EP3031939B1 - Ni-group superalloy strengthened by oxide-particle dispersion - Google Patents
Ni-group superalloy strengthened by oxide-particle dispersion Download PDFInfo
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- EP3031939B1 EP3031939B1 EP14834221.5A EP14834221A EP3031939B1 EP 3031939 B1 EP3031939 B1 EP 3031939B1 EP 14834221 A EP14834221 A EP 14834221A EP 3031939 B1 EP3031939 B1 EP 3031939B1
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- 239000002245 particle Substances 0.000 title claims description 54
- 229910000601 superalloy Inorganic materials 0.000 title claims description 31
- 239000006185 dispersion Substances 0.000 title description 4
- 239000013078 crystal Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000956 alloy Substances 0.000 description 45
- 229910045601 alloy Inorganic materials 0.000 description 44
- 239000000843 powder Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- 238000005728 strengthening Methods 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 21
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- 239000006104 solid solution Substances 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
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- 238000001556 precipitation Methods 0.000 description 12
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- 230000000694 effects Effects 0.000 description 9
- 238000005275 alloying Methods 0.000 description 7
- 238000001192 hot extrusion Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000009489 vacuum treatment Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 Y4Al2O9 Chemical compound 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000004881 precipitation hardening Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007789 sealing Methods 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
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
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- 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
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
-
- 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
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
Definitions
- the present invention relates to an oxide particle dispersion-strengthened Ni-base superalloy.
- Components to be exposed to high-temperature environments are required to be made of materials having high mechanical properties and high oxidation resistance in a wide temperature range from room temperature to high temperatures.
- materials used include superalloys such as Ni-base superalloys.
- Ni-base superalloys exhibit excellent properties based on solid solution strengthening and ⁇ ' phase precipitation strengthening mechanisms. Many excellent single crystal casting alloys have already been developed based on such strengthening mechanisms. However, the allowable temperature improvement based on these strengthening mechanisms gradually becomes difficult with increasing temperature.
- oxide particle dispersion-strengthened Ni-base superalloys are promising materials because it is considered that their allowable temperature can be improved based on an oxide fine particle dispersion strengthening mechanism in addition to the above strengthening mechanisms.
- Oxide particle dispersion-strengthened Ni-base superalloys have a characteristic structure in which a large number of oxide fine particles typically with sizes of 1 ⁇ m or less are dispersed in the matrix phase where elements other than Ni form a solid solution in Ni. Depending on alloy composition, they can also have a structure in which a precipitate such as the ⁇ ' phase is also dispersed in addition to the oxide particles.
- Oxide particle dispersion-strengthened Ni-base superalloys developed so far include MA6000 alloys (Patent Literatures 1 to 3 and Non Patent Literature 1) and TMO-2 alloys (Patent Literatures 4 to 5 and Non Patent Literature 2). Basically, these alloys are produced by a process that includes preparing an alloy powder by mechanical alloying and then consolidating the alloy powder by hot extrusion or other processes. TMO-2 alloys have a higher level of high-temperature strength because they have a tungsten (W) or tantalum (Ta) content higher than that of MA6000 alloys. Other oxide particle dispersion-strengthened Ni-base superalloys have also been proposed (Patent Literature 6). High-temperature corrosion and high-temperature oxidation of an yttria particle dispersion-strengthened alloy have also been examined and reported (Non Patent Literature 3).
- the TMO-2 alloys contains 12% by weight or more of W so as to have improved high-temperature strength.
- Such a high W content is effective in improving mechanical properties but may reduce high-temperature corrosion resistance.
- oxide particle dispersion-strengthened Ni-base superalloys have investigated the composition of oxide particle dispersion-strengthened Ni-base superalloys.
- the inventors have found that when having a ruthenium (Ru) content in the range of 0.1 % by weight to 14.0% by weight, oxide particle dispersion-strengthened Ni-base superalloys can have good high-temperature corrosion resistance and a higher level of mechanical properties such as high-temperature strength.
- the present invention has been accomplished based on such findings.
