US3549356A - High temperature corrosive resistant cobalt-base alloys - Google Patents
High temperature corrosive resistant cobalt-base alloys Download PDFInfo
- Publication number
- US3549356A US3549356A US789390A US3549356DA US3549356A US 3549356 A US3549356 A US 3549356A US 789390 A US789390 A US 789390A US 3549356D A US3549356D A US 3549356DA US 3549356 A US3549356 A US 3549356A
- Authority
- US
- United States
- Prior art keywords
- percent
- alloy
- high temperature
- cobalt
- strength
- 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
- 239000000956 alloy Substances 0.000 title description 33
- 229910045601 alloy Inorganic materials 0.000 title description 33
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910052727 yttrium Inorganic materials 0.000 description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052735 hafnium Inorganic materials 0.000 description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000567 combustion gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
Definitions
- Cobalt-base alloys having improved high temperature oxidation and corrosion resistance consist essentially of, in percent by weight, carbon 0.1 to 0.8, nickel 8.5 to 11.5, chromium 24 to 35, tungsten 6 to 9, tantalum 1 to 5, manganese up to 1 max., silicon up to 0.25 max., boron 0.005 to 0.5, yttrium 0.01 to 1.0, iron up to 2.0 max., hafnium 0.05 to 2.0, with the remainder essentially cobalt except for impurities.
- This invention relates to new and useful alloys. More particularly, it relates to alloys which are characterized by good high-temperature strength and at the same time are resistant to oxidation and corrosion by combustion gases at elevated temperatures.
- strong high-temperature corrosion-resistant cobalt base alloys having a percent by weight content of carbon 0.1 to 0.8, nickel 8.5 to 11.5, chromium 24 to 35, tungsten 6 to 9, tantalum 1 to 5, manganese up to 1 max., silicon up to 0.25 max., boron 0.005 to 0.5, yttrium 0.01 to 1.0, iron up to 2.0 max., hafnium 0.05 to 2.0, with the remainder essentially cobalt, except for incidental impurities such as phosphorus and sulfur which are preferably held below a maximum of about 0.015%.
- alloys of the above precisely balanced metallic composition are characterized by substantial improvement in corrosion resistance at elevated temperature, while at the same time retaining suitable 3,549,356 Patented Dec. 22, 1970 strength, ductility, and other physical characteristics for elevated temperature operation.
- the materials are also particularly useful in that they are particularly adapted to precision investment casting techniques permitting the formation of various shaped structures suitable for high-temgerature apparatus such as in the hot stages of gas turmes.
- the relatively high range of chromium is directly contrary to prior art teaching which states that cobalt-base alloys having a chromium content of over about 25% by weight exhibit increased scaling or deterioration due to corrosive influences at elevated temperatures.
- This prior art teaching is set forth, for example, in Journal of the Electrochemical Society, volume 103, No. 8, by Pfalnikar et al., entitled, High Temperature Scaling of Cobalt-Chromium Alloys.
- the present compositions comprise a carefully formulated combination of constituents, each of which contributes to the desirable characteristics obtained. Deviations in the proportions of the materials destroy this critical balance, and result in materials which have been found to be wanting in essential characteristics. For example, when the carbon content is lowered beyond that prescribed, an undesirable loss of strength results. On the other hand, increasing the carbon content above that stated would detract from the rupture ductility of the material and may also detract from weldability. Reduction of the chromium content below that set forth results in detrimental loss of oxidation resistance.
- the nickel
- iron and tungsten additives do not appear to be particularly critical for oxidation and corrosion resistance but it has been found desirable to have them present in the stated ranges for suitable structural mechanical properties.
- Boron imparts ductility to the alloy but increasing the boron beyond the content set forth causes detrimental low-melting phases to form in the alloy.
- Yttrium when used in lower amounts than that set forth above, results in decreased oxidation and corrosion resistance.
- amounts of yttrium greater than the upper prescribed limit are diflicult to retain effectively in the product by normal melting procedures. Within the prescribed limits, yttrium greatly improves the scale spalling resistance of the alloy under the thermal cycling conditions encountered in gas turbines, for instance.
- Hafnium contributes strength to the alloy in the amounts indicated by modifying the type of carbides present in favor of carbides with greater thermal stability. Lower amounts detract from this favorable characteristic while larger amounts than those indicated do not contribute any additional benefit.
