US2621122A - Alloy for heat and corrosion resisting coating - Google Patents

Alloy for heat and corrosion resisting coating Download PDF

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Publication number
US2621122A
US2621122A US778466A US77846647A US2621122A US 2621122 A US2621122 A US 2621122A US 778466 A US778466 A US 778466A US 77846647 A US77846647 A US 77846647A US 2621122 A US2621122 A US 2621122A
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US
United States
Prior art keywords
alloy
heat
corrosion resisting
resisting coating
per cent
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Expired - Lifetime
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US778466A
Inventor
Gresham Harold Ernest
Wheeler Marcus Alan
Hall Douglas Wilson
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Rolls Royce PLC
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Rolls Royce PLC
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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
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033Ni as the principal constituent
    • 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
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/939Molten or fused coating

Definitions

  • This invention is concerned with engineering parts which are exposed to stress and corrosion, particularly at high temperatures, e. g. 700 to 1000 C.
  • Examples of such parts are the exhaust valves of internal combustion engines, blades, or other parts of internal combustion turbines and some steam stop-valves also stop valves and valves to handle sea water and for dies for casting or forging.
  • This invention has for one of its objects to provide protection for metal parts exposed to stress and/or corrosion, more especially at high temperature, by covering the surface of such part with a firmly adhering metal coating of higher resistivity than the part proper so protected.
  • the protective coating provided according to this invention is composed of a nickel-chromium alloy containing a comparatively high percentage of aluminum, some molybdenum, and some cobalt.
  • the molybdenum may be replaced in whole or in part by tungsten.
  • Carbon is present as an impurity in most commercial materials and we prefer to keep it within the stated limits.
  • Silicon and manganese are added mainly as cleansing elements; also a small amount is 2 preferable for welding purposes. Excess, particularly of silicon, tends to decrease the anticorrosion properties.
  • Iron occurs as an impurity in many of the commercial metals used. It is definitely detrimental to corrosion resistance and while we prefer to keep it as low as possible it is dimcult entirely to eliminate.
  • One or more of the following elements may be added for cleaning or deoxidising purposes up to 0.5 per cent in total namely: calcium, magnesium, barium, boron, strontium and zinc, cerium and the other rare earth elements or misch-metal which act as grain controllers. Small residual amounts of calcium and/or cerium are particularly advantageous.
  • One or more of the following elements may be included as additional hardeners up to a maximum of 1 per cent of each and 2 per cent in total: titanium, vanadium, zirconium, tantalum, beryllium, niobium, silver, antimony and tin. Nitrogen may also be included up to 0.3 per cent.
  • the alloy may be heat treated to increase the hardness and strength. Suitable heat treatments are as follows: (1) ageing only at 500 to 800 C. (preferably at about 700 C.) for 8 to 16 hours, or (2) solution treatment at 1050 C. to 1250 C. for 2 to 8 hours followed by ageing as above.
  • the part is cooled in air.
  • the solution treatment is not recommended 'for internal combustion engine valves as little advantage is gained and considerable damage may be done to the underlying steel or alloy. It is not necessary to age coated valves for use at temperatures around 500 to 850 C. but for parts which are to operate at temperatures below 500 or for parts which are to be used at lower, normal or room temperatures it may be advisable to age as required for a given hardness.
  • the coating is applied by welding or by any other known method.
  • the preferred process is to cast the alloy into 3 In order to apply the alloy to the base material of the valve or other part it is found that a flux is usually necessary.
  • the flux in the form of a finely divided powder is thoroughly mixed, damped with water and a thin even coat applied to the welding rods (by a rag, sponge or brush) which should then be allowed to dry thoroughly and not be used immediately.
  • the resultant coat can be machined and has been found to have excellent strength and hardness at elevated temperatures as well as being heat and corrosion resistant.
  • An alloy consisting by weight of approximately 9.5% to 12% aluminium, 10% to 11% chromium, 1.5% to 3.5% molybdenum, 0.1% to 0.7% cobalt, carbon not exceeding approximately 0.15%, 0.05% to 0.5% manganese, 0.1% to 0.3% silicon, iron not exceeding approximately 1.0%,
  • An alloy consisting by weight of approximately 9.5% to 12% aluminium, 10% to 11% chromium, 1.5% to 3.5% molybdenum, 0.1% to 0.7% cobalt, up to 1.0% iron, and the balance essentially all nickel substantially as hereinabove described.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Description