- an oxide particle dispersion-strengthened Ni-base superalloy consisting of 0.1% by weight to 14.0% by weight of Ru, 0.1% by weight to 14.0% by weight of Al, and optionally at least one of 0.1% by weight to 14.0% by weight of Re, 0.1% by weight to 20.0% by weight of Co, 0.1% by weight to 20.0% by weight of Cr, 0.1% by weight to 15.0% by weight of Mo, 0.1% by weight to 20.0% by weight of W, 0.1% by weight to 10.0% by weight of Ti, 0.1% by weight to 10.0% by weight of Nb, 0.1% by weight to 15.0% by weight of Ta, 0.01% by weight to 10.0% by weight of Hf, 0.01% by weight to 10.0% by weight of Zr, 0.1% by weight to 5.0% by weight of V, 0.1% by weight to 10.0% by weight of Pt, 0.1% by weight to 10.0% by weight of Pd, 0.1% by weight to 10.0% by weight of lr, 0.001% by weight to 1.0% by weight of B, or 0.001% by weight
- the oxide particle dispersion-strengthened Ni-base superalloy of the present invention containing 0.1% by weight to 14.0% by weight of Ru can have good high-temperature corrosion resistance and a significantly improved level of high-temperature strength and other mechanical properties, such as a significantly improved level of mechanical properties after heating at a temperature in the range of 1,260°C to 1,300°C as shown in the examples below.
- an oxide particle dispersion-strengthened Ni-base superalloy of the present invention has a composition consisting of 0.1% by weight to 14.0% by weight of Ru, 0.1% by weight to 14.0% by weight of aluminum (Al), with the balance of Ni and inevitable impurities, wherein the superalloy has a crystal structure containing 0.01% by weight to 3.0% by weight of dispersed oxide particles based on the total amount of the superalloy.
- the oxide particle dispersion-strengthened Ni-base superalloy of the present invention also optionally includes 0.1% by weight to 14.0% by weight of Ru, 0.1% by weight to 14.0% by weight of Al, and at least one of 0.1% by weight to 14.0% by weight of Re, 0.1% by weight to 20.0% by weight of Co, 0.1% by weight to 20.0% by weight of Cr, 0.1% by weight to 15.0% by weight of Mo, 0.1% by weight to 20.0% by weight of W, 0.1% by weight to 10.0% by weight of Ti, 0.1% by weight to 10.0% by weight of Nb, 0.1% by weight to 15.0% by weight of Ta, 0.01% by weight to 10.0% by weight of Hf, 0.01% by weight to 10.0% by weight of Zr, 0.1% by weight to 5.0% by weight of V, 0.1% by weight to 10.0% by weight of Pt, 0.1% by weight to 10.0% by weight of Pd, 0.1% by weight to 10.0% by weight of lr, 0.001% by weight to 1.0% by weight of B, or 0.001% by
- Ru which is one of the elements characteristic of the present invention, can form a solid solution in the ⁇ phase as the matrix phase and increase the high-temperature strength by solid solution strengthening. Ru can suppress the precipitation of the TCP phase, which can form when Re or other elements are added, so that Ru can increase the high-temperature strength.
- the Ru content is preferably in the range of 0.1 to 14.0% by weight, more preferably in the range of 1.0 to 14.0% by weight. If the Ru content is less than 0.1% by weight, the TCP phase would precipitate at high temperatures, which can make it impossible to ensure a high level of high-temperature strength and thus is not preferred.
- the Ru content is more than 14% by weight, the ⁇ phase would precipitate to reduce the high-temperature strength, which is not preferred.
- the base metal price of Ru is about 200 to 300 times higher than that of Ni or other metals. Therefore, the Ru content is preferably as low as possible in the range where solid solution strengthening can be produced to increase the high-temperature strength. Economically, the Ru content preferably has an upper limit of 8.0% by weight.
- the addition of Al can cause the ⁇ ' phase precipitation and thus contribute to the improvement of strength by precipitation strengthening.
- the Al content is preferably in the range of 0.1 to 14.0% by weight. If the Al content is less than 0.1% by weight, the precipitation strengthening would be insufficient, which can make it impossible to ensure the desired high-temperature strength and thus is not preferred. If the Al content is more than 14.0% by weight, a large amount of a coarse ⁇ ' phase would be formed to degrade the mechanical properties.