- Example 1 600 20 405. 5 18. 2 48. 3 4 6 1, 700 226. 4 21. 4 57. 0 48. 3 1, 825 10 50. 9 1, 900 6 54. 2
- the rupture strength is indicative of the present alloy using room temperature tensile strength comparable to the prior art alloy; the present material, however, has about three times the ductility as measured by reduction in areas.
- the stress-rupture test results in Table I indicate that the stress-rupture strength of the present alloy using the Larsen-Miller parameter indicated has a strength comparable to the prior art alloy at high stresses, with a clear crossover at low stresses in favor of the present alloy. It will thus be seen that the present alloys are particularly adaptable to applications such as stationary nozzle guide vanes or partitions and similar applications which are characterized by high operating temperatures and relatively low stresses.
- Table II Shown in Table II is the hot-corrosion resistance of the present exemplary alloy as compared to the above prior art alloy.
- pin-shaped test pieces of the material of the above example and the prior art material were placed in the combustion gas stream flow in a simulated gas turbine burner apparatus at the 1900" F. indicated temperature using combustion Diesel oil (MIL-F- 16884) containing 1% by Weight sulfur at an air to fuel weight ratio of :1.
- MIL-F- 16884 combustion Diesel oil
- Five ppm. sea salt ASTM, D665-60
- the specimens were thermal cycled every fifty hours to simulate gas turbine shutdown, this procedure being properly rigorous as it evaluates adherence properties of the protective scale. After the times indicated, the surface loss and maximum penetration were measured for each sample in terms of mils per side.
- a cobalt base alloy characterized by good high temperature oxidation and corrosion resistance consisting essentially of about, by weight, carbon 0.1 to 0.8 percent, nickel 8.5 to 11.5 percent, chromium 24 to 35 percent, tungsten 6 to 9 percent, tantalum 1 to 5 percent, manganese up to 1 percent max., silicon up to 0.25 percent max., boron 0.005 to 0.5 percent, yttrium 0.01 to 1.0 percent, iron up to 2.0 percent max., hafnium 0.05 to 2.0 percent, with the remainder essentially cobalt except for impurities.
- a cobalt base alloy characterized by good high temperature oxidation and corrosion resistance consisting essentially of about, by weight, carbon 0.40 percent, nickel 10.7 percent, chromium 28.7 percent, tungsten 7.4 percent, tantalum 3.1 percent, manganese 0.30 percent, silicon 0.21 percent, boron 0.016 percent, yttrium 0.18 percent, iron 0.26 percent and hafnium 0.15 percent, with the remainder essentially cobalt except for impurities.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78939069A | 1969-01-06 | 1969-01-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3549356A true US3549356A (en) | 1970-12-22 |
Family
ID=25147501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US789390A Expired - Lifetime US3549356A (en) | 1969-01-06 | 1969-01-06 | High temperature corrosive resistant cobalt-base alloys |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3549356A (de) |
| CH (1) | CH527275A (de) |
| GB (1) | GB1244688A (de) |
| NL (1) | NL7000099A (de) |
| SE (1) | SE339572B (de) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2334759A1 (fr) * | 1975-12-08 | 1977-07-08 | United Technologies Corp | Superalliages a base de cobalt resistant a l'oxydation et procede de preparation |
| US4084964A (en) * | 1973-06-18 | 1978-04-18 | Massachusetts Institute Of Technology | High HfC-containing alloys |
| EP0186797A1 (de) * | 1984-12-04 | 1986-07-09 | General Electric Company | Superlegierung auf Kobaltbasis und daraus hergestellte gegossene und geschweisste Bauteile für Gasturbinen |
| FR2576914A1 (fr) * | 1985-02-04 | 1986-08-08 | Asahi Fibreglass Co | Alliages a base de co, resistant a la chaleur et au verre fondu |
| US4618474A (en) * | 1985-01-25 | 1986-10-21 | Asahi Fiber Glass Company, Limited | Co-base heat resistant alloy |
| US4668265A (en) * | 1985-06-18 | 1987-05-26 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy and method of making fibers |
