US3303023A - Use of cold-formable austenitic stainless steel for valves for internal-combustion engines - Google Patents

Use of cold-formable austenitic stainless steel for valves for internal-combustion engines Download PDF

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Publication number
US3303023A
US3303023A US389524A US38952464A US3303023A US 3303023 A US3303023 A US 3303023A US 389524 A US389524 A US 389524A US 38952464 A US38952464 A US 38952464A US 3303023 A US3303023 A US 3303023A
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United States
Prior art keywords
steel
steels
cold
columbium
carbon
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Expired - Lifetime
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US389524A
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English (en)
Inventor
Edward J Dulis
Kasak August
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Crucible Materials Corp
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Crucible Steel Company of America
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Priority to US389524A priority Critical patent/US3303023A/en
Priority to FR986051A priority patent/FR1405738A/fr
Priority to DK419364AA priority patent/DK105621C/da
Priority to GB34795/64A priority patent/GB1013240A/en
Priority to BE652281D priority patent/BE652281A/xx
Priority to ES0303475A priority patent/ES303475A1/es
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Publication of US3303023A publication Critical patent/US3303023A/en
Assigned to COLT INDUSTRIES OPERATING CORP. reassignment COLT INDUSTRIES OPERATING CORP. MERGER AND CHANGE OF NAME Assignors: CRUCIBLE CENTER COMPANY (INTO) CRUCIBLE INC. (CHANGED TO)
Assigned to CRUCIBLE MATERIALS CORPORATION reassignment CRUCIBLE MATERIALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: COLT INDUSTRIES OPERATING CORP.
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper

Definitions

  • This invention relates to chromium-nickel stainless steels that are substantially completely and stably austenitic, and more particularly to such steels which are readily formable at ambient temperature but exhibit high resistance to deformation at elevated temperature and high resistance to the corrosive attack of various media at elevated temperatures.
  • the outstanding high-temperature strength and corrosion resistance of our steels make them particularly well suited for the production of valves for use in internalcombustion engines and for the production of other vehicle-engine components.
  • the superior cold-formability of our steels makes them useful for the manufacture of valves and similar parts by extrusion and/or forging at ambient temperature.
  • Still another object of our invention is to provide a steel exhibiting, in combination with the above-mentioned properties, desirable weldability.
  • steel possessing the above-indicated combination of desirable properties may be produced by providing a strengthened, substantially completely and stably austenitic chromium-nickel steel having low contents of carbon, nitrogen, and silicon. More particularly, we provide steel containing up to 0.08% of carbon, up to 0.05% of nitrogen, with the sum of the carbon and the nitrogen contents being up to 0.08%, and up to 0.25%, but preferably not over about 0.12%, of silicon.
  • Our steel is strengthened to provide high-temperature creep strength substantially greater than that obtainable in a completely and stably aus-tenitic chromium-nickel steel to which no strengthening elements have been added, and desirably, the strengthening in our steel is done by the addition of small amounts of both columbium and boron, such as 0.01 to 0.15% columbium and 0.005 to 0.025% boron.
  • the steel also contains at least 13%, preferably at least 16%, of chromium, and sufficient nickel to render it stably austenitic, the balance being iron except for incidental impurities.
  • the columbium and boron contribute to the creep strength (elevated-temperature deformation resistance) of the steel, while the low contents of silicon and carbon plus nitrogen contribute to the cold formability of the steel, neither of these modifications having any substantial detrimental effect upon the corrosion resistance of the steel.
  • the boron content of the steel is preferably maintained low, i.e., not over about 0.009% or 0.01%, to avoid detrimental effects upon both the weldability and the cold formability of the steel. In this manner, a steel possessing the above-indicated desirable combination of properties is obtained.
  • the steels of our invention may be readily distinguished from known commercial steels and those disclosed in the prior art in certain important respects.
  • the steels of our invention are further distinguishable from prior-art and commercial austenitic stainless steels in their containing an effective, but small, amount of columbium.
  • columbium is usually used, when added, in an amount of at least ten times the carbon content, as an agent to precipitate the carbon remaining in the steel matrix and there by avoid impoverishment of the grain boundaries in chromium as the result of formation of chromium carbides, the intent of the columbium addition being to stabilize the steel against the intergranular corrosion that tends to occur when columbium, titanium or a similar strong carbideforming element is not added and the above-indicated grain-boundary chromium impoverishment is permitted to occur. From the above-indicated columbium range, it will be apparent that in our steel columbium is added in a considerably smaller amount, not more than about double the carbon content, and for a different purpose.
  • col umbium not being present in an amount greater than 0.15%.
  • composition for our invention encompassing steels having not only desired high strength and good cold forma'bility but also superior resistance to corrosive attack by combustion products of lead-containing fuels, is as follows:
  • the steel tends not to be completely and stably austenitic
  • Copper in the range 1 to 2% is preferred because it promotes cold-formability, and in certain instances when other strengthening elements are substituted for columbium, it improves the creep strength.
  • Phosphorus and sulfur may be present as impurities in the amounts usually permitted by commercial standards (about 0.025% maximum for each).
  • Tantalum may be substituted for columbium, in whole or in part, on the basis of two parts by weight of tantalum for one part of columbium.
  • Other strong carbideforming elements such as titanium, zirconium, vanadium, molybdenum, tungsten, and possibly hafnium and uranium, may find used, singly or in combination, as substitutes for columbium, in whole or in part, in amounts substantially stoichiometrically equivalent.
  • Small amounts of aluminum such as about 0.01 to 0.25%, may also be used in place of columbium, in whole or in part, as a strengthening addition.
  • steels, V-l, V-4, Steelv 1 5 (g/m' V-6, V-7, and V9 are within our invention, and the remaining steels are presented for comparison.
  • Steels V-Z and V-3 show the effect of omitting boron and/or columbium.
  • Steel V-5 shows the effect of using greater than 3% of manganese.
  • Steel V-8 shows the effect of using an insufficient amount of nickel.
  • Steels V-10 and V11 demonstrate the effect of using greater than the x specified quantity of carbon plus nitrogen.
  • Tables VI and VII show that boron contents over about 0.009% detrimentally affect the cold formability.
  • Table VI presents the results with steels different boron contents and Table VII shows the criterion used in arriving at the cold-formability rating.
  • steels V-l, V-4, V6, V-7, and V9 represent steels of our invention, and the remaining steels are presented for comparison. All the steels of the invention were free of tendency for cracking when upset 68%, and all except steels V-l and V-9 were free of tendency for cracking when upset 80%.
  • V2 and V3 exhibited poor creep strength
  • V-S had a tendency to stress cracking at the 80% upset level because of its manganese content
  • V8 was not completely austenitic
  • V10 and Vll developed stress 10 cracking during cold forming because of their contents of carbon and nitrogen.
  • V, Zr, Ti, and Al all have beneficial Columbium 0.01 to 0.15 effects similar to those obtained with Cb; therefore, similar Boron 0.0005 to 0.010 amounts of V, Zr, Ti, and Al can be used in our steels to Nitrogen Up to 0.05 achieve the cold-formable exhaust valve material that is Carbon plus nitrogen Up to 0.08 the object of our invention.
  • 60 Iron and incidental impurities Balance Data showing the beneficial eifect of copper on the stretch resistance (creep strength) of our steels are presented in the following Table XII.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
US389524A 1963-08-26 1964-08-11 Use of cold-formable austenitic stainless steel for valves for internal-combustion engines Expired - Lifetime US3303023A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US389524A US3303023A (en) 1963-08-26 1964-08-11 Use of cold-formable austenitic stainless steel for valves for internal-combustion engines
FR986051A FR1405738A (fr) 1963-08-26 1964-08-24 Alliages d'aciers inoxydables
GB34795/64A GB1013240A (en) 1963-08-26 1964-08-25 Stainless steel alloys
BE652281D BE652281A (da) 1963-08-26 1964-08-25
DK419364AA DK105621C (da) 1963-08-26 1964-08-25 Austenitisk rustfrit stål.
ES0303475A ES303475A1 (es) 1963-08-26 1964-08-26 Mejoras introducidas en la fabricaciën de aceros inoxidables austeniticos

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30431063A 1963-08-26 1963-08-26
US389524A US3303023A (en) 1963-08-26 1964-08-11 Use of cold-formable austenitic stainless steel for valves for internal-combustion engines

Publications (1)

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US3303023A true US3303023A (en) 1967-02-07

