US3046109A - High temperature niobium base alloy - Google Patents
High temperature niobium base alloy Download PDFInfo
- Publication number
- US3046109A US3046109A US810499A US81049959A US3046109A US 3046109 A US3046109 A US 3046109A US 810499 A US810499 A US 810499A US 81049959 A US81049959 A US 81049959A US 3046109 A US3046109 A US 3046109A
- Authority
- US
- United States
- Prior art keywords
- alloy
- base alloy
- niobium
- oxidation resistance
- titanium
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 229910052758 niobium Inorganic materials 0.000 title claims description 24
- 239000010955 niobium Substances 0.000 title claims description 24
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims description 24
- 229910045601 alloy Inorganic materials 0.000 title description 35
- 239000000956 alloy Substances 0.000 title description 35
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 3
- RLQJEEJISHYWON-UHFFFAOYSA-N flonicamid Chemical compound FC(F)(F)C1=CC=NC=C1C(=O)NCC#N RLQJEEJISHYWON-UHFFFAOYSA-N 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000753 refractory alloy Inorganic materials 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
Definitions
- This invention relates to a niobium base alloy having an outstanding combination of high hot strength, fabricability and oxidation resistance at elevated temperatures. It pertains particularly to a refractory metal alloy of this type which is designed for buckets and guide vanes of gas turbine engines in which metal temperatures reach 2000" F.
- the nickel base alloy and cobalt base alloy blades commonly used today in gas turbine engines for aircraft normally have maximum service temperatures of approximately 1800 F. to 1900 F. This limitation necessarily restricts the performance and efiiciency of these engines.
- Refractory metals such as niobium, tungsten, molybdenum and chromium, have satisfactory high melting temperatures and sufficient potential availability to warrant investigation as high temperature turbine blade materials.
- each of these metals exhibits poor oxidation resistance at temperatures of 2000 F. or above.
- Such metals are therefore unsatisfactory for use in turbine blades which necessarily are exposed to extremely hot oxidizing gases.
- attempts have been made to correct this deficiency by adding small amounts of various alloying elements to these refractory base metals. However, these attempts have been unsuccessful since the resultant products still did not possess adequate oxidation resistance at the very high temperatures under consideration.
- a principal object of the present invention is to provide a refractory alloy which can be employed as a turbine blade material at temperatures up to 2000 F. because of its oxidation resistance at such temperatures, coupled with good hot strength and other necessary physical properties. It is considered desirable that an alloy to be used for gas turbine service in air at 2000 F. have a 100-hour stress-rupture life at that temperature under a load of 15,000 p.s.i. Such an alloy also must possess adequate fabricability and a melting point of at least 3000 F. Of course, turbine blades formed of this alloy should have adequate room temperature ductility as Well as good oxidation resistance in air at a temperature of 2000 F.
- a refractory alloy comprising about 2% to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium and the balance (76% to 84%) substantially all niobium.
- Approximately 0.5% to 2% zirconium is preferably also included in the alloy and serves to increase its strength to an appreciable extent without adversely affecting its extreme high temperature oxidation resistance.
- the molybdenum serves to materially increase the oxidation resistance of the niobium base alloy and also contributes to its hot strength.
- the molybdenum content is lower than about 9% or higher than approximately 11%, the oxidation resistance of the alloy is noticeably reduced.
- Titanium also improves oxidation resistance, although it is also necessary in order to provide the niobium base alloy with the desired amount of ductility. If the amount of titanium present is less than about 2%, embrittlement of the alloy results. A titanium content of 5% produces greater oxidation resistance than 2% titanium, but when more than 5% titanium is present the hot strength of the alloy is reduced to an excessive extent.
- chromium contributes to the oxidation resistance of the niobium base alloy as well as increasing its hot strength.
- a chromium content of at least 4% is necessary for outstanding oxidation resistance, but if more than approximately 8% chromium is included the alloy becomes excessively brittle.
- the zirconium increases the strength of the niobium base alloy, and at least 0.5% zirconium is desirable to maintain this property at a sufiiciently high level. If zirconium is present in a quantity greater than about 2%, the niobium base alloy becomes susceptible to atmospheric contamination.
