear resistance, as evidenced by pin abrasion weight loss of Alloys A and B.
  • Additional titanium and niobium is needed to produce an alloy with sufficient wear resistance.
  • the commercial austenitic valve steels Alloys E and F have sufficient wear resistance for automotive exhaust valves so that hardfacing is not necessary.
  • the wear resistance of Example 4 is similar to that of Alloy E, which suggests that exhaust valves manufactured with an alloy similar to that of Example 4 may not need to be hardfaced.
  • Exhaust valves made from the alloy of Example 3 and the comparative alloys D and F were subjected to an elevated temperature simulation wear test.
  • the exhaust valves were tested at a valve seat face temperature of 1000 0 F (54O 0 C) under a load actuating the valve to simulate the combustion loads of about 500-550 lbs in a spark ignited internal combustion engine.
  • the mean wear depths (mm) were measured for the exhaust valves of Example 3 and those of comparative Alloy D and Alloy F.
  • the results, presented in FIG. 2 show that the mean wear depth of the exhaust valve of the present invention is less than that of each of the comparative exhaust valves.
  • the better wear resistance of the alloy of the present invention is believed to be attributed to the higher hardness and the presence of the primary carbides.
  • Hot hardness is the hardness measured at a given elevated temperature.
  • the hot hardness of an alloy also influences the wear resistance of the material. The higher the hot hardness the more wear resistant the alloy.
  • Hot hardness measurements are taken at room temperature and at temperatures between 1100°F (593°C) to 1400 0 F (76O 0 C). This test is conducted by placing a furnace around the specimen and indenter and the temperature within the furnace is slowly increased to the test temperature. The specimen is soaked at the temperature for about 30 minutes to ensure uniform heating throughout the specimen prior to testing the hardness. Hardness measurements are taken using the Rockwell A (HRA) scale. The hot hardness of the alloys of invention and the comparative commercially available alloys are shown in FIG. 3.
  • the hot hardness of the alloy of the invention is higher than that of comparative Alloys A, B, C and D, and much higher than the austenitic valve steels Alloys E and F.
  • the significant decrease in hot hardness in the austenitic valve steels is related to microstructural changes. This data further indicates the improved wear resistance of the alloys of invention.
  • the exhaust valves can be exposed to temperatures up to 1600 0 F (871 0 C). Therefore, the exhaust valve must have oxidation resistance.
  • Samples of the alloy of Example 2 and Alloy A were exposed at 1500 0 F (816°C) for 500hrs.
  • the depth of oxidation for the alloy of Example 2 is 0.0174 mm at 500 hours.
  • the depth of oxidation for Alloy A is 0.0333 mm at 500 hours. This indicates that Example 2 has improved oxidation resistance over Alloy A, a commercially available valve superalloy.
  • the elevated temperature tensile properties at 1500 0 F (816 0 C) of the alloy of Example 2 and of comparative valve alloys are given in Table 3.
  • the yield strength of the alloy of Example 2 is higher than that of Alloys A and B and much higher than the austenitic valve steels, Alloys F and G. Sufficient yield strength is needed to prevent the valve from deforming while operating in an engine.
  • the yield strength of the alloys of the invention as embodied by Example 2 is higher than that of other comparative commercially available Fe- based valve alloys, which indicates the alloys of invention have sufficient strength.
  • the tensile strength of the alloy of Example 2 is higher than that of Alloys B through G, and similar to that of Alloy A, which indicates that the alloys of the invention can be subjected to higher stress levels before catastrophic failure occurs. Table 3
  • the creep stress needed to rupture the alloys of invention and several comparative valve alloys in IOOhrs at 1500 0 F (816°C) is given in Table 4.
  • the creep rupture stress of the alloy of Example 2 is comparable to that of Alloys A and B and much better than the austenitic valve steels F and G.
  • the austenitic valve steels have sufficient creep rupture strength for exhaust valve applications to prevent failures due to creep in the fillet area of the valve. Therefore, the alloys of invention should also have sufficient creep strength to prevent failure.
  • Fatigue strength is needed to prevent fatigue related failures in the stem fillet area of a valve.
  • Rotating beam fatigue tests were conducted on the alloys of the invention and Alloys A, B and D at 1500 0 F (816°C) at 10 8 cycles with applied stresses of 25-45 ksi. The results are shown in FIG. 4.
  • the fatigue strength of the alloy of Example 3 of the invention is somewhat better than that of Alloys A and B. Therefore, the alloys of invention, as exemplified by Example 3, have sufficient fatigue strength for automotive valves.
  • the fatigue endurance limit of the alloy of Example 3 and that of comparative alloys B and D at 1600 0 F (871 0 C) at 10 8 cycles is shown in FIG. 5. At this temperature, the fatigue strength of the alloy of Example 3 is better that that of comparative Alloy B.
  • an engine valve for a motor vehicle comprising an alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1% Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1% to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities.
  • the engine valve alloy may contain elements that satisfy the following equation: Mo +0.5W ⁇ 0.75%, based on the weight percent of the elements in the alloy.
  • the alloy may contain the carbide containing elements titanium and niobium in amounts that satisfy the following equations: Ti+Nb ⁇ 4.5% and 13 ⁇ (Ti + Nb)/C ⁇ 50, on a weight percentage basis.
  • Exhaust valves made from the alloy of Example 3 were subjected to a 100 hour dyno test in a V-8 spark ignited gasoline engine and to a 500 hour dyno test in a heavy duty compression ignited diesel engine. The exhaust valves passed both wear tests, exhibiting acceptable wear resistance in each test.

Landscapes

  • 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)
  • Heat Treatment Of Articles (AREA)
  • Lift Valve (AREA)

Abstract

An Fe-Ni-based alloy that has improved wear resistance at high temperature over Ni-based superalloys is provided. The alloy is particularly useful for manufacturing engine exhaust valves and other high temperature engine components subjected to corrosion, wear and oxidation.