Patented Dec. 9, 1952 UNITED STATES PTEN'E' OFFICE ALLOY FOR HEAT AND CORROSION RESISTING COATING No Drawing. Application October 7, 1947, Serial No. 778,466. In Great Britain October 9, 1946 2 Claims.
This invention is concerned with engineering parts which are exposed to stress and corrosion, particularly at high temperatures, e. g. 700 to 1000 C. Examples of such parts are the exhaust valves of internal combustion engines, blades, or other parts of internal combustion turbines and some steam stop-valves also stop valves and valves to handle sea water and for dies for casting or forging.
This invention has for one of its objects to provide protection for metal parts exposed to stress and/or corrosion, more especially at high temperature, by covering the surface of such part with a firmly adhering metal coating of higher resistivity than the part proper so protected.
The protective coating provided according to this invention is composed of a nickel-chromium alloy containing a comparatively high percentage of aluminum, some molybdenum, and some cobalt.
According to this invention we form an alloy of the following elements in the following amounts all being percentages by weight of the whole alloy:
Per cent Aluminium 7.5 to 13.5 Chromium 9.0 to 25.0 Molybdenum 0.1 to 5.0 Cobalt 0.1 to 1.0
Remainder nickel.
The molybdenum may be replaced in whole or in part by tungsten.
The following elements may be present:
Per cent Carbon Up to 0.35 Manganese Up to 2.0 silicon Up to 1.0 Iron Up to 1.0
The preferred range is as follows:
Per cent Aluminium 9.5 to 12.0 Chromium 10 to 11 Molybdenum 1.5 to 3.5 Cobalt 0.1 to 0.7 Carbon 0.05 to 0.15 Manganese 0.05 to 0.5 Silicon 0.1 to 0.3 Iron 0.0 to 1.0
Nickel the remainder.
Carbon is present as an impurity in most commercial materials and we prefer to keep it within the stated limits.
Silicon and manganese are added mainly as cleansing elements; also a small amount is 2 preferable for welding purposes. Excess, particularly of silicon, tends to decrease the anticorrosion properties.
Iron occurs as an impurity in many of the commercial metals used. It is definitely detrimental to corrosion resistance and while we prefer to keep it as low as possible it is dimcult entirely to eliminate.
One or more of the following elements may be added for cleaning or deoxidising purposes up to 0.5 per cent in total namely: calcium, magnesium, barium, boron, strontium and zinc, cerium and the other rare earth elements or misch-metal which act as grain controllers. Small residual amounts of calcium and/or cerium are particularly advantageous.
One or more of the following elements may be included as additional hardeners up to a maximum of 1 per cent of each and 2 per cent in total: titanium, vanadium, zirconium, tantalum, beryllium, niobium, silver, antimony and tin. Nitrogen may also be included up to 0.3 per cent.
The alloy may be heat treated to increase the hardness and strength. Suitable heat treatments are as follows: (1) ageing only at 500 to 800 C. (preferably at about 700 C.) for 8 to 16 hours, or (2) solution treatment at 1050 C. to 1250 C. for 2 to 8 hours followed by ageing as above.
Afterwards the part is cooled in air.
The solution treatment is not recommended 'for internal combustion engine valves as little advantage is gained and considerable damage may be done to the underlying steel or alloy. It is not necessary to age coated valves for use at temperatures around 500 to 850 C. but for parts which are to operate at temperatures below 500 or for parts which are to be used at lower, normal or room temperatures it may be advisable to age as required for a given hardness.
The coating is applied by welding or by any other known method.
The preferred process is to cast the alloy into 3 In order to apply the alloy to the base material of the valve or other part it is found that a flux is usually necessary.
One flux which is suitable is as follows:
Per cent Boric anhydride 40 to 45 Silica 12 to 15 Fluorite 17 to 20 Lime 24 to 28 Iron oxide and other impurities up to about 0.5 per cent are also usually present in the flux.
The flux, in the form of a finely divided powder is thoroughly mixed, damped with water and a thin even coat applied to the welding rods (by a rag, sponge or brush) which should then be allowed to dry thoroughly and not be used immediately.
Slightly oxidising conditions are preferred during the welding operation, and a little additional dry flux should be available to the operator should it be desired.
During application great care should be taken to avoid excessive dilution and contamination of the alloy by the base material on which it is being welded and also to avoid entrapment of small particles of the slag which is formed.
The resultant coat can be machined and has been found to have excellent strength and hardness at elevated temperatures as well as being heat and corrosion resistant.
What we claim is:
1. An alloy consisting by weight of approximately 9.5% to 12% aluminium, 10% to 11% chromium, 1.5% to 3.5% molybdenum, 0.1% to 0.7% cobalt, carbon not exceeding approximately 0.15%, 0.05% to 0.5% manganese, 0.1% to 0.3% silicon, iron not exceeding approximately 1.0%,
4 and the balance essentially all nickel substan tially as hereinabove described.
2. An alloy consisting by weight of approximately 9.5% to 12% aluminium, 10% to 11% chromium, 1.5% to 3.5% molybdenum, 0.1% to 0.7% cobalt, up to 1.0% iron, and the balance essentially all nickel substantially as hereinabove described.
HAROLD ERNEST GRESHAM. MARCUS ALAN WHEELER. DOUGLAS WILSON HALL.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,273,877 Kuehrich July 30, 1918 2,071,645 McNeil Feb. 23, 1937 2,113,667 Swift Apr. 12, 1938 2,159,048 Pfeil May 23, 1939 2,246,078 Rohn et al June 17, 1941 2,403,128 Scott et al 1 July 21, 1946 2,432,149 Grifliths Dec. 9, 1947 2,450,803 Johnson Oct. 5, 1948 2,570,193 Bieber et al Oct. 9, 1951 FOREIGN PATENTS Number Country Date 342,868 Great Britain Feb. 12, 1931 371,334 Great Britain Apr. 13, 1932 591,641 Germany Jan. 24, 1934 425,614 Great Britain Mar. 15, 1935 OTHER REFERENCES Bureau of Standards Circular No. 100, Nickel and Its Alloys, 2nd ed., revised May 9, 1924, pp. 9-13. Published by G. P. 0., Wash., D. C.