- niobium base alloy has been prepared by alloying high purity elemental raw materials in an inert atmosphere of argon plus helium. It was found that the constituents of the alloy may be added either simultaneously or successively. Melting was accomplished with a nonconsumable tungsten electrode electric arc. After solidification of the alloy, it was crushed to fine particle size and re-melted in the above-described manner and cast in ingot form. This ingot was enclosed in a container formed of an alloy of molybdenum plus 0.5% titanium, heated to approximately 2700" F., and extruded.
- Sound extrusions may be obtained with the niobium base alloy of this invention by direct extrusion of the cast ingot, the extruded alloy having a fibrous appearing cold worked structure. Subsequent further working has been accomplished by both swaging and rolling.
- Stress-rupture test bars were machined from this extruded niobium base alloy bar stock and tested in an argon atmosphere at a temperature of 2000 F. under progressively increasing loads from 10,000 p.s.i. to 25,000 p.s.i.
- an alloy consisting of about 82% niobium, 10% molybdenum, 4% chromium, 2% titanium and 2% zirconium had a hot strength estimated to be appreciably in excess of 25,000 p.s.i. for more than hours at a temperature of 2000" F.
- the results of this particular test were as follows.
- a niobium base alloy characterized by good hot strength and outstanding oxidation resistance at elevated temperatures, said alloy consisting essentially of about 2% to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium, 0.5% to 2% zirconium and the balance substantially all niobium.
- a gas turbine blade characterized by outstanding oxidation resistance upon exposure to oxidizing gases at a temperature of 2000 B, said blade being formed of an alloy comprising about 2% to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium, 0.5% to 2% zirconium and 76% to 84% niobium.
- a high temperature niobium base alloy having an outstanding combination of hot strength, fabricability, oxidation resistance and a stress-rupture life of more than 100 hours under a load of 15,000 p.s.i. at a temperature of 2000 F., said alloy consisting essentially of about 2% 4 to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium, approximately 2% zirconium and 76% to 84% niobium.
- An oxidation-resistant high temperature niobium base alloy consisting essentially of about 2% titanium, 10% molybdenum, 4% chromium, 2% zirconium and the balance niobium.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Description
United States Patent Oiiice 3,046,109 Patented July 24, 1962 3,046,109 HIGH TEMPERATURE NIOBIUM BASE ALLOY Neil M. Lottridge, Jr., Warren, Mich., assignor to General Motors Corporation, Detroit, Mich., a corporation of Delaware No Drawing. Filed May 1, 1959, Ser. No. 810,499 4 Claims. (Cl. 75-174) This invention relates to a niobium base alloy having an outstanding combination of high hot strength, fabricability and oxidation resistance at elevated temperatures. It pertains particularly to a refractory metal alloy of this type which is designed for buckets and guide vanes of gas turbine engines in which metal temperatures reach 2000" F.
The nickel base alloy and cobalt base alloy blades commonly used today in gas turbine engines for aircraft normally have maximum service temperatures of approximately 1800 F. to 1900 F. This limitation necessarily restricts the performance and efiiciency of these engines. Refractory metals, such as niobium, tungsten, molybdenum and chromium, have satisfactory high melting temperatures and sufficient potential availability to warrant investigation as high temperature turbine blade materials. However, each of these metals exhibits poor oxidation resistance at temperatures of 2000 F. or above. Such metals are therefore unsatisfactory for use in turbine blades which necessarily are exposed to extremely hot oxidizing gases. During recent years attempts have been made to correct this deficiency by adding small amounts of various alloying elements to these refractory base metals. However, these attempts have been unsuccessful since the resultant products still did not possess adequate oxidation resistance at the very high temperatures under consideration.
Consequently, a principal object of the present invention is to provide a refractory alloy which can be employed as a turbine blade material at temperatures up to 2000 F. because of its oxidation resistance at such temperatures, coupled with good hot strength and other necessary physical properties. It is considered desirable that an alloy to be used for gas turbine service in air at 2000 F. have a 100-hour stress-rupture life at that temperature under a load of 15,000 p.s.i. Such an alloy also must possess adequate fabricability and a melting point of at least 3000 F. Of course, turbine blades formed of this alloy should have adequate room temperature ductility as Well as good oxidation resistance in air at a temperature of 2000 F.
