CN112226648A - Low-Re low-S heat-corrosion-resistant nickel-based single crystal superalloy - Google Patents
Low-Re low-S heat-corrosion-resistant nickel-based single crystal superalloy Download PDFInfo
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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
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
Abstract
The invention discloses a low-Re and low-S heat-corrosion-resistant nickel-based single crystal superalloy, and belongs to the technical field of nickel-based single crystal superalloys. The alloy comprises the following chemical components in percentage by weight: cr: 8.5-10.5%, Co: 5.0-7.0%, Mo: 0.5-1.2%, W: 6.0-7.5%, Ta: 4.0-5.5%, Al: 4.2-5.5%, Ti: 0.8-2.5%, Re: 1.0-2.0%, C: 0-0.1%, Hf: 0-0.2%, the rest is Ni, Ta/Cr is less than or equal to 0.5, NvLess than or equal to 2.1. The alloy not only has excellent heat-resistant corrosion resistance and oxidation resistance, but also has higher high-temperature mechanical property and good structure stability. The high-temperature component can be suitable for high-temperature components of gas turbines used on the ground and in ships, and can also be suitable for high-temperature components of aircraft engines in service in offshore and oceanic environments.
Description
Technical Field
The invention relates to the technical field of nickel-based single crystal high-temperature alloys, in particular to a low-Re and low-S heat corrosion resistant nickel-based single crystal high-temperature alloy which is mainly suitable for parts and components bearing higher stress under the high-temperature hot corrosion condition.
Background
The development of the scientific and technological fields of offshore aircraft engines, naval vessel gas turbines, ground gas turbines and the like requires that the high-temperature alloy material used by the turbine blades of the engines has good heat-resisting corrosion resistance and long-term structure stability, and the high-temperature mechanical property of the high-temperature alloy material is obviously superior to that of the first generation single crystal high-temperature alloy (close to or up to that of the second generation single crystal high-temperature alloy). However, it should be noted that the space for designing the composition of such an alloy is extremely narrow.
At present, the hot corrosion resistant nickel-based single crystal superalloy developed in China mainly comprises DD8, DD10, DD413 and the like, and the alloys have good hot corrosion resistance, but the strength of the alloys is far below the level of the second generation single crystal superalloy at home and abroad. In addition, the second generation high-strength nickel-based single crystal superalloy developed in China mainly comprises DD6, DD5 and the like, but the alloy has low Cr content and does not have hot corrosion resistance. Therefore, at present, the types of hot corrosion resistant single crystal alloys having high strength are extremely small in China.
Against the background, people expect to obtain a low-Re hot corrosion resistant nickel-based single crystal superalloy which has good hot corrosion resistant performance and long-term structure stability, has medium and low temperature durability reaching the level of a typical second generation high-strength single crystal alloy, and has high-strength hot corrosion resistant single crystal superalloy which is obviously superior to a typical first generation high-strength single crystal alloy (between the typical first generation high-strength single crystal alloy and the typical second generation high-strength single crystal alloy) in high temperature durability.