- the content of oxide particles added for dispersion strengthening should be 0.01% by weight to 3.0% by weight.
- the oxide particles may be of any type.
- the oxide particles are preferably of yttrium oxide, which has high chemical stability at high temperatures.
- yttrium oxide which has high chemical stability at high temperatures.
- a complex oxide of yttrium oxide and aluminum oxide, such as Y 4 Al 2 O 9 is also preferably used instead of yttrium oxide.
- alloying elements may preferably include 0.1% by weight to 14.0% by weight of Re, 0.1% by weight to 20.0% by weight of Co, 0.1% by weight to 20.0% by weight of Cr, 0.1% by weight to 15.0% by weight of Mo, 0.1% by weight to 20.0% by weight of W, 0.1% by weight to 10.0% by weight of Ti, 0.1% by weight to 10.0% by weight of Nb, 0.1% by weight to 15.0% by weight of Ta, 0.01% by weight to 10.0% by weight of Hf, 0.01% by weight to 10.0% by weight of Zr, 0.1% by weight to 5.0% by weight of V, 0.1% by weight to 10.0% by weight of Pt, 0.1% by weight to 10.0% by weight of Pd, 0.1% by weight to 10.0% by weight of Ir, 0.001 % by weight to 1.0% by weight of B, or 0.001% by weight to 1.0% by weight of C.
- a more preferred composition may be as follows.
- Re can form a solid solution in the ⁇ phase as the matrix phase and increase the high-temperature strength by solid solution strengthening. Re can also be effective in improving corrosion resistance. However, the addition of a large amount of Re may cause the TCP phase to precipitate as a harmful phase at high temperatures and thus reduce the high-temperature strength.
- the Re content is more preferably in the range of 0.1 to 14.0% by weight.
- the Re content is less than 0.1% by weight, the solid solution strengthening of the ⁇ phase may be insufficient, which can make it impossible to ensure the desired high-temperature strength and thus is not preferred. If the Re content is more than 14.0% by weight, the TCP phase may precipitate at high temperatures, which can make it impossible to ensure a high level of high-temperature strength and thus is not preferred.
- Cr is an element highly resistant to oxidation and can increase the high-temperature corrosion resistance. If the Cr content is less than 0.1% by weight, the high-temperature corrosion resistance can fail to be achieved. A Cr content of more than 20.0% by weight can suppress the ⁇ ' phase precipitation and cause the production of a harmful phase such as the ⁇ or ⁇ phase, which can reduce the high-temperature strength and thus is not preferred.
- Co can increase the solid solution limit of Al, Ta or other elements in the matrix phase at high temperatures and can cause the ⁇ ' phase precipitation and thus increase the high-temperature strength. If the Co content is less than 0.1% by weight, the ⁇ ' phase precipitation can be insufficient, which can make it impossible to increase the high-temperature strength. If the Co content is more than 20.0% by weight, the balance between Co and any of other elements such as Al, Ta, Mo, W, Hf, and Cr can be broken, which can cause the precipitation of a harmful phase and the reduction of the high-temperature strength and thus is not preferred.
- Mo can form a solid solution in the ⁇ phase as the matrix phase when coexisting with W and Ta so that Mo can increase the high-temperature strength and contribute to the high-temperature strength by precipitation hardening. If the Mo content is less than 0.1% by weight, these effects can be insufficient, which can make it impossible to increase the high-temperature strength. A Mo content of more than 15.0% by weight can reduce the high-temperature corrosion resistance and thus is not preferred.
- W can increase the high-temperature strength by the action of solid solution strengthening and precipitation hardening when coexisting with Mo and Ta. If the W content is less than 0.1% by weight, the formation of the solid solution in the ⁇ and ⁇ ' phases can be insufficient, which can make it impossible to increase the high-temperature strength.
- the W content is preferably 20.0% by weight or less. This is because a W content of more than 20.0% by weight may reduce the high-temperature corrosion resistance.
- the content of each of these elements should be at least 0.1% by weight.
