US2245366A - Hardening cobalt-nickel-chromiumiron alloys - Google Patents

Hardening cobalt-nickel-chromiumiron alloys Download PDF

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Publication number
US2245366A
US2245366A US247696A US24769638A US2245366A US 2245366 A US2245366 A US 2245366A US 247696 A US247696 A US 247696A US 24769638 A US24769638 A US 24769638A US 2245366 A US2245366 A US 2245366A
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alloys
nickel
temperatures
cobalt
hardening
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US247696A
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Rohn Wilhelm
Bollenrath Franz
Cornelius Heinrich
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    • 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
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49229Prime mover or fluid pump making
    • Y10T29/49298Poppet or I.C. engine valve or valve seat making

Definitions

  • This invention relates to a method of hardening certain cobalt-nickel-chromium-iron alloys having improved mechanical properties at elevated temperatures.
  • alloys which in addition to nickel as main constituent contain alternatively proportions of chromium, molybdenum or tungsten as well as on occasion iron, show a high creep resistance in hard rolled condition at operating temperatures between about 400 and 600 C.
  • the alloys according to this invention contain as main constituents cobalt and nickel in a total quantity of 50 to 70% the cobalt content amounting to at least 10% and the nickel content amounting to at least 0.05%.
  • Tungsten and molybdenum may be present separately or together in amounts of from 0.05% up to for example from 2.5 to 15%, and the chromium content amounts to between 8 and
  • the alloys may contain up to of iron, for instance, from 0.5 to 30% of iron.
  • a particularly good composition is 14 to 17% chromium, 14 to 16% iron, 5 to 7% molybdenum, 0 .to 5% tungsten, 15 to 27% (particularly 21%) of cobalt, and the remainder essentially nickel apart from the usual deoxidising and manufacturing additions, for example of manganese and silicon.
  • the manganese content may for example amount up to 1.5% and the silicon content up to 0.5%.
  • the advance over the known alloys is clear if the creep limit as such is not taken for comparison, but creep with time which is frequently adopted for comparison, that is to say the elongation per unit of time which a test piece undergoes when loaded with a given weight at constant temperature for a long time.
  • a comparative investigation about the creep resistance shows that the rate of creep of the cobalt-containing alloys according to the invention at constant temperature under a given load is only about one fifth to one tenth as compared with the abovementioned alloys of known composition.
  • the alloys according to the invention which show no transition point up to 1000 C. can be considerably hardened (up to about 300 Brinell) This is important in the case of valves for internal combustion engines, the stems of which in use are frequently deficient of lubrication.
  • the stem When annealed at high temperature to obtain high creep resistance, which is particularly necessary for the valve head and its neck, the stem is too soft to withstand operation in the dry or semidry state.
  • the stem may be provided with a thin hardened surface layer by hammering, pressing, pressure polishing or pressure rolling and thus valuable running properties under conditions of deficient lubrication obtained.
  • a further improvement, in particular as regards the resistance to creep at high temperatures, can be attained with the said alloys if an addition is made of. one or more of the elements of the first column of the fourth group of the peri-.- odic system of elements (titanium, zirconium, thorium) or of. metals of the first column of the fifth group of the periodic system of elements (vanadium, niobium, tantalum).
  • the amounts in which these elements may be contained in the alloy are Tantalum from 0.05% up to 15%
  • the lower limit of these additions is generally not below 0.3% and the upper limit of the additions together not above 15%.
  • the alloys so modified can be subjected to still higher mechanical load at high temperatures, that is to say the mechanical properties at a given temperature are better than those of the alloys without the specified additions, or the temperature at which the alloys can stand a predetermined mechanical load may be higher.
  • the abovementioned annealing at excessive temperatures before use for improving the properties as regards creep limit at temperatures above the recrystallisation temperature, or the above mentioned forging, rolling, drawing, or hammering at temperatures between the recrystallisation temperature and the temperature at which the alloys are to be used, for the purpose of increasing the creep resistance at temperatures below the recrystallisation temperature and the surface hardening by means of cold working can also be applied to the alloys with the additions 01' titanium, tantalum, niobium, vanadium, zirconium and thorium with good results.
  • the composition 01 the alloys with the said additions so far as the main constituents are concerned, lies within the limits given above.
  • a particularly advantageous alloy can be obtained with about 15 to 27% cobalt, 14 to 17% chromium, 6 to 16% iron, 5 to 7% molybdenum, 0 to 7% tungsten, especially 3 to 7% tungsten, besides nickel as main constituents, with addition of up to 5% titanium, up to 15% tantalum, up to 15% niobium, up to 8% thorium, and possibly the usual deoxidising and manufacturing additions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Forging (AREA)