Claims (1)

1. AN ALLOY CONSISTING BY WEIGHT OF APPROXIMATELY 9.5% TO 12% ALUMINUM, 10% TO 11% CHROMIUM, 1.5% T 3.5% MOLYBDENUM, 0.1% TO 0.7% COBALT, CARBON NOT EXCEEDING APPROXIMATELY 0.15%, 0.05% TO 0.5% MANGANESE, 0.1% TO 0.3% SILICON, IRON NOT EXCEEDING APPROXIMATELY 1.0%, AND THE BALANCE ESSENTIALLY ALL NICKEL SUBSTANTIALLY AS HEREINABOVE DESCRIBED.
US778466A 1946-10-09 1947-10-07 Alloy for heat and corrosion resisting coating Expired - Lifetime US2621122A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005704A (en) * 1958-07-23 1961-10-24 Union Carbide Corp Nickel base alloy for service at high temperatures
US3720537A (en) * 1970-11-25 1973-03-13 United Aircraft Corp Process of coating an alloy substrate with an alloy
DE3234090A1 (en) * 1981-09-14 1983-04-28 United Technologies Corp., 06101 Hartford, Conn. SINGLE CRYSTAL ITEM FROM A NICKEL-BASED SUPER ALLOY
US4556534A (en) * 1983-12-20 1985-12-03 Dentsply Research & Development Corp. Nickel based casting alloy
US4592890A (en) * 1983-08-08 1986-06-03 Dentsply Research & Development Corp. Dental prostheses alloy
US4685977A (en) * 1984-12-03 1987-08-11 General Electric Company Fatigue-resistant nickel-base superalloys and method
US5360496A (en) * 1991-08-26 1994-11-01 Aluminum Company Of America Nickel base alloy forged parts
US5374323A (en) * 1991-08-26 1994-12-20 Aluminum Company Of America Nickel base alloy forged parts
WO2001015837A1 (en) * 1999-09-01 2001-03-08 Brush Wellman, Inc. Improved dies for die casting aluminum and other metals
US6974508B1 (en) 2002-10-29 2005-12-13 The United States Of America As Represented By The United States National Aeronautics And Space Administration Nickel base superalloy turbine disk
US20100243192A1 (en) * 2009-03-24 2010-09-30 Nonferrous Materials Technology Development Centre Molten metal casting die
US20120111525A1 (en) * 2010-11-05 2012-05-10 Bochiechio Mario P High temperature die casting apparatus and method therefor