Description

TITLE: WEAR RESISTANT HIGH TEMPERATURE ALLOY
This application claims the benefit of U. S. Provisional Application Nos. 60/806,743 filed July 7, 2006 and 60/868,606 filed December 5, 2006, the contents of which are hereby incorporated by reference in their entirety.
Technical Field
The present invention relates to a Fe-Ni-based alloy that has improved wear resistance at high temperature over Ni-based superalloys. The alloy is particularly useful for manufacturing engine exhaust valves and other high temperature engine components.
Background
High temperature strength, abrasion resistance and corrosion/oxidation resistance are required for materials of exhaust valves, which are generally subjected to temperatures exceeding 8000C. The exhaust valves used in most reciprocating engines can generally be divided into three sections; the head, stem and stem tip. The head and a portion of the head leading from the stem consist of a high temperature, high strength and corrosion resistant alloy such as an austenitic stainless steel or a superalloy. The sealing surface of the valve often includes a weld overlay material, such as a cobalt based, high temperature alloy. The remainder of the stem often is made of a hardenable martensitic steel welded to the high-temperature heat-resistant alloy of the valve head end.
As improved internal combustion engines are developed, addressing the increasing temperatures resulting from higher fuel economy, reduced emissions and yet higher output through newly designed engines has prompted the need for new cost effective materials. In addition, because the demand for and cost of nickel is on the rise, alternatives for high nickel content alloys are desired.
Austenitic stainless steels such as 21-2N, 21-4N-Nb-W and 23-8N have been used for the manufacture of engine valves for many decades. However, due to mechanical property limitations, these alloys are not suitable at operating temperatures above 1472°F (8000C) for current durability expectations.
Superalloys, including Fe-Ni-based and Ni-based alloys, have been used for exhaust valve applications typically when the less expensive iron- based stainless valve steel would not provide sufficient high-temperature strength or corrosion resistance, or both, for a given application. Some of the higher nickel alloys used for valve applications include Alloy 751 , Alloy 8OA, Pyromet 31 and Ni30, for example. Alloys 751, 8OA and Pyromet 31 contain high amounts of Ni and are therefore expensive. Valves manufactured from these higher content Ni alloys are susceptible to abrasive and adhesive wear on the seat face due to the lack of wear resistance. Therefore, valves manufactured from some of the higher Ni alloys must be hard faced with a Co-based alloy on the seat face to improve wear resistance. This adds a manufacturing step that further increases the cost of the valve. Thus, there is a need for an intermediate strength valve alloy with properties and cost between that of the austenitic valve steels and the Ni-based superalloys such that the alloy has sufficient wear resistance without requiring a hard facing step.
Summary
In one aspect of the invention, there is provided a wear resistant alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1% Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1% to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities; wherein Mo +0.5W < 0.75%; Ti+Nb > 4.5% and 13 < (Ti + Nb)/C < 50, also on a weight percentage basis.
In another aspect of the invention, there is provided an engine valve for a motor vehicle that comprises an alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1 % Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1% to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities; wherein Mo +0.5W ≤ 0.75%; Ti+Nb > 4.5% and 13 < (Ti + Nb)/C < 50, on a weight percentage basis.
Brief Description of the Drawings
FIG. 1A and FIG. 1B are optical photomicrographs of the alloy of Example 4 of the present invention and a comparative alloy, respectively.
FIG. 2 is a bar graph of the relative wear depths of an embodiment of an exhaust valve the present invention and comparative alloy exhaust valves.
FIG. 3 is a graph of the hot hardness versus temperature for an embodiment of the alloy of the present invention and several comparative alloys.
FIG. 4 is a bar graph of the fatigue endurance limit determined using a standard RR Moore type rotating beam test at 816°C at 108 cycles for an embodiment of the present invention and several comparative alloys.
FIG. 5 is a bar graph of the fatigue endurance limit determined using a standard RR Moore type rotating beam test at 8710C at 108 cycles for an embodiment of the present invention and several comparative alloys.
Detailed Description
The present invention relates to an iron-nickel-based alloy. The hot hardness, high temperature strength, fatigue strength and wear resistance of the alloy make it useful in a variety of high temperature applications. The alloy is particularly useful in internal combustion engines as cylinder head intake valves, exhaust valves and exhaust gas recirculation valves. Other applications of the alloy include turbine applications, fasteners, afterburner parts, combustion chamber parts, shields for exhaust system oxygen sensors and other parts exposed to elevated temperature and exhaust gas and condensate environments.
Iron-based alloys achieve high temperature mechanical properties through precipitation hardening and solid solution strengthening. The desired properties of iron-based alloys are developed by heat treatment sequences usually involving solution treatment to dissolve strengthening constituents, followed by aging heat treatments to precipitate phases in morphologies and distributions that will produce the desired mechanical properties. In the invention alloys, the precipitation of a finely dispersed, stable and ordered intermetallic phase, (Fe,Ni)3(AI, Ti1Nb), commonly referred to as gamma prime (γ!), contributes to the high temperature strength of the alloy. In addition, the alloy contains primary carbides and carbonitrides for enhanced wear resistance.
The alloy, in one embodiment, comprises in weight percent, 0.15% up to 0.35% C; up to 1% Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1 % to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities.
Carbon may be present in the alloy in an amount ranging from 0.15% to about 0.35% by weight. In one embodiment, carbon is present in an amount of greater than 0.15% to about 0.3%, or from about 0.16% to about 0.3% by weight. Improved wear resistance properties are attributed, at least in part, to the microstructure and hardness of the alloy. Carbon is added to the alloy to promote the formation of niobium-titanium rich primary carbides during ingot solidification. In one embodiment of the invention, the total primary carbide volume fraction of the alloy is greater than 1 % and up to 4%. These primary carbides positively influence the adhesive and abrasion wear resistance of the alloy, particularly at elevated temperatures.
Chromium may be present in the alloy in an amount of 15 to about 25 weight percent. In one embodiment, chromium is present in an amount between about 15 to about 20 weight percent. Chromium provides a desirable combination of corrosion resistance such as resistance to acid attack, wear resistance and oxidation resistance. The chromium in the alloy is believed to form a tenacious chromium oxide scale on the surface of the alloy that inhibits progressive high temperature oxidation formation and minimizes oxidation, corrosion and wear rates.
Nickel is added to stabilize the austenitic matrix and to promote the formation of the y' phase, which improves the high temperature strength of the alloy. Nickel can also advantageously increase resistance to attack from acids formed from exhaust condensates, resistance to oxidation and lead (Pb) corrosion and can also increase the hardness. However, nickel can increase low temperature wear rates and add to the cost of the alloy. Thus, the nickel content is within the range of greater than 25% to less than 40% by weight. In one embodiment, the Ni content is greater than 25% to about 35% by weight, or about 29% to about 35% by weight, or about 30% to about 35%. Higher levels of nickel have also been shown to cause significant sulfidation attack due to the high affinity of nickel to sulfur based constituents present in the engine oil or certain fuels.