In accordance with this invention, I have found that the foregoing requirements are satisfied to an outstanding degree by a refractory alloy comprising about 2% to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium and the balance (76% to 84%) substantially all niobium. Approximately 0.5% to 2% zirconium is preferably also included in the alloy and serves to increase its strength to an appreciable extent without adversely affecting its extreme high temperature oxidation resistance. An alloy composed of about 82% niobium, 10% molybdenum, 2% titanium, 4% chromium and 2% zirconium, for example, had a total surface metal loss of less than 5 mils in thickness after 100 hours cyclic exposure in air at a temperature of 2000 F. Small quantities of various other elements, usually less than 1%, can be tolerated in the alloy without detracting from its mechanical properties.
The molybdenum serves to materially increase the oxidation resistance of the niobium base alloy and also contributes to its hot strength. When the molybdenum content is lower than about 9% or higher than approximately 11%, the oxidation resistance of the alloy is noticeably reduced.
Titanium also improves oxidation resistance, although it is also necessary in order to provide the niobium base alloy with the desired amount of ductility. If the amount of titanium present is less than about 2%, embrittlement of the alloy results. A titanium content of 5% produces greater oxidation resistance than 2% titanium, but when more than 5% titanium is present the hot strength of the alloy is reduced to an excessive extent.
Likewise, chromium contributes to the oxidation resistance of the niobium base alloy as well as increasing its hot strength. A chromium content of at least 4% is necessary for outstanding oxidation resistance, but if more than approximately 8% chromium is included the alloy becomes excessively brittle.
The zirconium increases the strength of the niobium base alloy, and at least 0.5% zirconium is desirable to maintain this property at a sufiiciently high level. If zirconium is present in a quantity greater than about 2%, the niobium base alloy becomes susceptible to atmospheric contamination.
The above-described niobium base alloy has been prepared by alloying high purity elemental raw materials in an inert atmosphere of argon plus helium. It was found that the constituents of the alloy may be added either simultaneously or successively. Melting was accomplished with a nonconsumable tungsten electrode electric arc. After solidification of the alloy, it was crushed to fine particle size and re-melted in the above-described manner and cast in ingot form. This ingot was enclosed in a container formed of an alloy of molybdenum plus 0.5% titanium, heated to approximately 2700" F., and extruded. Sound extrusions may be obtained with the niobium base alloy of this invention by direct extrusion of the cast ingot, the extruded alloy having a fibrous appearing cold worked structure. Subsequent further working has been accomplished by both swaging and rolling.
Stress-rupture test bars were machined from this extruded niobium base alloy bar stock and tested in an argon atmosphere at a temperature of 2000 F. under progressively increasing loads from 10,000 p.s.i. to 25,000 p.s.i. For example, an alloy consisting of about 82% niobium, 10% molybdenum, 4% chromium, 2% titanium and 2% zirconium had a hot strength estimated to be appreciably in excess of 25,000 p.s.i. for more than hours at a temperature of 2000" F. The results of this particular test were as follows.
Stress-Rupture Test at 2000" F. in Argon Atmosphere Stress in p.s.i.: Hours prior to next higher stress 10,000 1 20 15,000 100 20,000 20 25,000 102 (failed) Total elongation, measured on the machined test bar halves after rupture, was approximately 47%. A reduction in area of 54.6% was measured in the test bar gauge length. These data show that the niobium base alloy possesses the combination of excellent oxidation resistance at extreme temperatures and high hot strength. The alloy has a melting point materially in excess of 3000 F the desired minimum hereinbefore mentioned.
While my invention has been described by means of certain specific examples, it is to be understood that the scope of the invention is not to be limited thereby except as defined by the following claims.
I claim:
1. A niobium base alloy characterized by good hot strength and outstanding oxidation resistance at elevated temperatures, said alloy consisting essentially of about 2% to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium, 0.5% to 2% zirconium and the balance substantially all niobium.
2. A gas turbine blade characterized by outstanding oxidation resistance upon exposure to oxidizing gases at a temperature of 2000 B, said blade being formed of an alloy comprising about 2% to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium, 0.5% to 2% zirconium and 76% to 84% niobium.