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US (1) US3303023A (da)
BE (1) BE652281A (da)
DK (1) DK105621C (da)
ES (1) ES303475A1 (da)
GB (1) GB1013240A (da)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3431100A (en) * 1965-03-11 1969-03-04 Witten Edelstahl Austenitic steel suitable for exhaust valves subject to great stresses
US3440037A (en) * 1965-11-05 1969-04-22 Atomic Energy Commission Stainless steel alloy exhibiting resistance to embrittlement by neutron irradiation
US3475164A (en) * 1966-10-20 1969-10-28 Int Nickel Co Steels for hydrocracker vessels containing aluminum,columbium,molybdenum and nickel
US3476556A (en) * 1966-03-23 1969-11-04 Hitachi Ltd Austenitic heat-resisting steel containing niobium and vanadium
US3479157A (en) * 1965-06-25 1969-11-18 Int Nickel Co Welded articles and alloys containing hafnium and nickel
US3533780A (en) * 1966-02-10 1970-10-13 Sumitomo Metal Ind High-strength austenitic stainless steel for a boiler
US3537846A (en) * 1966-10-21 1970-11-03 Sandvikens Jernverks Ab Welding wire and welding strip for cladding stainless layers on unalloyed and low-alloyed structural steels and for other purposes where a stainless filler material with high chromium and nickel contents is required
US3716353A (en) * 1970-03-10 1973-02-13 Nippon Kokan Kk Austenitic heat resisting steel
US3751244A (en) * 1970-12-14 1973-08-07 Gijutsa Kenkyushon Nippon Koka Austenitic heat resisting steel
DE2421604A1 (de) * 1973-05-04 1974-11-14 Nippon Steel Corp Rostfreier stahl
US3902899A (en) * 1974-05-13 1975-09-02 Amax Inc Austenitic castable high temperature alloy
US3910788A (en) * 1973-04-21 1975-10-07 Nisshin Steel Co Ltd Austenitic stainless steel
US3957545A (en) * 1970-07-28 1976-05-18 Nippon Kokan Kabushiki Kaisha Austenitic heat resisting steel containing chromium and nickel
US3969161A (en) * 1973-11-07 1976-07-13 Nippon Kokan Kabushiki Kaisha Cr-Ni system austenitic heat-resisting steel
US4022586A (en) * 1969-12-29 1977-05-10 Armco Steel Corporation Austenitic chromium-nickel-copper stainless steel and articles
US4050928A (en) * 1976-02-17 1977-09-27 The International Nickel Company, Inc. Corrosion-resistant matrix-strengthened alloy
US4162930A (en) * 1976-03-30 1979-07-31 Nippon Steel Corporation Austenitic stainless steel having excellent resistance to intergranular and transgranular stress corrosion cracking
US4222773A (en) * 1979-05-29 1980-09-16 Fagersta Ab Corrosion resistant austenitic stainless steel containing 0.1 to 0.3 percent manganese
EP0340631A1 (en) * 1988-04-28 1989-11-08 Sumitomo Metal Industries, Ltd. Low silicon high-temperature strength steel tube with improved ductility and toughness
WO1994014992A1 (en) * 1992-12-18 1994-07-07 Electric Power Research Institute, Inc. Manufacture of materials and workpieces having fine grain for components in nuclear plant applications
WO1994014993A1 (en) * 1992-12-18 1994-07-07 Electric Power Institute, Inc. Manufacture of materials and workpieces for components in nuclear plant applications

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6220857A (ja) * 1985-07-19 1987-01-29 Daido Steel Co Ltd 高強度ステンレス鋼
JP2760004B2 (ja) * 1989-01-30 1998-05-28 住友金属工業株式会社 加工性に優れた高強度耐熱鋼

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2150901A (en) * 1938-02-01 1939-03-21 Arness William Bell Rustless iron
US2496248A (en) * 1948-08-25 1950-01-31 Armco Steel Corp Internal-combustion engine valve
US2624671A (en) * 1951-01-19 1953-01-06 Union Carbide & Carbon Corp Ferritic chromium steels
US2784125A (en) * 1954-05-19 1957-03-05 Armco Steel Corp Wrought stainless steel
US3107997A (en) * 1961-07-31 1963-10-22 Int Nickel Co Unfired pressure vessel
US3139337A (en) * 1962-05-31 1964-06-30 Gen Electric Alloys

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2150901A (en) * 1938-02-01 1939-03-21 Arness William Bell Rustless iron
US2496248A (en) * 1948-08-25 1950-01-31 Armco Steel Corp Internal-combustion engine valve
US2624671A (en) * 1951-01-19 1953-01-06 Union Carbide & Carbon Corp Ferritic chromium steels
US2784125A (en) * 1954-05-19 1957-03-05 Armco Steel Corp Wrought stainless steel
US3107997A (en) * 1961-07-31 1963-10-22 Int Nickel Co Unfired pressure vessel
US3139337A (en) * 1962-05-31 1964-06-30 Gen Electric Alloys