Disclosure of Invention
The invention aims to provide a low-Re and low-S hot corrosion resistant nickel-based single crystal superalloy which has good hot corrosion resistance and long-term structure stability and also has mechanical properties obviously superior to those of a typical first-generation high-strength single crystal superalloy.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the low-Re and low-S heat-corrosion-resistant nickel-based single crystal superalloy comprises the following alloy components in percentage by weight:
cr: 8.5-10.5%, Co: 5.0-7.0%, Mo: 0.5-1.2%, W: 6.0-7.5%, Ta: 4.0-5.5%, Al: 4.2-5.5%, Ti: 0.8-2.5%, Re: 1.0-2.0%, C: 0-0.1%, Hf: 0-0.2%, the rest is Ni, Ta/Cr is less than or equal to 0.5, Nv≤2.1。
The low-Re and low-S heat-corrosion-resistant nickel-based single crystal superalloy provided by the invention has the following optimized alloy component ranges in percentage by weight:
cr: 9.2-10.0%, Co: 5.5-6.5%, Mo: 0.5-0.8%, W: 6.5-7.5%, Ta: 4.5-5.0%, Al: 4.5-5.2%, Ti: 0.9-1.2%, Re: 1.2-1.7%, C: 0.04-0.08%, Hf: 0.05-0.15 percent, the balance of Ni, Ta/Cr is less than or equal to 0.5, and Nv≤2.1。
The low-Re and low-S heat corrosion resistant nickel-based single crystal superalloy provided by the invention has the following impurity components and mass percentage content meeting the following requirements: o is less than or equal to 0.001, N is less than or equal to 0.001, S is less than or equal to 0.001, Zr is less than or equal to 0.0075, Mn is less than or equal to 0.01, Si is less than or equal to 0.1, P is less than or equal to 0.005, Cu is less than or equal to 0.05, Mg is less than or equal to 0.008, Se is less than or equal to 0.0003, Pb is less than or equal to 0.0002, Te is less than or equal to 0.00005, Bi is less than or.
The chemical composition design of the alloy (alloy brand is named as DD413G) is mainly based on the following reasons:
the most obvious feature of hot corrosion resistant nickel based single crystal superalloys is the high Cr content (typically greater than 12 wt.%) to ensure excellent hot corrosion resistance. Under the condition of hot corrosion, Cr is oxidized to form Cr2O3And the alloy matrix is protected from being corroded by molten salt. In addition, Cr can capture sulfur entering the alloy matrix to generate solid CrS, prevent the sulfur from further diffusing into the matrix or generate liquid nickel sulfide. However, the solid solution strengthening effect of Cr is small, and the addition of other solid solution strengthening elements (W, Mo, Ta, Re and the like) is limited by the high Cr content, otherwise, TCP harmful phases can appear in the alloy to cause performance deterioration. Therefore, the high-strength hot corrosion resistant single crystal alloy needs to reduce the Cr content properly in the aspect of component design, and the Cr content is 8.5-10.5%.
Based on a large number of experiments, the two refractory elements Re and Ta can not only improve the mechanical property of the alloy, but also improve the heat-resistant corrosion performance of the alloy.
Re is an effective solid solution strengthening element in the high-temperature alloy, can reduce the diffusion rate of elements in the high-temperature creep and lasting process, and obviously improves the mechanical property of the alloy. Meanwhile, Re improves the activity of Cr and Ti elements and promotes the single crystal alloy Cr2O3And NiTiO3Inhibit the formation of NiO and ensure the Cr on the surface of the alloy2O3The complete compactness of the film prolongs the hot corrosion incubation period of the alloy and improves the hot corrosion performance of the single crystal alloy. Earlier studies have shown that the hot corrosion performance of 2Re +9Cr alloys is comparable to that of 0Re +12Cr alloys. In addition, when the content of Re is more than or equal to 1.0 percent, the alloy hot corrosion kinetic curve also obviously has a multi-stage parabolic law. However, excessive Re also promotes TCP phase precipitation. In addition, Re is a strategic resource and is expensive. Therefore, the content of Re is controlled to 1.0 to 2.0%.
The influence of Ta on the hot corrosion behavior of nickel-based single crystal superalloys is related to the Cr content of the alloy itself. For alloys with Cr contents between 5.0% and 12.0%, the interaction of Ta and Cr on hot corrosion behavior can be described by Ta/Cr (wt.%): Ta/Cr<0.5 time, Ta2O5For Cr2O3The film plays a role of doping and quickens the Cr2O3Growth rate of (3), alloy formation of intact Cr2O3The film has good hot corrosion resistance; when Ta/Cr is 0.5, Ta promotes the formation of Ta-containing spinel, reduces the diffusion rate of ions, and the alloy forms complete Cr2O3The film has good hot corrosion resistance; 0.5<Ta/Cr<1 time, Ta2O5And Cr2O3Competitive growth, the alloy can not form complete Cr2O3The hot corrosion resistance of the film, alloy is reduced; Ta/Cr>1 time, Ta2O5And Cr2O3Competitive growth, NiO as the oxide film on the surface of the alloy, and poor hot corrosion resistance. Therefore, the content of Ta in the high-strength heat-corrosion-resistant single crystal alloy is 4.0-5.5%, and Ta/Cr is required to be less than or equal to 0.5.