3. A high temperature niobium base alloy having an outstanding combination of hot strength, fabricability, oxidation resistance and a stress-rupture life of more than 100 hours under a load of 15,000 p.s.i. at a temperature of 2000 F., said alloy consisting essentially of about 2% 4 to 5% titanium, 9% to 11% molybdenum, 4% to 8% chromium, approximately 2% zirconium and 76% to 84% niobium.
4. An oxidation-resistant high temperature niobium base alloy consisting essentially of about 2% titanium, 10% molybdenum, 4% chromium, 2% zirconium and the balance niobium.
Rhodin Apr. 14, 1959 Wainer Apr. 21, 1959
Claims (1)
- 2. A GAS TURBINE BLADE CHARACTERIZED BY OUTSTANDING OXIDATION RESISTANCE UPON EXPOSURE TO OXIDIZING GASES AT A TEMPERATURE OF 2000* F., SAID BLADE BEING FORMED OF AN ALLOY COMPRISING ABOUT 2% TO 5% TITANIUM, 9% TO 11% MOLYBDENUM, 4% TO 8% CHRONIUM, 0.5% TO 5% ZIRCONIUM AND 79% TO 84% NIOBIUM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US810499A US3046109A (en) | 1959-05-01 | 1959-05-01 | High temperature niobium base alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US810499A US3046109A (en) | 1959-05-01 | 1959-05-01 | High temperature niobium base alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3046109A true US3046109A (en) | 1962-07-24 |
Family
ID=25203998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US810499A Expired - Lifetime US3046109A (en) | 1959-05-01 | 1959-05-01 | High temperature niobium base alloy |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3046109A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3296038A (en) * | 1962-12-21 | 1967-01-03 | United Aircraft Corp | High temperature columbium base alloys |
| US3346379A (en) * | 1961-11-15 | 1967-10-10 | Union Carbide Corp | Niobium base alloy |
| US20110146848A1 (en) * | 2008-11-21 | 2011-06-23 | General Electric Company | Oxide-forming protective coatigns for niobium-based materials |
| RU2618038C2 (en) * | 2015-10-13 | 2017-05-02 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Method for obtaining a heat-resistant alloy based on niobium |
| US11198927B1 (en) * | 2019-09-26 | 2021-12-14 | United States Of America As Represented By The Secretary Of The Air Force | Niobium alloys for high temperature, structural applications |
| US11846008B1 (en) | 2019-09-26 | 2023-12-19 | United States Of America As Represented By Secretary Of The Air Force | Niobium alloys for high temperature, structural applications |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2882146A (en) * | 1957-09-27 | 1959-04-14 | Du Pont | High temperature niobium base alloy |
| US2883282A (en) * | 1957-05-21 | 1959-04-21 | Horizons Inc | Protection of niobium from oxidation |
-
1959
- 1959-05-01 US US810499A patent/US3046109A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2883282A (en) * | 1957-05-21 | 1959-04-21 | Horizons Inc | Protection of niobium from oxidation |
| US2882146A (en) * | 1957-09-27 | 1959-04-14 | Du Pont | High temperature niobium base alloy |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3346379A (en) * | 1961-11-15 | 1967-10-10 | Union Carbide Corp | Niobium base alloy |
| US3296038A (en) * | 1962-12-21 | 1967-01-03 | United Aircraft Corp | High temperature columbium base alloys |
| US20110146848A1 (en) * | 2008-11-21 | 2011-06-23 | General Electric Company | Oxide-forming protective coatigns for niobium-based materials |
| US8247085B2 (en) * | 2008-11-21 | 2012-08-21 | General Electric Company | Oxide-forming protective coatings for niobium-based materials |
| RU2618038C2 (en) * | 2015-10-13 | 2017-05-02 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Method for obtaining a heat-resistant alloy based on niobium |
| US11198927B1 (en) * | 2019-09-26 | 2021-12-14 | United States Of America As Represented By The Secretary Of The Air Force | Niobium alloys for high temperature, structural applications |
| US11846008B1 (en) | 2019-09-26 | 2023-12-19 | United States Of America As Represented By Secretary Of The Air Force | Niobium alloys for high temperature, structural applications |
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