Aluminum may be present in the alloy in an amount greater than 1.6% by weight and up to 3% by weight. Aluminum enhances the high temperature strength of the alloy by combining with Ni to precipitate the y' phase. When the aluminum content is lower than 1.6%, the γJ phase becomes unstable and can transform to the η [(Fe,Ni)3(Ti, Al)] phase which degrades the mechanical properties of the alloy. In one embodiment, the Al content is between 1.63 % to about 2.3% by weight.
The titanium content of the alloy is about 1% to about 3.5% by weight. In one embodiment, the Ti content is about 2.0% to about 3.5% by weight. The high temperature strength of the alloy of the invention is enhanced by the precipitation of the γ! phase, which includes titanium, aluminum, iron and nickel. If the titanium content is too high, the workability of the alloy may decrease and the high temperature strength and toughness deteriorate because the deleterious η phase is liable to precipitate. In addition, the titanium combines with carbon and niobium to precipitate the primary carbides that are necessary for wear resistance.
Niobium may be present in the alloy in an amount greater than 1.1% up to about 3.0% by weight. In one embodiment, Nb is present in an amount ranging from about 1.8% to about 2.5% by weight. Niobium partitions to both the Y' phase and the primary carbides. The primary carbides impart wear resistance to the alloy. Due to the chemical similarity between Nb and Ta, Ta can replace some of the Nb. However, the cost of Ta is high, so that a large amount of Ta may be prohibitive. The amount of Nb and Ta together may be 1.1% to about 3.0% by weight, or about 1.8% to about 2.5% by weight.
To achieve a high level of wear resistance, the alloy should contain a minimum amount of the carbide forming elements Ti and Nb. In one embodiment, the elements of the alloy satisfy the equation: Ti + Nb ≥ 4.5, based on weight percent of the elements in the alloy. In addition, the amount of carbide forming elements must be balanced with the carbon content to achieve the desired wear resistance through the precipitation of primary carbides. The ratio of carbide forming elements to carbon content, in one embodiment, is generally in the range of 13 < (Ti + Nb)/C < 50, based on the weight percent of the elements in the alloy. In one embodiment, the ratio is within the range 15 < (Ti + Nb)/C < 35, or within the range 17 < (Ti + Nb)/C < 30.
Small amounts of boron can improve the strength of the alloy and can improve grain refinement. The distribution of boron can be both intragranular (within a grain) and intergranular (along grain boundaries). Excessive boron, however, can segregate to grain boundaries and degrade the toughness of the alloy. The boron content in the alloy may be up to about 0.015% by weight. In one embodiment, the boron content is between from about 0.010% to 0.015% by weight.
Molybdenum may be present in the alloy in an amount up to about 0.5% by weight. In one embodiment, the amount of Mo is from about 0.05% to about 0.5% by weight. In one embodiment, molybdenum is not intentionally added to the alloy, but may be present as an inevitable impurity. Molybdenum may be added in an amount effective to promote solid solution hardening of the alloy and provide resistance to creep of the alloy when exposed to elevated temperatures. Molybdenum can also combine with carbon to form primary carbides.
Tungsten may be present in the alloy in an amount up to about 0.5% by weight. In one embodiment, the amount of W is from between about 0.05 to about 0.25% by weight. In one embodiment, tungsten is not intentionally added to the alloy, but may be present as an inevitable impurity. Like molybdenum, tungsten may be added to the alloy to promote solid solution hardening of the alloy and provide resistance to creep of the alloy when exposed to elevated temperatures. In one embodiment, the amount (by weight percent) of molybdenum and tungsten in the alloy satisfies the equation: Mo + 0.5W < 0.75%.
In the alloys, silicon may be present in an amount up to about 1.0 weight percent. Manganese may be present in an amount up to about 1.0 weight percent. Silicon and manganese can form a solid solution with iron and increase the strength of the alloy through solid solution strengthening as well as increase the resistance to oxidation. When the alloy is formed into parts by casting, the addition of silicon and manganese can contribute to de- oxidation and/or degassing of the alloy. Silicon can also improve the castability of the material. In the case where the part is not cast, silicon and manganese can be reduced or omitted from the alloy.
The balance of the alloy is preferably iron (Fe) and incidental impurities. The alloy can contain trace amounts of sulphur, nitrogen, phosphorous and oxygen. Other alloy additions that do not adversely affect corrosion, wear and/or hardness properties of the alloy may be added to the alloy.
In one embodiment, the alloy does not contain any intentionally added vanadium. The presence of significant amounts of vanadium may adversely affect the desirable properties of the alloy due to the formation of the low melting temperature oxide, V2O5.
In one embodiment, the alloy does not contain any intentionally added copper, which is generally added when the alloy will be cold worked into the desired geometry.
The alloy of the present invention has good pin abrasion wear resistance. In one embodiment, the alloy has a pin abrasion wear loss of less than 100 mg after solution treating and aging.
The alloy of the present invention can be prepared using conventional practices. The elemental materials may be melted by vacuum induction melting, air induction melting, arc melting/AOD (argon-oxygen decarburization), ESR (electoslag remelting), or combinations thereof. The melted materials are then cast into ingots. Each of the resulting ingots is then subjected to a soaking treatment, and then scarfed, and further subjected to forging and rolling to form a bar.
EXAMPLES
Alloys of the invention shown in Table 1 are produced in the form of 50 Ib. (22.7kg) ingots by vacuum induction melting, and forged into octagonal bars 1 inch in diameter. Mechanical test specimens are cut from the bars and are solution treated at 16500F (9000C) for 30 minutes, air or water cooled, and then aged at 1350°F (730°C) for 4 hours and air cooled. Examples 1-8 are embodiments of the present invention and Alloys A-G are comparative alloys. Comparative alloys A, C and D are commercially available superalloys and comparative alloys E-G are commercially available austenitic valve steels. Alloy B is a modification of Alloy A, wherein the amount of carbon is increased to show the effect of carbon on the mechanical properties of Alloy A.
Table 1
Figure imgf000009_0001
* not intentionally added
Heat Treatment
The alloys of the present invention require solution treating at 1650°F (899°C) for 30 minutes and aging at 13500F (732°C) for four hours to produce a hardness of 36/39 HRC. The solution treating temperature is lower than that typically used to solution treat commercially available superalloys including the Alloys A, C and D. These superalloys are typically solution treated at 19500F (10660C) and above and generally require a two-step aging process to produce adequate hardness. The alloys of the present invention can be aged in a single step at one temperature for adequate hardness response. Microstructural Evaluation
The etched microstructure of the alloy of Example 4 of the present invention that was solution treated at 16500F (8990C) for 30 minutes and aged at 1350°F (732°C) for four hours is shown in FIG. 1A. The etched microstructure of comparative Alloy A that was solution treated at 1950° (1066°C) for 30 minutes and aged at 13800F (749°C) for four hours is shown in FlG. 1B. These microstructures consist of primary carbides in an austenitic matrix. The primary carbides are those that precipitate during ingot solidification.
The primary carbides impart wear resistance to the alloy. As the volume fraction of primary carbides increase, the wear resistance of the alloy increases. The volume fraction of primary carbides in the alloys of Example 4 and comparative Alloy A are also shown in FIG. 1. The carbide volume fraction in the alloy of Example 4 is about 2.1%. The carbide volume fraction of comparative Alloy A is about 0.4%.