Mo and W are the most important solids in high-temperature alloyThe solution strengthening elements, which are elements promoting the formation of the TCP phase, are very unfavorable for the structural stability of the alloy. W, Mo is easy to form volatile oxide in high temperature oxidation environment, and is difficult to form dense oxide film in the presence of Na2SO4In the environment of (2), acid melting reaction is easily caused, severe hot corrosion is generated, and particularly, catastrophic corrosion often occurs on high-Mo alloy. Therefore, the Mo content of the high-strength heat-corrosion-resistant single crystal alloy is 0.5-1.2%, and the W content is 6.0-7.5%.
Co and Ni can be completely dissolved mutually, and the stacking fault energy of the matrix is also obviously reduced, so that the cross slip of screw dislocation becomes very difficult. However, recent studies have found that high Co alloys also promote TCP phase precipitation. Too high a Co content also lowers the solution temperature, resulting in a reduction in the high temperature performance of the alloy. Therefore, in order to ensure the addition of refractory elements, the content of Co in the high-strength heat-corrosion-resistant single crystal alloy is controlled to be 5.0-7.0%.
Al is the most predominant precipitation-strengthening γ' phase-forming element in superalloys. Al can also obviously improve the oxidation resistance of the alloy, but the Al can also obviously improve the oxidation resistance of the alloy to liquid Na2SO4The protective performance of the alloy is extremely poor, and the Al content of the alloy is less than 4.0 percent in general. However, it has been found that Re can inhibit the adverse effect of Al on the hot corrosion performance of the alloy. In addition, when the Al content is more than or equal to 4.2 percent, the volume fraction of the gamma 'strengthening phase of the alloy can reach more than 60 percent (the mechanical property of the alloy is mainly determined by the content and the size of the gamma' strengthening phase). Therefore, the Al content of the high-strength heat-corrosion-resistant single crystal alloy is 4.5-5.2%.
Ti is also the most predominant precipitation-strengthening γ' phase-forming element in superalloys. Ti can also improve the antiphase domain boundary energy of gamma' phase and the high-temperature strength of the alloy. However, the Ti content is too high, the stability of the alloy structure is poor, the eutectic content is high, the heat treatment of the alloy is extremely difficult, and the Ti content is controlled to be 0.8-2.5% by combining the factors.
The addition of a proper amount of C can improve the casting performance of the alloy and reduce the recrystallization tendency of the alloy, and particularly, the addition of C can generate small-size granular carbide which can strengthen grain boundaries, so that the small-angle grain boundary tolerance of the single crystal alloy is improved, and the yield of the alloy is further improved. However, the addition of excessive C lowers the alloy properties, and therefore, the C content is controlled to 0 to 0.1%.
The addition of a proper amount of Hf can improve the plasticity and the adhesive force of an oxide film, obviously increase the cyclic oxidation resistance of the alloy and improve the compatibility of a coating and a matrix. Therefore, the Hf content is controlled to 0 to 0.2%.
The increase of the content of S in ppm level obviously reduces the hot corrosion incubation period of the alloy, leads the final oxidation weight increase of the alloy to be increased in sequence, and deteriorates the hot corrosion performance of the alloy. The increase of the S content of ppm level reduces the stability of an external oxide layer in molten salt and promotes reticular Al2O3The formation of (b) and the occurrence of internal sulfidation, leading to surface bulging and spalling of the alloy, reducing the hot corrosion resistance of the alloy. Therefore, the S content is controlled to 0.001% or less.
The low Re and low S heat corrosion resistant nickel-based single crystal superalloy disclosed by the invention has the advantages that the heat corrosion resistance is equivalent to that of K438 alloy, the mechanical property is close to the level of a typical second-generation high-strength single crystal superalloy, and no TCP phase is precipitated after long-term aging.