- the content of each of these elements is preferably 10.0% by weight or less, more preferably 6.0% by weight or less.
- Ta, Ti, and Nb can contribute to precipitation strengthening by substituting for Al sites in the ⁇ ' phase. Ta, Ti, and Nb can also increase the high-temperature strength by the action of solid solution strengthening and precipitation strengthening when coexisting with Mo and W. If the Ta content is less than 0.1% by weight, these effects can fail to be achieved.
- the Ta content is preferably 15.0% by weight or less. This is because a Ta content of more than 15.0% by weight can cause the formation of the ⁇ or ⁇ phase and thus reduce the high-temperature strength. If the content of each of Ti and Nb is less than 0.1% by weight, it can be impossible to achieve precipitation strengthening or solid solution strengthening in the co-presence of Mo and W.
- the content of each of Ti and Nb is preferably 10.0% by weight or less. This is because if the Ti or Nb content is more than 10.0% by weight, a harmful phase may form to reduce the high-temperature strength.
- V is an element that can form a solid solution in the ⁇ ' phase and strengthen the ⁇ ' phase. If the V content is less than 0.1%by weight, these effects can fail to be achieved.
- the V content is preferably 5.0% by weight or more. This is because if the V content is more than 5.0% by weight, the creep strength may decrease.
- Hf is a grain boundary segregating element which can segregate at the grain boundary between the ⁇ and ⁇ ' phases to strengthen the grain boundary, so that it can increase the high-temperature strength.
- the Hf content should be at least 0.01% by weight. If the Hf content is more than 10.0% by weight, local melting can occur, which may reduce the high-temperature strength and thus is not preferred.
- the B is a grain boundary strengthening element which can increase the high-temperature strength.
- the B content should be at least 0.001 % by weight. If the B content is more than 1.0% by weight, a harmful carbide can precipitate at grain boundaries, which is not preferred.
- examples of the elemental composition of the oxide dispersion-strengthened Ni-base superalloy of the present invention include the following as well as those of the examples shown below.
- the oxide particle dispersion-strengthened Ni-base superalloy of the present invention can be produced by a process that includes producing an alloy powder by mechanical alloying, then sealing the alloy powder in a case, and then consolidating the alloy powder by hot extrusion or other techniques.
- the alloy powder may be solidified by hot isostatic pressing (HIP), hot pressing, or other techniques.
- the oxide particle dispersion-strengthened Ni-base superalloy of the present invention may be produced by solidifying the alloy powder by any of these techniques and then subjecting the solidified product to hot extrusion or hot rolling.
- the combination of base and additive elements for constituting a heat-resistant alloy is determined depending on the intended use of the alloy and cost effectiveness.
- alloys for gas turbines are required to have high-temperature strength in the temperature range of 400 to 500°C, when they are for use in turbine disks, or required to have high strength and high-temperature corrosion resistance in the temperature range of about 800 to about 1,000°C, when they are for use in combustors, nozzles, turbine blades, shrouds, and other components.
- the dispersed particle size distribution is preferably in the range of 0.001 ⁇ m to 5 ⁇ m, and thus the oxide particles to be used preferably has a primary particle size distribution of 1 ⁇ m or less, taking into account particle aggregation during the production.
- the content of the oxide particles, for example, in the Ni-base alloy for gas turbines is, in particular, preferably 0.5 to 3.0% based on the total amount of the alloy in order to obtain high-temperature strength at 800°C or higher.
- the particle size distribution of the alloy or metal powder to be used may have an upper limit of, for example, 250 ⁇ m, so that mechanical alloying and sintering for consolidation can be performed with improved efficiency.
- the ratio of the mixture power weight to the steel ball weight is preferably 1/10 to 1/20 in an attritor and 1/5 to 1/10 in a planet ball mill, and the rotational speed of the ball mill is preferably 50 to 400 rpm although it depends on the ball mill size.
- the alloying is preferably performed for 20 hours or more. In case of oxygen contamination during the alloying, purging the inside of the ball mill tank with an inert atmosphere such as argon (Ar) is preferably performed as a pre-alloying treatment.