Wear Resistance
The abrasive wear resistance of the alloys was evaluated using a pin abrasive wear test according to ASTM G132. This test uses % inch diameter specimens that are heat treated to application hardness. A 15-Ib load is applied to the specimen as it rotates at 22 rpm. The specimen traverses 500 inches (12.7m) in a non-overlapping pattern on a 150 mesh garnet paper. The weight of the specimen before and after the test is used to determine the pin abrasion weight loss. The lower the weight loss, the more resistant the alloy is to abrasive wear. The data is given in Table 2. Example 4 has a weight loss of 93 mg, which is lower than that of the superalloys Alloys A through D. The wear resistance is directly related to the amount of primary carbides (and, thus, the total titanium and niobium content) in an alloy. For example, Example 4 and Alloy A have a total carbide volume fraction of about 2.1% and 0.4%, respectively, and Example 4 has better wear resistance. Increasing carbon content of Alloy A will not result in a sufficient increase in wear resistance, as evidenced by pin abrasion weight loss of Alloys A and B. Additional titanium and niobium is needed to produce an alloy with sufficient wear resistance. The commercial austenitic valve steels Alloys E and F have sufficient wear resistance for automotive exhaust valves so that hardfacing is not necessary. The wear resistance of Example 4 is similar to that of Alloy E, which suggests that exhaust valves manufactured with an alloy similar to that of Example 4 may not need to be hardfaced.
Table 2
Figure imgf000011_0001
Wear Resistance (Exhaust Valves)
Exhaust valves made from the alloy of Example 3 and the comparative alloys D and F were subjected to an elevated temperature simulation wear test. The exhaust valves were tested at a valve seat face temperature of 10000F (54O0C) under a load actuating the valve to simulate the combustion loads of about 500-550 lbs in a spark ignited internal combustion engine. The mean wear depths (mm) were measured for the exhaust valves of Example 3 and those of comparative Alloy D and Alloy F. The results, presented in FIG. 2, show that the mean wear depth of the exhaust valve of the present invention is less than that of each of the comparative exhaust valves. The better wear resistance of the alloy of the present invention is believed to be attributed to the higher hardness and the presence of the primary carbides.
Hot Hardness
Hot hardness is the hardness measured at a given elevated temperature. The hot hardness of an alloy also influences the wear resistance of the material. The higher the hot hardness the more wear resistant the alloy. Hot hardness measurements are taken at room temperature and at temperatures between 1100°F (593°C) to 14000F (76O0C). This test is conducted by placing a furnace around the specimen and indenter and the temperature within the furnace is slowly increased to the test temperature. The specimen is soaked at the temperature for about 30 minutes to ensure uniform heating throughout the specimen prior to testing the hardness. Hardness measurements are taken using the Rockwell A (HRA) scale. The hot hardness of the alloys of invention and the comparative commercially available alloys are shown in FIG. 3. The hot hardness of the alloy of the invention is higher than that of comparative Alloys A, B, C and D, and much higher than the austenitic valve steels Alloys E and F. The significant decrease in hot hardness in the austenitic valve steels is related to microstructural changes. This data further indicates the improved wear resistance of the alloys of invention.
Oxidation Resistance
During engine operation, the exhaust valves can be exposed to temperatures up to 16000F (8710C). Therefore, the exhaust valve must have oxidation resistance. Samples of the alloy of Example 2 and Alloy A were exposed at 15000F (816°C) for 500hrs. The depth of oxidation for the alloy of Example 2 is 0.0174 mm at 500 hours. The depth of oxidation for Alloy A is 0.0333 mm at 500 hours. This indicates that Example 2 has improved oxidation resistance over Alloy A, a commercially available valve superalloy.
Elevated Temperature Tensile Properties
The elevated temperature tensile properties at 15000F (8160C) of the alloy of Example 2 and of comparative valve alloys are given in Table 3. The yield strength of the alloy of Example 2 is higher than that of Alloys A and B and much higher than the austenitic valve steels, Alloys F and G. Sufficient yield strength is needed to prevent the valve from deforming while operating in an engine. The yield strength of the alloys of the invention as embodied by Example 2 is higher than that of other comparative commercially available Fe- based valve alloys, which indicates the alloys of invention have sufficient strength. The tensile strength of the alloy of Example 2 is higher than that of Alloys B through G, and similar to that of Alloy A, which indicates that the alloys of the invention can be subjected to higher stress levels before catastrophic failure occurs. Table 3
Figure imgf000013_0001
Creep Rupture Stress
Sufficient creep strength is needed to prevent creep related failure in the fillet area of valves. The creep stress needed to rupture the alloys of invention and several comparative valve alloys in IOOhrs at 15000F (816°C) is given in Table 4. The creep rupture stress of the alloy of Example 2 is comparable to that of Alloys A and B and much better than the austenitic valve steels F and G. The austenitic valve steels have sufficient creep rupture strength for exhaust valve applications to prevent failures due to creep in the fillet area of the valve. Therefore, the alloys of invention should also have sufficient creep strength to prevent failure.
U-Notch Impact Toughness
During engine operation, the valve seat face impacts against the insert. Sufficient toughness is required to prevent cracking of the seat face. The U- notch impact toughness (specification JIS Z2202) of the alloy of Example 2 and several comparative valve alloys after heat treating and after heat treating and a 400hr exposure at 1472°F (8000C) was tested. The results are given in Table 4. After the 400hr exposure, the alloys of the invention, as exemplified by Example 2, have significantly better impact toughness than Alloy F and is similar to Alloy A. The results show that the toughness of the alloys of the invention is suitable for automotive valve applications. Table 4
Figure imgf000014_0001
Fatigue Strength
Fatigue strength is needed to prevent fatigue related failures in the stem fillet area of a valve. Rotating beam fatigue tests were conducted on the alloys of the invention and Alloys A, B and D at 15000F (816°C) at 108 cycles with applied stresses of 25-45 ksi. The results are shown in FIG. 4. The fatigue strength of the alloy of Example 3 of the invention is somewhat better than that of Alloys A and B. Therefore, the alloys of invention, as exemplified by Example 3, have sufficient fatigue strength for automotive valves. The fatigue endurance limit of the alloy of Example 3 and that of comparative alloys B and D at 16000F (8710C) at 108 cycles is shown in FIG. 5. At this temperature, the fatigue strength of the alloy of Example 3 is better that that of comparative Alloy B.
The alloys of the present invention can be used to produce engine valves. In one embodiment, there is provided an engine valve for a motor vehicle comprising an alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1% Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1% to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities. The engine valve alloy may contain elements that satisfy the following equation: Mo +0.5W ≤ 0.75%, based on the weight percent of the elements in the alloy. The alloy may contain the carbide containing elements titanium and niobium in amounts that satisfy the following equations: Ti+Nb ≥ 4.5% and 13 < (Ti + Nb)/C ≤ 50, on a weight percentage basis.
Exhaust Valve Wear Resistance
Exhaust valves made from the alloy of Example 3 were subjected to a 100 hour dyno test in a V-8 spark ignited gasoline engine and to a 500 hour dyno test in a heavy duty compression ignited diesel engine. The exhaust valves passed both wear tests, exhibiting acceptable wear resistance in each test.
While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