The advantages and beneficial effects of the invention are illustrated as follows:
(1) compared with other existing high-strength nickel-based single crystal high-temperature alloys, the alloy disclosed by the invention has excellent hot corrosion resistance, and the hot corrosion capacity at 900 ℃ is equivalent to that of the K438 alloy.
(2) Compared with other existing single crystal high temperature alloys with heat corrosion resistance, the alloy of the invention has excellent oxidation resistance, and the alloy at 1050 ℃ is completely oxidation resistant.
(3) The medium-low temperature endurance performance of the alloy reaches the level of typical second generation high-strength single crystal high-temperature alloy, the high-temperature endurance performance is obviously superior to the level of typical first generation single crystal high-temperature alloy, the endurance life is more than 150h at 980 ℃/248MPa, the endurance life is more than 80h at 1000 ℃/235MPa, and the alloy is high-strength hot corrosion resistant single crystal high-temperature alloy.
(4) The alloy of the invention has lower Re content and stable long-term aging structure at 900 ℃.
Drawings
FIG. 1 is a graph comparing the Larson-Miller curves for the alloy of the present invention with the prior art first generation single crystal superalloys PWA1483 and second generation single crystal superalloys Re ń e N5;
FIG. 2 is a graph showing the 900 ℃ hot corrosion performance of the alloy of the present invention;
FIG. 3 is a graph showing the effect of different ppm S contents on the macro morphology of the alloy hot-etched at 900 deg.C
FIG. 4 shows the microstructure of the alloy of the present invention after long-term aging at 1000 ℃ for 8000 h.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Examples 1 to 5:
the chemical compositions of the nickel-based single crystal superalloy samples of the present invention are shown in table 1. The alloy of the invention is prepared by smelting pure Ni, Co, Cr, W, Mo, Ta, Ti, Al, Re, C, Hf and other elements in a vacuum induction furnace (refining temperature: 1500 +/-10 ℃, refining time 20min, refining period vacuum degree less than or equal to 3Pa), casting into a mother alloy with chemical components meeting requirements, remelting by directional solidification equipment (high-speed solidification method or liquid metal cooling method, casting at 1500 ℃, directional solidification drawing rate of 3mm/min), and directionally solidifying into a single crystal test bar by using a spiral crystal selector or a seed crystal method. It is subjected to heat treatment before use. The heat treatment system is as follows: 1280 ℃/2h/AC +1305 ℃/6h/AC +1130 ℃/4h/AC +900 ℃/20h/AC (AC: air cooling).
For comparison, the chemical compositions of a typical first generation nickel-based single crystal superalloy PWA1483 and a typical second generation single crystal superalloy Re ń e N5 are also listed in table 1.
TABLE 1 list of chemical compositions (in wt.%) of the alloys of the invention (examples 1-9) and PWA1483, Re ń e N5
| Alloy (I) | Cr | Co | W | Mo | Ta | Al | Ti | Re | C | Hf | Ni |
| Example 1 | 10.1 | 5.2 | 7.3 | 0.7 | 5.0 | 4.3 | 1.2 | 1.3 | 0.04 | 0.1 | Surplus |
| Example 2 | 9.0 | 5.7 | 6.2 | 0.8 | 4.5 | 5.1 | 0.9 | 1.7 | 0.02 | 0.09 | Surplus |
| Example 3 | 9.5 | 6.0 | 7.0 | 0.9 | 4.7 | 4.9 | 1.1 | 1.5 | 0.03 | 0.15 | Surplus |
| Example 4 | 9.5 | 6.0 | 7.0 | 0.9 | 4.7 | 5.4 | 1.4 | 1.5 | 0.03 | 0.1 | Surplus |
| Example 5 | 9.5 | 6.0 | 7.5 | 1.2 | 4.7 | 4.9 | 1.0 | 1.7 | 0.03 | 0.15 | Surplus |
| PWA 1483 | 12.0 | 9.0 | 4.0 | 1.9 | 5.0 | 3.4 | 4.0 | - | 0.06 | - | Surplus |
| Reńe N5 | 7.0 | 8.0 | 5.0 | 2.0 | 7.0 | 6.2 | - | 3.0 | 0.05 | 0.1 | Surplus |
Note: the "remainder" in the column of Ni content in the table means "remainder".