- the consolidation of the dispersed alloy-forming powder by sintering can be performed by a powder metallurgy process that includes charging the powder into a mild steel vessel and then subjecting the powder to hot extrusion or HIP.
- the sintering of the powder to form the Ni-base alloy is preferably performed in the temperature range of 1,000 to 1,300°C taking into account diffusion, fusion, and densification between the particles, the formation of more solid solution of alloy atoms, and the high-temperature stability limit of the oxide particles.
- the inside of the vessel is subjected to a vacuum treatment as a pretreatment for the purpose of removing water, oxygen, and other contaminants, which exist in or adsorb on the space in the vessel, the inner surface of the vessel, and the surface of the powder.
- the vacuum treatment is preferably a heat treatment under a vacuum of 10 -1 to 10 -3 torr at a temperature of 100°C to 600°C for 10 minutes to 10 hours depending on the size of the facility so that oxygen can be prevented as much as possible from being added to the dispersion alloy and a strong oxide can be prevented from forming on the surface of the powder.
- An extruded material with a composition of Ni-6.4Co-4.5Cr-1.1Mo-4.0W-5.8Al-7.5Ta-0.1 Hf-6.3Re-4.9Ru-1.1Y 2 O 3 was prepared as described below.
- Raw material powders were mixed to reach the target composition as a whole and then subjected to a mechanical alloying process using an attritor. After the process, the alloy powder was charged into a case and subjected to a vacuum treatment, and the case was sealed. The alloy powder was then consolidated by hot isostatic pressing (HIP) at a heating temperature of 1,180°C and a pressure of 118 MPa. The resulting HIP product was subjected to hot extrusion under the conditions of a heating temperature of 1,200°C and an extrusion ratio of 5 to form a round bar-shaped extruded material.
- HIP hot isostatic pressing
- Fig. 1 is a chart showing the result of X-ray diffraction of the extruded material in comparison with that of the mechanical alloying powder.
- the X-ray diffraction chart (chart A) of the mechanical alloying powder mainly had the (111) and (200) diffraction peaks of the Ni solid solution.
- the (110) diffraction peak of the ⁇ ' phase was observed in addition to the diffraction peaks of the Ni solid solution. This indicates that the extruded material is composed mainly of the Ni solid solution ( ⁇ ) phase in which the ⁇ ' phase is precipitated.
- Fig. 2 shows the structure of the extruded material observed with a transmission electron microscope.
- the arrows indicate oxide particles.
- the structure was found to contain a large number of fine oxide particles of several tens of nanometers dispersed in crystal grains.
- the high-temperature corrosion resistance of the resulting alloy was evaluated by a molten salt corrosion test.
- a cylindrical piece with a diameter of 6 mm and a height of 4.5 mm was cut from the extruded material in such a way that the axis direction coincided with the extrusion direction.
- the cut piece was immersed in a molten salt and heated at a temperature of 800°C for 4 hours.
- the molten salt used as a corrosive medium was a 3 : 1 mixture of sodium sulfate and sodium chloride.
- a crucible was charged with the mixed salt in such an amount that the cylindrical sample could be completely immersed in the salt.
- the mixed salt was preheated at 800°C in a heating furnace. After the temperature was stabilized sufficiently, the cylindrical sample was immersed in the molten salt.
- the rate of reduction in the sample diameter between before and after the test was calculated to be 0.17%.
- An extruded material with a composition of Ni-5.9Co-3.8Cr-0.9Mo-3.9W-6.1Al-8.6Ta-0.2Hf-5.3Re-4.6Ru-1.2Y 4 Al 2 O 9 (each numerical value is in units of % by weight) was prepared as described below.
- Raw material powders were mixed to reach the target composition as a whole and then subjected to a mechanical alloying process using an attritor. After the process, the alloy powder was charged into a case and subjected to a vacuum treatment, and the case was sealed. The alloy powder was then subjected to hot extrusion under the conditions of a heating temperature of 1,050°C and an extrusion ratio of 15 to form a round bar-shaped, extruded material.
- the high-temperature corrosion resistance of the resulting alloy was evaluated by the molten salt corrosion test under the same conditions as in Example 1.