We claim:
1. A wear resistant alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1 % Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1% to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities; wherein Mo +0.5W ≤ 0.75%; Ti+Nb > 4.5% and 13 < (Ti + Nb)/C < 50, on a weight percentage basis.
2. The alloy of claim 1 wherein the following elements are present in the following amounts, in weight percent: greater than 0.15% to 0.3% C; 1.7% to 2.5% total of Nb and Ta.
3. The alloy of claim 2 wherein the elements W, Mo and V are not present in the alloy in greater than inevitable impurity amounts.
4. The alloy of claim 1 wherein the total primary carbide volume fraction is greater than 1% and up to 4%.
5. The alloy of claim 1 wherein the alloy has good pin abrasion wear resistance as measured by a pin abrasion wear loss of less than 100 mg after solution treating and aging.
6. The alloy of claim 1 wherein the elements of the alloy satisfy the equation: 15 < (Ti + Nb)/C ≤ 35, on a weight percentage basis.
7. The alloy of claim 1 wherein the elements of the alloy satisfy the equation: 17 ≤ (Ti + Nb)/C ≤ 30, on a weight percentage basis.
8. A wear resistant alloy consisting essentially of, by weight, greater than 0.15% up to 0.3% C; up to 1% Si; up to 1% Mn; 29% to 35% Ni; 15% to 20% Cr; up to 0.25% Mo; up to 0.25% W; 1.63% to 2.3% Al; 2.0% to 3.5% Ti; 1.8% to 2.5% total of Nb and Ta; 0.005% to 0.015% B; and the balance being Fe and inevitable impurities; wherein Ti+Nb ≥ 4.5% and 13 ≤ (Ti + Nb)/C < 50, on a weight percentage basis.
9. The alloy of claim 8 wherein the elements W and Mo are not present in the alloy in greater than inevitable impurity amounts.
10. The alloy of claim 8 wherein the elements of the alloy satisfy the equation: 15 ≤ (Ti + Nb)/C < 35, on a weight percentage basis.
11. The alloy of claim 8 wherein the elements of the alloy satisfy the equation: 17 ≤ (Ti + Nb)/C < 30, on a weight percentage basis.
12. An engine valve for a motor vehicle comprising an alloy consisting essentially of, by weight, 0.15% up to 0.35% C; up to 1% Si; up to 1% Mn; greater than 25% to less than 40% Ni; 15% to 25% Cr; up to 0.5% Mo; up to 0.5% W; greater than 1.6% to 3% Al; 1 % to 3.5% Ti; greater than 1.1 to 3% total of Nb and Ta; up to 0.015% B; and the balance being Fe and inevitable impurities; wherein Mo +0.5W<0.75%; Ti+Nb>4.5% and 13< (Ti + Nb)/C <50, on a weight percentage basis.
13. The engine valve of claim 12 wherein the following elements are present in the alloy in the following amounts, in weight percent: greater than 0.15% to 0.3% C; 1.7% to 2.5% total of Nb and Ta.
14. The engine valve of claim 12 wherein the elements W, Mo and V are not present in the alloy in greater than inevitable impurity amounts.
15. The engine valve of claim 12 wherein the total primary carbide volume fraction of the alloy is greater than 1% and up to 4%.
16. The engine valve of claim 12 wherein the elements of the alloy satisfy the equation: 15 ≤ (Ti + Nb)/C ≤ 35, on a weight percentage basis.
17. The engine valve of claim 12 wherein the elements of the alloy satisfy the equation: 17 ≤ (Ti + Nb)/C ≤ 30, on a weight percentage basis.
PCT/IB2007/001860 2006-07-07 2007-07-05 Wear resistant high temperature alloy WO2008007190A2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA2658234A CA2658234C (en) 2006-07-07 2007-07-05 Wear resistant high temperature alloy
EP07804566.3A EP2038444B1 (en) 2006-07-07 2007-07-05 Wear resistant high temperature alloy
BRPI0713237A BRPI0713237B1 (en) 2006-07-07 2007-07-05 wear resistant alloy and automobile engine valve
CN2007800257108A CN101484597B (en) 2006-07-07 2007-07-05 Wear resistant high temperature alloy
JP2009518991A JP5302192B2 (en) 2006-07-07 2007-07-05 Abrasion resistant heat resistant alloy