Description

Patented June 10, 1941 HARDENING COBALT-NICKEL-CHROMIUM- IRON ALLOYS Wilhelm Rohn, Hanau on the Main, Franz Bollenrath, Berlin-Johannisthal, and Heinrich Cornelius, Berlin-Adlershoi, Germany No Drawing. Original application July 26, 1938,
Serial N 0. 221,394.
Divided and this application December 24, 1938, Serial No. 247,696. In- Germany April 24, 1936 1 Claim.
This application is a division of our copending patent application Ser. No. 221,394, filed July 26, 1938.
This invention relates to a method of hardening certain cobalt-nickel-chromium-iron alloys having improved mechanical properties at elevated temperatures. v
It is known that alloys which in addition to nickel as main constituent contain alternatively proportions of chromium, molybdenum or tungsten as well as on occasion iron, show a high creep resistance in hard rolled condition at operating temperatures between about 400 and 600 C.
Investigations by the applicants have now led to the development of alloys which on the one hand exhibit particularly high values of creep resistance at temperatures between 400 and 600 C. and which probably in this range show the optimum with regard to strength at high temperatures and which on the other handstill show also a high creep resistance at higher temperatures that is to say at temperatures up to and above 900 0. Consequently they are for example suitable for the exhaust valves of internal combustion engines and exhaust turbines which operate in the temperature range of 600 to 900 C.
The alloys according to this invention contain as main constituents cobalt and nickel in a total quantity of 50 to 70% the cobalt content amounting to at least 10% and the nickel content amounting to at least 0.05%. Tungsten and molybdenum may be present separately or together in amounts of from 0.05% up to for example from 2.5 to 15%, and the chromium content amounts to between 8 and In addition the alloys may contain up to of iron, for instance, from 0.5 to 30% of iron. A particularly good composition is 14 to 17% chromium, 14 to 16% iron, 5 to 7% molybdenum, 0 .to 5% tungsten, 15 to 27% (particularly 21%) of cobalt, and the remainder essentially nickel apart from the usual deoxidising and manufacturing additions, for example of manganese and silicon. The manganese content may for example amount up to 1.5% and the silicon content up to 0.5%. If the alloys are to be used at temperatures above their recrystallisation temperatures, the highest creep resistance is exhibited by the alloys stated when they have been annealed prior to their use at temperatures exceeding the temperatures of use, for example at 1150 to 1300 C. If desired the alloys can also be employed in cast condition. If the alloys are to be used at temperatures below their recrystallisation temperatures the creep resistance may be increased by forging, rolling,
be used, and the recrystallisation temperature.
By this special method not only the creep resistance but especially the elongation under the first loading of the material is decreased.
An alloy with about 16% chromium, about 15% iron, about 6% molybdenum, about nickel and about 21% cobalt besides small proportions of de-oxidising and manufacturing additions exceeds by about 10 to 15% as regards creep resistance in the temperature range 500 to 600 C. an alloy hitherto considered as particularly good in this respect and consisting of 60% nickel, 15% chromium, 7% molybdenum and 18% iron. The advance over the known alloys is clear if the creep limit as such is not taken for comparison, but creep with time which is frequently adopted for comparison, that is to say the elongation per unit of time which a test piece undergoes when loaded with a given weight at constant temperature for a long time.
A comparative investigation about the creep resistance shows that the rate of creep of the cobalt-containing alloys according to the invention at constant temperature under a given load is only about one fifth to one tenth as compared with the abovementioned alloys of known composition.
By cold working, the alloys according to the invention which show no transition point up to 1000 C. can be considerably hardened (up to about 300 Brinell) This is important in the case of valves for internal combustion engines, the stems of which in use are frequently deficient of lubrication. When annealed at high temperature to obtain high creep resistance, which is particularly necessary for the valve head and its neck, the stem is too soft to withstand operation in the dry or semidry state. As a result of the considerable hardening which can be efiected by cold Working the stem may be provided with a thin hardened surface layer by hammering, pressing, pressure polishing or pressure rolling and thus valuable running properties under conditions of deficient lubrication obtained.
A further improvement, in particular as regards the resistance to creep at high temperatures, can be attained with the said alloys if an addition is made of. one or more of the elements of the first column of the fourth group of the peri-.- odic system of elements (titanium, zirconium, thorium) or of. metals of the first column of the fifth group of the periodic system of elements (vanadium, niobium, tantalum). The amounts in which these elements may be contained in the alloy are Tantalum from 0.05% up to 15% The lower limit of these additions is generally not below 0.3% and the upper limit of the additions together not above 15%. The alloys so modified can be subjected to still higher mechanical load at high temperatures, that is to say the mechanical properties at a given temperature are better than those of the alloys without the specified additions, or the temperature at which the alloys can stand a predetermined mechanical load may be higher.
The abovementioned annealing at excessive temperatures before use for improving the properties as regards creep limit at temperatures above the recrystallisation temperature, or the above mentioned forging, rolling, drawing, or hammering at temperatures between the recrystallisation temperature and the temperature at which the alloys are to be used, for the purpose of increasing the creep resistance at temperatures below the recrystallisation temperature and the surface hardening by means of cold working can also be applied to the alloys with the additions 01' titanium, tantalum, niobium, vanadium, zirconium and thorium with good results. The composition 01 the alloys with the said additions so far as the main constituents are concerned, lies within the limits given above. Thus a particularly advantageous alloy can be obtained with about 15 to 27% cobalt, 14 to 17% chromium, 6 to 16% iron, 5 to 7% molybdenum, 0 to 7% tungsten, especially 3 to 7% tungsten, besides nickel as main constituents, with addition of up to 5% titanium, up to 15% tantalum, up to 15% niobium, up to 8% thorium, and possibly the usual deoxidising and manufacturing additions.
We claim:
Method of hardening an alloy consisting of from 14 to 17% chromium, 14 to 16% iron, 5 to 7% molybdenum, 15 to 27% cobalt, and 52 to 33% nickel, which method'consists in cold working the said alloy.
WILHELM ROHN. FRANZ BOLLENRATH. HEINRICH CORNELIUS.
US247696A 1938-07-26 1938-12-24 Hardening cobalt-nickel-chromiumiron alloys Expired - Lifetime US2245366A (en)