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1273877A (en) * 1916-06-17 1918-07-30 Paul Richard Kuehnrich Alloy.
GB342868A (en) * 1930-01-13 1931-02-12 Heraeus Vacuumschmelze Ag Improvements relating to sulphur resisting alloys
GB371334A (en) * 1929-10-11 1932-04-13 Commentry Fourchambault Et Dec Process for improving the mechanical properties of ferro-nickelchromium alloys
DE591641C (en) * 1931-07-11 1934-01-25 Heraeus Vacuumschmelze Akt Ges Objects that require high resistance to sulfur and sulfur compounds
GB425614A (en) * 1933-09-15 1935-03-15 Henry Winder Brownsdon Improvements in or relating to heat resisting alloys
US2071645A (en) * 1933-12-29 1937-02-23 Int Nickel Co Electrode and electrical contact
US2113667A (en) * 1934-10-18 1938-04-12 American Brass Co Method of coating ferrous materials with a copper-rich alloy
US2159048A (en) * 1935-10-15 1939-05-23 Int Nickel Co Method of improving the workability of nickel and nickel alloys
US2246078A (en) * 1937-07-31 1941-06-17 Rohn Wilhelm Valve made of cobalt-nickel-chromium-iron alloy
US2403128A (en) * 1942-06-24 1946-07-02 Westinghouse Electric Corp Heat resistant alloys
US2432149A (en) * 1935-05-09 1947-12-09 Int Nickel Co Heat resistant nickel alloys
US2450803A (en) * 1942-01-24 1948-10-05 Thompson Prod Inc Method of making sheathed valves
US2570193A (en) * 1946-04-09 1951-10-09 Int Nickel Co High-temperature alloys and articles

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1273877A (en) * 1916-06-17 1918-07-30 Paul Richard Kuehnrich Alloy.
GB371334A (en) * 1929-10-11 1932-04-13 Commentry Fourchambault Et Dec Process for improving the mechanical properties of ferro-nickelchromium alloys
GB342868A (en) * 1930-01-13 1931-02-12 Heraeus Vacuumschmelze Ag Improvements relating to sulphur resisting alloys
DE591641C (en) * 1931-07-11 1934-01-25 Heraeus Vacuumschmelze Akt Ges Objects that require high resistance to sulfur and sulfur compounds
GB425614A (en) * 1933-09-15 1935-03-15 Henry Winder Brownsdon Improvements in or relating to heat resisting alloys
US2071645A (en) * 1933-12-29 1937-02-23 Int Nickel Co Electrode and electrical contact
US2113667A (en) * 1934-10-18 1938-04-12 American Brass Co Method of coating ferrous materials with a copper-rich alloy
US2432149A (en) * 1935-05-09 1947-12-09 Int Nickel Co Heat resistant nickel alloys
US2159048A (en) * 1935-10-15 1939-05-23 Int Nickel Co Method of improving the workability of nickel and nickel alloys
US2246078A (en) * 1937-07-31 1941-06-17 Rohn Wilhelm Valve made of cobalt-nickel-chromium-iron alloy
US2450803A (en) * 1942-01-24 1948-10-05 Thompson Prod Inc Method of making sheathed valves
US2403128A (en) * 1942-06-24 1946-07-02 Westinghouse Electric Corp Heat resistant alloys
US2570193A (en) * 1946-04-09 1951-10-09 Int Nickel Co High-temperature alloys and articles

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005704A (en) * 1958-07-23 1961-10-24 Union Carbide Corp Nickel base alloy for service at high temperatures
US3720537A (en) * 1970-11-25 1973-03-13 United Aircraft Corp Process of coating an alloy substrate with an alloy
DE3234090A1 (en) * 1981-09-14 1983-04-28 United Technologies Corp., 06101 Hartford, Conn. SINGLE CRYSTAL ITEM FROM A NICKEL-BASED SUPER ALLOY
US4592890A (en) * 1983-08-08 1986-06-03 Dentsply Research & Development Corp. Dental prostheses alloy
US4556534A (en) * 1983-12-20 1985-12-03 Dentsply Research & Development Corp. Nickel based casting alloy
US4685977A (en) * 1984-12-03 1987-08-11 General Electric Company Fatigue-resistant nickel-base superalloys and method
US5360496A (en) * 1991-08-26 1994-11-01 Aluminum Company Of America Nickel base alloy forged parts
US5374323A (en) * 1991-08-26 1994-12-20 Aluminum Company Of America Nickel base alloy forged parts
WO2001015837A1 (en) * 1999-09-01 2001-03-08 Brush Wellman, Inc. Improved dies for die casting aluminum and other metals
US20030098100A1 (en) * 1999-09-01 2003-05-29 Amitava Guha Dies for die casting aluminum and other metals
US6974508B1 (en) 2002-10-29 2005-12-13 The United States Of America As Represented By The United States National Aeronautics And Space Administration Nickel base superalloy turbine disk
US20100243192A1 (en) * 2009-03-24 2010-09-30 Nonferrous Materials Technology Development Centre Molten metal casting die
US8418744B2 (en) * 2009-03-24 2013-04-16 Nonferrous Materials Technology Development Centre Molten metal casting die
US20120111525A1 (en) * 2010-11-05 2012-05-10 Bochiechio Mario P High temperature die casting apparatus and method therefor

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