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US80674306P 2006-07-07 2006-07-07
US60/806,743 2006-07-07
US86860606P 2006-12-05 2006-12-05
US60/868,606 2006-12-05

Publications (2)

Publication Number Publication Date
WO2008007190A2 true WO2008007190A2 (en) 2008-01-17
WO2008007190A3 WO2008007190A3 (en) 2008-03-20

Family

ID=38792040

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2007/001860 WO2008007190A2 (en) 2006-07-07 2007-07-05 Wear resistant high temperature alloy

Country Status (7)

Country Link
US (1) US7651575B2 (en)
EP (1) EP2038444B1 (en)
JP (1) JP5302192B2 (en)
CN (1) CN101484597B (en)
BR (1) BRPI0713237B1 (en)
CA (1) CA2658234C (en)
WO (1) WO2008007190A2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014001328A1 (en) 2014-02-04 2015-08-06 VDM Metals GmbH Curing nickel-chromium-iron-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
DE102014001329A1 (en) 2014-02-04 2015-08-06 VDM Metals GmbH Curing nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
DE102014001330A1 (en) 2014-02-04 2015-08-06 VDM Metals GmbH Curing nickel-chromium-cobalt-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
US10086453B2 (en) 2014-03-24 2018-10-02 Thermocompact Process for manufacturing a closed loop of cutting wire

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090081073A1 (en) * 2007-06-07 2009-03-26 Celso Antonio Barbosa Alloys with high corrosion resistance for engine valve applications
DE102009039228A1 (en) * 2009-08-28 2011-03-03 Emitec Gesellschaft Für Emissionstechnologie Mbh Thermoelectric device
WO2011029165A1 (en) * 2009-09-09 2011-03-17 Villares Metals S/A Alloys with high corrosion resistance for engine valve applications
WO2011029164A1 (en) * 2009-09-09 2011-03-17 Villares Metals S/A Nickel-based superalloy for valves of internal combustion engines
CN105579607A (en) * 2013-09-13 2016-05-11 伊顿公司 Wear resistant alloy
CN104152750A (en) * 2014-07-30 2014-11-19 钢铁研究总院 Nickel-saving type gas valve alloy and preparation method thereof
CN104263998B (en) * 2014-09-18 2016-06-22 中国华能集团公司 A kind of Technology for Heating Processing of ni-fe-cr-boron system high temperature alloy
CN106480445B (en) * 2015-09-02 2019-02-26 沈阳大陆激光工程技术有限公司 The alloy material of wear-resisting heat resistanceheat resistant composite coating is prepared on coiler pinch-roll surface
CN105603260A (en) * 2015-12-24 2016-05-25 宁波天阁汽车零部件有限公司 High-temperature-resistant turbocharger turbine wheel
GB2546808B (en) * 2016-02-01 2018-09-12 Rolls Royce Plc Low cobalt hard facing alloy
GB2546809B (en) * 2016-02-01 2018-05-09 Rolls Royce Plc Low cobalt hard facing alloy
KR101893831B1 (en) * 2016-10-20 2018-08-31 주식회사 고영테크놀러지 Board inspection apparatus and board inspection method using the same
US11255003B2 (en) 2019-04-02 2022-02-22 Ut-Battelle, Llc Ta-containing Fe-Ni based superalloys with high strength and oxidation resistance for high-temperature applications
CN110465667B (en) * 2019-09-25 2022-04-22 广西科技大学 Turbocharger blade and preparation method thereof
CN112281068A (en) * 2020-10-29 2021-01-29 钢铁研究总院 Preparation method of valve alloy equiaxial crystal grains
CN113278862A (en) * 2021-05-31 2021-08-20 沈阳工业大学 Nitrogen-containing low-nickel special high-temperature wear-resistant alloy and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH492792A (en) * 1966-08-16 1970-06-30 Deutsche Edelstahlwerke Ag Use of a nickel alloy for the manufacture of tough hot and cold formable articles which are exposed to the attack of combustion products of vanadium and / or sulfur containing fuels at temperatures above 500 ° C
US5660938A (en) * 1993-08-19 1997-08-26 Hitachi Metals, Ltd., Fe-Ni-Cr-base superalloy, engine valve and knitted mesh supporter for exhaust gas catalyzer
JPH10226837A (en) * 1997-02-17 1998-08-25 Hitachi Ltd Heat resistant steel for gas turbine disk
JPH11229059A (en) * 1998-02-09 1999-08-24 Hitachi Metals Ltd Heat resistant alloy for engine valve
EP1464718A1 (en) * 2003-03-18 2004-10-06 HONDA MOTOR CO., Ltd. High-strength, heat-resistant alloy for exhaust valves with improved overaging-resistance