The Larson-Miller curves of the alloys of examples 1-2 of the present invention are shown in FIG. 1 in comparison with the Larson-Miller curves of a typical first generation nickel based single crystal superalloy PWA1483 and a typical second generation single crystal superalloy Re ń e N5. The endurance performance of the alloy of the invention is close to that of Re ń e N5 alloy and is obviously higher than that of PWA1483 alloy.
The 900 ℃ hot corrosion performance of the alloy of example 3 of the invention is compared with that of the hot corrosion resistant alloy K438 and the second generation single crystal superalloy Re ń e N5 shown in FIG. 2. The hot corrosion performance of the alloy of the invention is equivalent to that of the alloy K438 which is a hot corrosion resistant alloy, and is obviously superior to that of the second generation single crystal superalloy Re ń e N5 alloy.
The effect of different ppm S contents on the 900 ℃ hot corrosion macro morphology of the alloy of example 4 of the present invention is shown in fig. 3. When the S content is more than 10ppm, the hot corrosion performance of the alloy is obviously reduced.
After the alloy is completely heat treated, a long-term aging experiment at 1000 ℃ is carried out, and no TCP phase is precipitated after long-term aging for 8000 h. The structure of the alloy of example 5 of the invention after long-term aging is shown in FIG. 4.
Claims (4)
1. A low Re, low S heat corrosion resistant nickel base single crystal superalloy is characterized in that: the alloy comprises the following chemical components in percentage by weight:
cr: 8.5-10.5%, Co: 5.0-7.0%, Mo: 0.5-1.2%, W: 6.0-7.5%, Ta: 4.0-5.5%, Al: 4.2-5.5%, Ti: 0.8-2.5%, Re: 1.0-2.0%, C: 0-0.1%, Hf: 0-0.2%, and the balance of Ni.
2. The low Re, low S hot corrosion resistant nickel based single crystal superalloy according to claim 1, wherein: in the alloy, the weight ratio of Ta to Cr is as follows: Ta/Cr is less than or equal to 0.5; n is a radical ofv≤2.1。
3. The low Re, low S hot corrosion resistant nickel based single crystal superalloy according to claim 2, wherein: the alloy comprises the following chemical components in percentage by weight:
cr: 9.2-10.0%, Co: 5.5-6.5%, Mo: 0.5-0.8%, W: 6.5-7.5%, Ta: 4.5-5.0%, Al: 4.5-5.2%, Ti: 0.9-1.2%, Re: 1.2-1.7%, C: 0.04-0.08%, Hf: 0.05-0.15%, and the balance of Ni.
4. A low Re, low S hot corrosion resistant nickel based single crystal superalloy according to any of claims 1 to 3, wherein: according to the weight percentage, the impurity content in the nickel-based single crystal superalloy is required to be as follows: o is less than or equal to 0.001, N is less than or equal to 0.001, S is less than or equal to 0.001, Zr is less than or equal to 0.0075, Mn is less than or equal to 0.01, Si is less than or equal to 0.1, P is less than or equal to 0.005, Cu is less than or equal to 0.05, Mg is less than or equal to 0.008, Se is less than or equal to 0.0003, Pb is less than or equal to 0.0002, Te is less than or equal to 0.00005, Bi is less than or.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117684047A (en) * | 2024-02-04 | 2024-03-12 | 四川航大新材料有限公司 | High-temperature alloy for turbine blade of gas turbine, and preparation method and application thereof |
| CN117684047B (en) * | 2024-02-04 | 2024-04-26 | 四川航大新材料有限公司 | High-temperature alloy for turbine blade of gas turbine, and preparation method and application thereof |
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Application publication date: 20210115 |