- the sample was immersed in the molten salt and heated at a temperature of 800°C for 4 hours.
- the rate of reduction in the sample diameter between before and after the test was calculated to be 0.17%.
- An extruded material with a composition of Ni-6.1Co-3.8Cr-0.9Mo-4.2W-6.3Al-9.2Ta-0.2Hf-5.0Re-4.7Ru-1.2Y 4 Al 2 O 9 (each numerical value is in units of % by weight) was prepared as described below.
- Raw material powders were mixed to reach the target composition as a whole and then subjected to a mechanical alloying process using an attritor. After the process, the alloy powder was charged into a case and subjected to a vacuum treatment, and the case was sealed. The alloy powder was then subjected to hot extrusion under the conditions of a heating temperature of 1,050°C and an extrusion ratio of 15 to form a round bar-shaped, extruded material.
- the high-temperature corrosion resistance of the resulting alloy was evaluated by the molten salt corrosion test under the same conditions as in Examples 1 and 2.
- the sample was immersed in the molten salt and heated at a temperature of 800°C for 4 hours.
- the rate of reduction in the sample diameter between before and after the test was calculated to be 0.17%.
- Non Patent Literature 2 shows the results of the micro Vickers hardness test of an extruded TMO-2 alloy material after an isothermal heat treatment.
- the extruded material has an alloy composition of Ni-9.8Co-5.9Cr-2.0Mo-12.4W-4.2Al-4.7Ta-0.8Ti-0.05Zr-0.05C-0.01B-1.1Y 2 O 3 (each numerical value is in units of % by weight). It should be noted that this alloy has a W content about three times higher than that of the alloy composition of the examples.
- Non Patent Literature 3 shows the results of the molten salt corrosion test of this alloy under the same conditions as in Examples 1 to 3. This extruded material shows a diameter reduction rate of 29.0%.
- Fig. 3 is a graph showing plots of micro Vickers hardness versus annealing temperature for a comparison between the materials of Examples 1 to 3 and Comparative Example after the isothermal annealing (1 hour). Open circles represent the results of Example 1, triangles those of Example 2, squares those of Example 3, and solid circles those of Comparative Example. The graph shows that although having a significantly reduced W content, the oxide particle dispersion-strengthened Ni-base superalloy of the present invention has improved mechanical properties after heating at a temperature in the range of 1,260°C to 1,300°C because it contains Ru.
- Examples 1 to 3 all show a diameter reduction rate of 0.17% whereas Comparative Example shows a diameter reduction rate of 29.0%, which indicates that Examples 1 to 3 have a significantly improved level of high-temperature corrosion resistance. This would be because the alloys of Examples 1 to 3 have a W content significantly lower than that of the alloy of Comparative Example.
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JP2013162525 | 2013-08-05 | ||
PCT/JP2014/070501 WO2015020007A1 (ja) | 2013-08-05 | 2014-08-04 | 酸化物粒子分散強化型Ni基超合金 |
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EP3031939A1 EP3031939A1 (en) | 2016-06-15 |
EP3031939A4 EP3031939A4 (en) | 2017-02-15 |
EP3031939B1 true EP3031939B1 (en) | 2018-04-11 |
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EP14834221.5A Active EP3031939B1 (en) | 2013-08-05 | 2014-08-04 | Ni-group superalloy strengthened by oxide-particle dispersion |