Family Cites Families (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2432617A (en) * 1945-06-13 1947-12-16 Electro Metallurg Co Ferrous alloys for high temperature use
US2432618A (en) * 1946-05-09 1947-12-16 Electro Metallurg Co Ferrous alloys for high-temperature use
US2744821A (en) * 1951-12-13 1956-05-08 Gen Electric Iron base high temperature alloy
US2750283A (en) * 1953-05-27 1956-06-12 Armco Steel Corp Stainless steels containing boron
JPS5040099B1 (en) * 1971-03-09 1975-12-22
JPS5631345B2 (en) * 1972-01-27 1981-07-21
JPS5927369B2 (en) 1979-05-11 1984-07-05 三菱マテリアル株式会社 Co-based alloy for diesel engine valves and valve seats
JPS5620148A (en) 1979-07-25 1981-02-25 Daido Steel Co Ltd Alloy for exhaust valve
JPS58189359A (en) 1982-04-30 1983-11-05 Hitachi Metals Ltd Heat resistant alloy for exhaust valve
JPS6046343A (en) 1983-08-23 1985-03-13 Daido Steel Co Ltd Alloy for exhaust valve
JPS61130464A (en) 1984-11-30 1986-06-18 Nippon Steel Corp Non-magnetic steel for drill collar having superior corrosion resistance and high strength
JPS62214149A (en) 1986-03-14 1987-09-19 Kobe Steel Ltd Heat resistant alloy for exhaust valve
US5019332A (en) 1988-03-16 1991-05-28 Carpenter Technology Corporation Heat, corrosion, and wear resistant steel alloy
US4929419A (en) 1988-03-16 1990-05-29 Carpenter Technology Corporation Heat, corrosion, and wear resistant steel alloy and article
DE68912689T2 (en) 1988-07-30 1994-06-16 Fukuda Metal Foil Powder Alloy for armoring valves.
JPH06344183A (en) 1993-06-11 1994-12-20 Mitsubishi Materials Corp Fe base alloy powder having excellent hot wear resistance for cladding by welding
US5495837A (en) 1993-06-11 1996-03-05 Mitsubishi Materials Corporation Engine valve having improved high-temperature wear resistance
JP3058794B2 (en) * 1993-08-19 2000-07-04 日立金属株式会社 Fe-Ni-Cr based super heat resistant alloy, knit mesh for engine valve and exhaust gas catalyst
JP3308090B2 (en) 1993-12-07 2002-07-29 日立金属株式会社 Fe-based super heat-resistant alloy
JP2963842B2 (en) 1994-06-15 1999-10-18 大同特殊鋼株式会社 Alloy for exhaust valve
US5674449A (en) 1995-05-25 1997-10-07 Winsert, Inc. Iron base alloys for internal combustion engine valve seat inserts, and the like
JPH09279309A (en) 1996-04-12 1997-10-28 Daido Steel Co Ltd Iron-chrome-nickel heat resistant alloy
US5951789A (en) 1996-10-25 1999-09-14 Daido Tokushuko Kabushiki Kaisha Heat resisting alloy for exhaust valve and method for producing the exhaust valve
JPH10219377A (en) 1997-02-07 1998-08-18 Daido Steel Co Ltd Manufacture of high corrosion resistant valve for intake and exhaust valve for diesel engine and intake and exhaust valve
US5916384A (en) 1997-03-07 1999-06-29 The Controller, Research & Development Organization Process for the preparation of nickel base superalloys by brazing a plurality of molded cavities
JP3671271B2 (en) 1997-10-03 2005-07-13 大同特殊鋼株式会社 Manufacturing method of engine exhaust valve
JPH11117019A (en) * 1997-10-09 1999-04-27 Daido Steel Co Ltd Production of heat resistant parts
JPH11117020A (en) * 1997-10-09 1999-04-27 Daido Steel Co Ltd Production of heat resistant parts
JPH11199987A (en) 1997-11-10 1999-07-27 Hitachi Metals Ltd Heat resistant alloy suitable for cold working
US5945067A (en) 1998-10-23 1999-08-31 Inco Alloys International, Inc. High strength corrosion resistant alloy
IL145175A (en) 1999-03-08 2005-08-31 Crs Holdings Inc Stainless-steel alloy
US6436338B1 (en) 1999-06-04 2002-08-20 L. E. Jones Company Iron-based alloy for internal combustion engine valve seat inserts
KR100372482B1 (en) 1999-06-30 2003-02-17 스미토모 긴조쿠 고교 가부시키가이샤 Heat resistant Ni base alloy
JP4057208B2 (en) 1999-12-16 2008-03-05 日立金属株式会社 Fe-base heat-resistant alloy for engine valves with good cold workability and high-temperature strength
CN1100890C (en) * 1999-12-17 2003-02-05 黄进峰 High-temperature high-strength antioxidant anticorrosive austenite alloy
US6485678B1 (en) 2000-06-20 2002-11-26 Winsert Technologies, Inc. Wear-resistant iron base alloys
US6372181B1 (en) * 2000-08-24 2002-04-16 Inco Alloys International, Inc. Low cost, corrosion and heat resistant alloy for diesel engine valves
US6685881B2 (en) 2000-09-25 2004-02-03 Daido Steel Co., Ltd. Stainless cast steel having good heat resistance and good machinability
US6461452B1 (en) 2001-05-16 2002-10-08 Crs Holdings, Inc. Free-machining, martensitic, precipitation-hardenable stainless steel
US6916444B1 (en) 2002-02-12 2005-07-12 Alloy Technology Solutions, Inc. Wear resistant alloy containing residual austenite for valve seat insert
JP4277113B2 (en) 2002-02-27 2009-06-10 大同特殊鋼株式会社 Ni-base alloy for heat-resistant springs
DE60323795D1 (en) 2002-08-16 2008-11-13 Alloy Technology Solutions Inc Wear-resistant and corrosion-resistant austenitic iron-based alloy
US6702905B1 (en) 2003-01-29 2004-03-09 L. E. Jones Company Corrosion and wear resistant alloy
US7611590B2 (en) 2004-07-08 2009-11-03 Alloy Technology Solutions, Inc. Wear resistant alloy for valve seat insert used in internal combustion engines
JP4830466B2 (en) 2005-01-19 2011-12-07 大同特殊鋼株式会社 Heat-resistant alloy for exhaust valves that can withstand use at 900 ° C and exhaust valves using the alloys
US20060286526A1 (en) * 2005-05-27 2006-12-21 Marshall Montgomery Vehicle for experimental demonstration of laws of motion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH492792A (en) * 1966-08-16 1970-06-30 Deutsche Edelstahlwerke Ag Use of a nickel alloy for the manufacture of tough hot and cold formable articles which are exposed to the attack of combustion products of vanadium and / or sulfur containing fuels at temperatures above 500 ° C
US5660938A (en) * 1993-08-19 1997-08-26 Hitachi Metals, Ltd., Fe-Ni-Cr-base superalloy, engine valve and knitted mesh supporter for exhaust gas catalyzer
JPH10226837A (en) * 1997-02-17 1998-08-25 Hitachi Ltd Heat resistant steel for gas turbine disk
JPH11229059A (en) * 1998-02-09 1999-08-24 Hitachi Metals Ltd Heat resistant alloy for engine valve
EP1464718A1 (en) * 2003-03-18 2004-10-06 HONDA MOTOR CO., Ltd. High-strength, heat-resistant alloy for exhaust valves with improved overaging-resistance