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US362236A US2247643A (en) 1938-12-24 1940-10-22 Hardening cobalt-nickel-chromium-iron alloys

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2513472A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for use at high temperatures
US2513469A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for use at high temperatures
US2513467A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy article for use at elevated temperatures
US2513470A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Ferrous alloy articles having great strength at high temperatures
US2513468A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for high temperature service
US2513471A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for high-temperature service
US2524660A (en) * 1947-05-03 1950-10-03 Elgin Nat Watch Co Watch mainspring
US2678894A (en) * 1947-05-03 1954-05-18 Elgin Nat Watch Co Process of making articles of high elastic strength
US2777766A (en) * 1952-06-04 1957-01-15 Union Carbide & Carbon Corp Corrosion resistant alloys
DE971412C (en) * 1944-12-12 1959-01-22 Elgin Nat Watch Company Use of a cobalt-chromium-nickel alloy for watch winding springs
US2977223A (en) * 1957-12-10 1961-03-28 Westinghouse Electric Corp Stabilized and precipitation-hardened nickel-base alloys
US3087812A (en) * 1960-05-11 1963-04-30 Joseph H Doss Metallurgical composition
US3234015A (en) * 1961-05-01 1966-02-08 Dougles E Jones Heavy duty, wear resistant machine element
US20040025989A1 (en) * 2000-09-19 2004-02-12 Akihiko Chiba Co-ni base heat-resistant alloy and method for producing thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE971412C (en) * 1944-12-12 1959-01-22 Elgin Nat Watch Company Use of a cobalt-chromium-nickel alloy for watch winding springs
US2513470A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Ferrous alloy articles having great strength at high temperatures
US2513467A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy article for use at elevated temperatures
US2513472A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for use at high temperatures
US2513468A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for high temperature service
US2513471A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for high-temperature service
US2513469A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for use at high temperatures
US2524660A (en) * 1947-05-03 1950-10-03 Elgin Nat Watch Co Watch mainspring
US2678894A (en) * 1947-05-03 1954-05-18 Elgin Nat Watch Co Process of making articles of high elastic strength
US2777766A (en) * 1952-06-04 1957-01-15 Union Carbide & Carbon Corp Corrosion resistant alloys
US2977223A (en) * 1957-12-10 1961-03-28 Westinghouse Electric Corp Stabilized and precipitation-hardened nickel-base alloys
US3087812A (en) * 1960-05-11 1963-04-30 Joseph H Doss Metallurgical composition
US3234015A (en) * 1961-05-01 1966-02-08 Dougles E Jones Heavy duty, wear resistant machine element
US20040025989A1 (en) * 2000-09-19 2004-02-12 Akihiko Chiba Co-ni base heat-resistant alloy and method for producing thereof

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