| US4668266A (en) * | 1985-06-18 | 1987-05-26 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy having a high chromium content and method of making fibers |
| US4765817A (en) * | 1985-06-18 | 1988-08-23 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy containing hafnium |
| US4767432A (en) * | 1985-06-18 | 1988-08-30 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy containing hafnium and a high proportion of chromium |
| WO1988009393A1 (en) * | 1987-05-18 | 1988-12-01 | Owens-Corning Fiberglas Corporation | Glass corrosion resistant cobalt-based alloy having high strength |
| US4938805A (en) * | 1984-12-04 | 1990-07-03 | General Electric Company | Novel cobalt-base superalloy and cast and welded industrial gas turbine components thereof and method |
| EP0457503A1 (de) * | 1990-05-18 | 1991-11-21 | General Electric Company | Hartlotlegierungen und ihre Verwendung |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3005705A (en) * | 1959-07-30 | 1961-10-24 | Westinghouse Electric Corp | High temperature alloys |
| US3202506A (en) * | 1963-01-23 | 1965-08-24 | David E Deutsch | High-temperature oxidation-resistant cobalt base alloys |
| US3346378A (en) * | 1965-03-22 | 1967-10-10 | Gen Electric | Cobalt base alloys |
-
1969
- 1969-01-06 US US789390A patent/US3549356A/en not_active Expired - Lifetime
- 1969-11-20 SE SE15987/69A patent/SE339572B/xx unknown
- 1969-12-09 GB GB60007/69A patent/GB1244688A/en not_active Expired
- 1969-12-29 CH CH1936269A patent/CH527275A/de not_active IP Right Cessation
-
1970
- 1970-01-06 NL NL7000099A patent/NL7000099A/xx unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3005705A (en) * | 1959-07-30 | 1961-10-24 | Westinghouse Electric Corp | High temperature alloys |
| US3202506A (en) * | 1963-01-23 | 1965-08-24 | David E Deutsch | High-temperature oxidation-resistant cobalt base alloys |
| US3346378A (en) * | 1965-03-22 | 1967-10-10 | Gen Electric | Cobalt base alloys |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4084964A (en) * | 1973-06-18 | 1978-04-18 | Massachusetts Institute Of Technology | High HfC-containing alloys |
| US4078922A (en) * | 1975-12-08 | 1978-03-14 | United Technologies Corporation | Oxidation resistant cobalt base alloy |
| FR2334759A1 (fr) * | 1975-12-08 | 1977-07-08 | United Technologies Corp | Superalliages a base de cobalt resistant a l'oxydation et procede de preparation |
| US4938805A (en) * | 1984-12-04 | 1990-07-03 | General Electric Company | Novel cobalt-base superalloy and cast and welded industrial gas turbine components thereof and method |
| EP0186797A1 (de) * | 1984-12-04 | 1986-07-09 | General Electric Company | Superlegierung auf Kobaltbasis und daraus hergestellte gegossene und geschweisste Bauteile für Gasturbinen |
| US4618474A (en) * | 1985-01-25 | 1986-10-21 | Asahi Fiber Glass Company, Limited | Co-base heat resistant alloy |
| FR2576914A1 (fr) * | 1985-02-04 | 1986-08-08 | Asahi Fibreglass Co | Alliages a base de co, resistant a la chaleur et au verre fondu |
| US4668265A (en) * | 1985-06-18 | 1987-05-26 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy and method of making fibers |
| US4765817A (en) * | 1985-06-18 | 1988-08-23 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy containing hafnium |
| US4767432A (en) * | 1985-06-18 | 1988-08-30 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy containing hafnium and a high proportion of chromium |
| US4668266A (en) * | 1985-06-18 | 1987-05-26 | Owens-Corning Fiberglas Corporation | Corrosion resistant cobalt-base alloy having a high chromium content and method of making fibers |
| WO1988009393A1 (en) * | 1987-05-18 | 1988-12-01 | Owens-Corning Fiberglas Corporation | Glass corrosion resistant cobalt-based alloy having high strength |
| US4820324A (en) * | 1987-05-18 | 1989-04-11 | Owens-Corning Fiberglas Corporation | Glass corrosion resistant cobalt-based alloy having high strength |
| EP0457503A1 (de) * | 1990-05-18 | 1991-11-21 | General Electric Company | Hartlotlegierungen und ihre Verwendung |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7000099A (de) | 1970-07-08 |
| GB1244688A (en) | 1971-09-02 |
| SE339572B (de) | 1971-10-11 |
| CH527275A (de) | 1972-08-31 |
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