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015117585A3 (en) * 2014-02-04 2015-10-22 VDM Metals GmbH Hardened nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and workability
DE102014001329A1 (en) 2014-02-04 2015-08-06 VDM Metals GmbH Curing nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
DE102014001330A1 (en) 2014-02-04 2015-08-06 VDM Metals GmbH Curing nickel-chromium-cobalt-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
WO2015117583A1 (en) 2014-02-04 2015-08-13 VDM Metals GmbH Hardening nickel-chromium-cobalt-titanium-aluminium alloy with good wear resistance, creep strength, corrosion resistance and processability
WO2015117584A1 (en) 2014-02-04 2015-08-13 VDM Metals GmbH Hardening nickel-chromium-iron-titanium-aluminium alloy with good wear resistance, creep strength, corrosion resistance and processability
WO2015117585A2 (en) 2014-02-04 2015-08-13 VDM Metals GmbH Hardened nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and workability
DE102014001328A1 (en) 2014-02-04 2015-08-06 VDM Metals GmbH Curing nickel-chromium-iron-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
DE102014001328B4 (en) * 2014-02-04 2016-04-21 VDM Metals GmbH Curing nickel-chromium-iron-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
DE102014001329B4 (en) * 2014-02-04 2016-04-28 VDM Metals GmbH Use of a thermosetting nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
DE102014001330B4 (en) * 2014-02-04 2016-05-12 VDM Metals GmbH Curing nickel-chromium-cobalt-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability
US10870908B2 (en) 2014-02-04 2020-12-22 Vdm Metals International Gmbh Hardening nickel-chromium-iron-titanium-aluminium alloy with good wear resistance, creep strength, corrosion resistance and processability
US11098389B2 (en) 2014-02-04 2021-08-24 Vdm Metals International Gmbh Hardened nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and workability
US10086453B2 (en) 2014-03-24 2018-10-02 Thermocompact Process for manufacturing a closed loop of cutting wire

Also Published As

Publication number Publication date
EP2038444A2 (en) 2009-03-25
US20080008617A1 (en) 2008-01-10
BRPI0713237B1 (en) 2018-09-11
CN101484597A (en) 2009-07-15
CA2658234A1 (en) 2008-01-17
WO2008007190A3 (en) 2008-03-20
JP2009542919A (en) 2009-12-03
JP5302192B2 (en) 2013-10-02
BRPI0713237A2 (en) 2012-04-17
CN101484597B (en) 2011-03-30
CA2658234C (en) 2014-08-26
EP2038444B1 (en) 2015-08-19
US7651575B2 (en) 2010-01-26

Similar Documents

Publication Publication Date Title
US7651575B2 (en) Wear resistant high temperature alloy
CN109402518B (en) High performance iron-based alloys for engine valvetrain applications, methods of making and uses thereof
US9334547B2 (en) Iron-based alloys and methods of making and use thereof
JP4830466B2 (en) Heat-resistant alloy for exhaust valves that can withstand use at 900 ° C and exhaust valves using the alloys
US20060266439A1 (en) Heat and corrosion resistant cast austenitic stainless steel alloy with improved high temperature strength
US5019332A (en) Heat, corrosion, and wear resistant steel alloy
EP0639654B1 (en) Fe-Ni-Cr-base super alloy, engine valve and knitted mesh supporter for exhaust gas catalyzer
US20110236247A1 (en) Heat resistant steel for exhaust valve
US5660938A (en) Fe-Ni-Cr-base superalloy, engine valve and knitted mesh supporter for exhaust gas catalyzer
JP3458971B2 (en) Austenitic heat-resistant cast steel with excellent high-temperature strength and machinability, and exhaust system parts made of it
EP0359085B1 (en) Heat-resistant cast steels
JP2860260B2 (en) High corrosion resistance Ni-based alloy
JPH03177543A (en) Valve steel
JP3375001B2 (en) Austenitic heat-resistant cast steel with excellent castability and machinability and exhaust system parts made of it
JP2000204449A (en) Iron base superalloy excellent in cold workability and high temperature thermal stability
JPH06228713A (en) Austenitic heat resistant cast steel excellent in strength at high temperature and machinability and exhaust system parts using same
JPH07238349A (en) Heat resistant steel
US11685972B2 (en) Ni-based alloy and valve
JPH07113139B2 (en) Exhaust manifold and automobile turbine housing with excellent castability and heat fatigue resistance
CN114836682A (en) Martensitic wear-resistant alloy strengthened by aluminium nitride
Poweleit Steel castings properties
JPH0112827B2 (en)
JPH10130789A (en) Heat resistant alloy excellent in cold workability

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780025710.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07804566

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 5177/KOLNP/2008

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2658234

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2009518991

Country of ref document: JP

Ref document number: 2007804566

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

ENP Entry into the national phase

Ref document number: PI0713237

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20090107