US3617264A - High-temperature oxidation-resistant cobalt base alloys - Google Patents
High-temperature oxidation-resistant cobalt base alloys Download PDFInfo
- Publication number
- US3617264A US3617264A US889344A US3617264DA US3617264A US 3617264 A US3617264 A US 3617264A US 889344 A US889344 A US 889344A US 3617264D A US3617264D A US 3617264DA US 3617264 A US3617264 A US 3617264A
- Authority
- US
- United States
- Prior art keywords
- percent
- effective amount
- temperature
- alloy
- cobalt
- 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
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 47
- 239000000956 alloy Substances 0.000 title claims abstract description 47
- 239000010941 cobalt Substances 0.000 title claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 13
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 230000003313 weakening effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 208000003629 Rupture Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000009466 transformation 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
- 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 strength, ductility, and oxidation resistance consist essentially of, in percent by weight, chromium 20-35, carbon 0.05-L5, tungsten 2-12, tantalum an effective amount of about 1 up to 7, iron 3-17, boron an effective amount of about 0.005 up to 0.1, yttrium 0.05-0.4, titanium an effective amount of about 0.1 up to 3, zirconium an effective amount of about 0.1 up to 3, with the remainder essentially cobalt except for impurities.
- This invention relates to new and useful cobalt base alloys which are particularly characterized by improved high-temperature strength and ductility and have increased resistance to oxidation and hot corrosion at elevated temperatures.
- an increase in operating temperature of a typical gas turbine from about 1,500 to l,600 F. produces an increase in power output of about 14 percent and an increase in efficiency of up to 1 about percent.
- the constant search for such high-temperature alloys will thus be appreciated, and it is a principal object of this invention to provide new and useful alloys which will permit the operation of equipment such as gas turbines at temperatures of up to about 1,900" to 2,000 F. or even higher.
- Another object of the invention is to provide improved materials of construction for high-temperature equipment in general which are subjected to oxidative atmospheres such as furnaces and the like.
- the present invention economical, high-temperature, oxidation-resistant, cobalt base alloys which are also characterized by good room temperature and elevated temperature strength characteristics and goodhot corrosion resistance which have a percent by weight composition of chromium -35, carbon 0.05-l.5, tungsten 2-12, tantalum an effective amount of about 1 upto 7, iron 3-17, boron an effective amount of about 0.005 up to 0.1, yttrium ODS-0.4, titanium an effective amount of about 0.1 up to 3, zirconium an effective amount of about 0.1 up to 3, with the remainder essentially cobalt except for impurities such as manganese, silicon, sulfur, and phosphorus.
- the manganese is kept below a maximum of about 1.2 percent, the silicon below about 1 percent, and the sulfur and phosphorus each below about 0.04 percent.
- alloys of the above precisely balanced composition are characterized by substantial improvements in oxidation resistance at elevated temperatures, at the same time retaining suitable strength, ductility, and other physical characteristics for operation at such temperatures.
- the alloys are also particularly useful in that they are adapted to precision investment casting techniques and other molding techniques which permit the precision formation of various shaped structures suitable for high-temperature apparatus such as buckets and such of the hot stages of gas turbines.
- compositions represent a carefully balanced formulation of constituents, each of which contributes in the amounts stated to the desirable end results obtained. Deviations in the amounts of materials destroy this critical balance resulting in materials which have been found to be lacking in one or more desired characteristics. For example reduction of the chromium content below that prescribed results in a detrimental loss of oxidation resistance while excessive amounts of chromium produce precipitation of a cobalt plus chromiumrich sigma phase intermetallic compound, which precipitation embrittles the alloy during service and further renders it brittle at room temperature. When the carbon is lowered beyond that indicated, undesirable weakening occurs, whereas increasing the carbon content above that set forth results in an embrittling tendency due to excessive precipitation of metal carbides at thealloy grain boundaries.
- nickel As a matrix stabilizer.