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3431100A (en) * 1965-03-11 1969-03-04 Witten Edelstahl Austenitic steel suitable for exhaust valves subject to great stresses
US3479157A (en) * 1965-06-25 1969-11-18 Int Nickel Co Welded articles and alloys containing hafnium and nickel
US3440037A (en) * 1965-11-05 1969-04-22 Atomic Energy Commission Stainless steel alloy exhibiting resistance to embrittlement by neutron irradiation
US3533780A (en) * 1966-02-10 1970-10-13 Sumitomo Metal Ind High-strength austenitic stainless steel for a boiler
US3476556A (en) * 1966-03-23 1969-11-04 Hitachi Ltd Austenitic heat-resisting steel containing niobium and vanadium
US3475164A (en) * 1966-10-20 1969-10-28 Int Nickel Co Steels for hydrocracker vessels containing aluminum,columbium,molybdenum and nickel
US3537846A (en) * 1966-10-21 1970-11-03 Sandvikens Jernverks Ab Welding wire and welding strip for cladding stainless layers on unalloyed and low-alloyed structural steels and for other purposes where a stainless filler material with high chromium and nickel contents is required
US4022586A (en) * 1969-12-29 1977-05-10 Armco Steel Corporation Austenitic chromium-nickel-copper stainless steel and articles
US3716353A (en) * 1970-03-10 1973-02-13 Nippon Kokan Kk Austenitic heat resisting steel
US3957545A (en) * 1970-07-28 1976-05-18 Nippon Kokan Kabushiki Kaisha Austenitic heat resisting steel containing chromium and nickel
US3751244A (en) * 1970-12-14 1973-08-07 Gijutsa Kenkyushon Nippon Koka Austenitic heat resisting steel
US3910788A (en) * 1973-04-21 1975-10-07 Nisshin Steel Co Ltd Austenitic stainless steel
DE2421604A1 (de) * 1973-05-04 1974-11-14 Nippon Steel Corp Rostfreier stahl
US3969161A (en) * 1973-11-07 1976-07-13 Nippon Kokan Kabushiki Kaisha Cr-Ni system austenitic heat-resisting steel
US3902899A (en) * 1974-05-13 1975-09-02 Amax Inc Austenitic castable high temperature alloy
US4050928A (en) * 1976-02-17 1977-09-27 The International Nickel Company, Inc. Corrosion-resistant matrix-strengthened alloy
US4162930A (en) * 1976-03-30 1979-07-31 Nippon Steel Corporation Austenitic stainless steel having excellent resistance to intergranular and transgranular stress corrosion cracking
US4222773A (en) * 1979-05-29 1980-09-16 Fagersta Ab Corrosion resistant austenitic stainless steel containing 0.1 to 0.3 percent manganese
EP0340631A1 (en) * 1988-04-28 1989-11-08 Sumitomo Metal Industries, Ltd. Low silicon high-temperature strength steel tube with improved ductility and toughness
WO1994014992A1 (en) * 1992-12-18 1994-07-07 Electric Power Research Institute, Inc. Manufacture of materials and workpieces having fine grain for components in nuclear plant applications
WO1994014993A1 (en) * 1992-12-18 1994-07-07 Electric Power Institute, Inc. Manufacture of materials and workpieces for components in nuclear plant applications

Also Published As

Publication number Publication date
BE652281A (da) 1965-02-25
DK105621C (da) 1966-10-17
ES303475A1 (es) 1965-01-01
GB1013240A (en) 1965-12-15

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Owner name: COLT INDUSTRIES OPERATING CORP.

Free format text: MERGER AND CHANGE OF NAME;ASSIGNOR:CRUCIBLE CENTER COMPANY (INTO) CRUCIBLE INC. (CHANGED TO);REEL/FRAME:004120/0308

Effective date: 19821214

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Owner name: CRUCIBLE MATERIALS CORPORATION, A DE CORP.

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:COLT INDUSTRIES OPERATING CORP.;REEL/FRAME:004194/0621

Effective date: 19831025

Owner name: CRUCIBLE MATERIALS CORPORATION, PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:COLT INDUSTRIES OPERATING CORP.;REEL/FRAME:004194/0621

Effective date: 19831025