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US (1) | US20160160323A1 (ja) |
EP (1) | EP3031939B1 (ja) |
JP (2) | JPWO2015020007A1 (ja) |
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DE102016202837A1 (de) * | 2016-02-24 | 2017-08-24 | MTU Aero Engines AG | Wärmebehandlungsverfahren für Bauteile aus Nickelbasis-Superlegierungen |
WO2019088158A1 (ja) | 2017-10-31 | 2019-05-09 | 日立金属株式会社 | 合金材、該合金材の製造方法、該合金材を用いた製造物、および該製造物を有する流体機械 |
CN114466943A (zh) * | 2019-10-03 | 2022-05-10 | 东京都公立大学法人 | 耐热合金、耐热合金粉末、耐热合金成型体及其制造方法 |
Family Cites Families (20)
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US3926568A (en) | 1972-10-30 | 1975-12-16 | Int Nickel Co | High strength corrosion resistant nickel-base alloy |
CA1004881A (en) | 1972-10-30 | 1977-02-08 | John S. Benjamin | High strength corrosion resistant nickel-base alloy |
US4386976A (en) | 1980-06-26 | 1983-06-07 | Inco Research & Development Center, Inc. | Dispersion-strengthened nickel-base alloy |
US4402746A (en) * | 1982-03-31 | 1983-09-06 | Exxon Research And Engineering Co. | Alumina-yttria mixed oxides in dispersion strengthened high temperature alloys |
US4427447A (en) * | 1982-03-31 | 1984-01-24 | Exxon Research And Engineering Co. | Alumina-yttria mixed oxides in dispersion strengthened high temperature alloy powders |
JPS6299433A (ja) | 1985-10-26 | 1987-05-08 | Natl Res Inst For Metals | イツトリヤ粒子分散型γ′相析出強化ニツケル基耐熱合金 |
JPS6353232A (ja) | 1986-08-25 | 1988-03-07 | Ishikawajima Harima Heavy Ind Co Ltd | 酸化物分散強化超耐熱合金 |
US5338379A (en) * | 1989-04-10 | 1994-08-16 | General Electric Company | Tantalum-containing superalloys |
JPH0344438A (ja) * | 1989-07-13 | 1991-02-26 | Natl Res Inst For Metals | イットリア粒子分散型γ′相析出強化ニッケル基耐熱合金 |
JP3421758B2 (ja) * | 1993-09-27 | 2003-06-30 | 株式会社日立製作所 | 酸化物分散強化型合金及び該合金から構成される高温機器 |
JPH10193174A (ja) * | 1996-12-27 | 1998-07-28 | Daido Steel Co Ltd | 酸化物分散強化型合金溶接用溶加材 |
JP3941845B2 (ja) * | 1997-07-30 | 2007-07-04 | 株式会社日立製作所 | 産業用ガスタービン |
JP4028122B2 (ja) * | 1999-02-25 | 2007-12-26 | 独立行政法人物質・材料研究機構 | Ni基超合金、その製造方法およびガスタービン部品 |
CN101146931B (zh) * | 2005-03-28 | 2010-06-23 | 独立行政法人物质·材料研究机构 | 耐热构件 |
JP5177559B2 (ja) * | 2006-09-13 | 2013-04-03 | 独立行政法人物質・材料研究機構 | Ni基単結晶超合金 |
CA2680650C (en) * | 2007-03-12 | 2012-07-03 | Ihi Corporation | Ni-based single crystal superalloy and turbine blade incorporating the same |
JP5467307B2 (ja) * | 2008-06-26 | 2014-04-09 | 独立行政法人物質・材料研究機構 | Ni基単結晶超合金とそれよりえられた合金部材 |
EP2327807A4 (en) * | 2008-08-20 | 2016-07-27 | Univ Hokkaido Nat Univ Corp | OXIDDISPERSION REINFORCED ALLOY |
US8449262B2 (en) * | 2009-12-08 | 2013-05-28 | Honeywell International Inc. | Nickel-based superalloys, turbine blades, and methods of improving or repairing turbine engine components |
KR20120105693A (ko) * | 2011-03-16 | 2012-09-26 | 한국기계연구원 | 크리프 특성이 향상된 단결정 니켈기 초내열합금 |
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- 2014-08-04 US US14/909,799 patent/US20160160323A1/en not_active Abandoned
- 2014-08-04 EP EP14834221.5A patent/EP3031939B1/en active Active
- 2014-08-04 WO PCT/JP2014/070501 patent/WO2015020007A1/ja active Application Filing
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EP3031939A1 (en) | 2016-06-15 |
JPWO2015020007A1 (ja) | 2017-03-02 |
JP2018162522A (ja) | 2018-10-18 |
EP3031939A4 (en) | 2017-02-15 |
WO2015020007A1 (ja) | 2015-02-12 |
US20160160323A1 (en) | 2016-06-09 |
JP6552137B2 (ja) | 2019-07-31 |
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