- iron which is much less. expensivethan nickel, effectively stabilizes the alloy, matrix. That is, an equal percentage substitution of iron for nickel more effectively inhibits transformation of the matrix crystallographic structure from the high-temperature face centered cubic polymorph to the low-temperature, less ductile hexagonal closely packed polymorph.
- nickel is in world. wide short supply while iron is widely available, which increases the practicality of this alloy dramatically while at the same time sharply decreasing the price. Greater amounts of iron than those set forth, however, unduly weaken the alloy.
- boron strengthens the alloy through precipitationof metal borides and creation of thermodynamic grain boundary perfection. in excess amounts, howcvenmetal boride precipitation at the alloy grain boundaries severely embrittles the alloy.
- Yttrium is particularly critical to the oxidation and hot corrosion resistance of these alloys, by the manner in which properties of the predominant oxide, C50 are improved. Adherence of this scale, particularly under thermal cycling conditions, is markedly improved due to the mechanical keying of scale to alloy substrate afforded by the presence of yttrium-rich oxide particles formed near the oxidizing surface. These same particles inhibit the free flow of chromium atoms to the surface, thereby reducing the rate at which the alloy oxidizes.
- EXAMPLE 1 There was prepared by vacuum induction melting techniques an alloy consisting of by weight percent: chromium 24, carbon 0.65, tungsten 7, tantalum 3.5, iron 10, boron 0.015, yttrium 0.15, titanium 0.2, zirconium 0.5, manganese 0.3, silicon 0.1, sulfur 0.015, and phosphorus 0.015, with the remainder essentially cobalt except for other incidental impurities.
- This alloy was poured into ceramic molds to prepare test bars 3 inches long by 0.252 inch diameter.
- a first heat, heat No. I had a casting temperature of 2,850 F., a mold temperature of 1,500 F., and was cooled in the enclosed mold.
- Heat No. 2 had a casting temperature of 2,680 F., a
- Shown in table ll is the hot corrosion resistance of the present exemplary alloy as compared to the above prior art alloy.
- disc-shaped test pieces of the, above example and the prior art material were placed in the combustion gas stream flow in a simulated gas turbineburner apparatus at the temperatures indicated using natural gas as a fuel at an air-tofuel weight ratio of 50 to l.
- TI-Ie specimens were thermal cycled" every 50 hours to simulate gas turbine shutdown, this procedure being particularly rigorous-as it evaluates the adherence properties of the protective scale. After the times indicated, the surface loss and maximum-penetration were measured metallographically for each sample in terms of mils per side.
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)
- Powder Metallurgy (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88934469A | 1969-12-30 | 1969-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3617264A true US3617264A (en) | 1971-11-02 |
Family
ID=25394935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US889344A Expired - Lifetime US3617264A (en) | 1969-12-30 | 1969-12-30 | High-temperature oxidation-resistant cobalt base alloys |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3617264A (enrdf_load_stackoverflow) |
| DE (1) | DE2063719A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2074477A5 (enrdf_load_stackoverflow) |
| GB (1) | GB1304060A (enrdf_load_stackoverflow) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3202506A (en) * | 1963-01-23 | 1965-08-24 | David E Deutsch | High-temperature oxidation-resistant cobalt base alloys |
-
1969
- 1969-12-30 US US889344A patent/US3617264A/en not_active Expired - Lifetime
-
1970
- 1970-12-18 GB GB6013370A patent/GB1304060A/en not_active Expired
- 1970-12-24 DE DE19702063719 patent/DE2063719A1/de active Pending
- 1970-12-30 FR FR7047341A patent/FR2074477A5/fr not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3202506A (en) * | 1963-01-23 | 1965-08-24 | David E Deutsch | High-temperature oxidation-resistant cobalt base alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2063719A1 (de) | 1971-07-01 |
| FR2074477A5 (enrdf_load_stackoverflow) | 1971-10-01 |
| GB1304060A (enrdf_load_stackoverflow) | 1973-01-24 |
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