CN112593122B - Long-life high-strength hot-corrosion-resistant single crystal high-temperature alloy - Google Patents
Long-life high-strength hot-corrosion-resistant single crystal high-temperature alloy Download PDFInfo
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- CN112593122B CN112593122B CN202011449792.2A CN202011449792A CN112593122B CN 112593122 B CN112593122 B CN 112593122B CN 202011449792 A CN202011449792 A CN 202011449792A CN 112593122 B CN112593122 B CN 112593122B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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%
Abstract
The invention discloses a long-life high-strength hot corrosion resistant 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:10 to 12%, co:4 to 6%, mo:0 to 0.5%, W:5 to 7%, ta:6 to 8%, al:3.5 to 4.5%, ti: 3.5-4.5%, C:0 to 0.1%, hf:0 to 0.2 percent, and the balance of Ni, ta/(W +2 Mo) =1 to 1.1. The alloy not only has excellent dynamic and static structure stability, but also has better heat-resisting corrosion resistance and oxidation resistance, and higher high-temperature mechanical property. 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 belongs to the technical field of nickel-based single crystal superalloy, and particularly relates to a long-life high-strength hot corrosion resistant single crystal superalloy, which is mainly suitable for long-life single crystal superalloy components serving in a high-temperature hot corrosion environment.
Background
The development of the scientific and technological fields of offshore long-life aircraft engines, next-generation ship gas turbines, ground gas turbines and the like requires that high-temperature alloy materials used for turbine blades of engines have excellent high-temperature structure stability and good heat corrosion resistance. Meanwhile, the high-temperature mechanical property of the alloy is required to be obviously superior to that of the first 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 and the like, and the alloys have better hot corrosion resistance, but the strength of the alloys can not reach 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 alloys have high cost (containing 2-3% of Re), and relatively poor long-term structure stability and hot corrosion resistance. Therefore, at present, the types of hot corrosion resistant single crystal alloys having a long life and high strength are very few in China.
Against the background, it is desired to obtain a Re-free long-life high-strength hot-corrosion-resistant single crystal superalloy having good hot corrosion resistance, high-temperature mechanical properties, and excellent dynamic and static structure stability.
Disclosure of Invention
The invention aims to provide a long-life high-strength hot corrosion resistant 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 hot corrosion resistant single crystal superalloy.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the long-life high-strength hot corrosion resistant single crystal high temperature alloy comprises the following chemical components in percentage by weight:
cr:10 to 12%, co:4 to 6 percent, mo:0 to 0.5%, W:5 to 7%, ta:6 to 8%, al:3.5 to 4.5 percent, ti: 3.5-4.5%, C:0 to 0.1%, hf:0 to 0.2 percent, and the balance of Ni.
The invention provides a long-life high-strength hot-corrosion-resistant single crystal high-temperature alloy which comprises the following preferred alloy components in percentage by weight:
cr:11.2 to 11.8%, co:4.5 to 5.5 percent, mo:0.2 to 0.4%, W:5.7 to 6.3%, ta:6.7 to 7.3%, al:3.8 to 4.2 percent, ti: 3.8-4.2%, C: 0.04-0.08%, hf:0.05 to 0.15 percent, and the balance of Ni.
The chemical components of the alloy in percentage by weight are Ta/(W +2 Mo) = 1-1.1,N v ≤2.4。
In the chemical components of the long-life high-strength thermal corrosion resistant single crystal high-temperature alloy provided by the invention, the mass percentage of impurity elements meets 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 equal to 0.00003, and Sn is less than or equal to 0.0015.
The chemical composition design of the alloy (alloy brand is named as DD 413M) is mainly based on the following reasons:
the most obvious feature of hot corrosion resistant nickel based single crystal superalloys is their 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 Cr 2 O 3 And 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 CrSmaller, higher Cr content limits the addition of other solid solution strengthening elements (W, mo, ta, re, etc.), otherwise TCP deleterious phases can appear in the alloy, causing performance degradation. Therefore, the high-strength hot corrosion resistant single crystal alloy needs to reduce the Cr content properly in the component design, and the Cr content is 10-12%.
Mo and W are the most important solid solution strengthening elements in the high-temperature alloy, but both of them are elements for promoting the formation of the TCP phase, and are very disadvantageous to the structural stability of the alloy. In addition, W and Mo are easy to generate volatile oxides in a high-temperature oxidation environment, and a compact oxide film is difficult to form in the presence of Na 2 SO 4 The environment of (2) is easy to cause acid melting reaction, severe hot corrosion is generated, and particularly, the alloy with high Mo content often generates catastrophic corrosion. Therefore, the content of Mo in the high-strength heat-corrosion-resistant single crystal alloy is 0 to 0.5 percent, and the content of W in the high-strength heat-corrosion-resistant single crystal alloy is 5 to 7 percent.
Ta can effectively improve the hot corrosion resistance of the alloy. This is because the increase in Ta content promotes the alloy solid NaTaO 3 Inhibit the formation of liquid Na 2 (Mo,W)O 4 The formation of the alloy and the occurrence of the alloy melting reaction prolong the hot corrosion incubation period of the alloy. In addition, increasing the Ta content also promotes solid TaS 2 The method can inhibit the generation of liquid NiSx, further replace Cr to play a role in fixing S, and obviously improve the hot corrosion resistance of the alloy. Therefore, the Ta content of the high-strength heat-corrosion-resistant single crystal alloy is 6-8%. In addition, researches show that when Ta/(W +2 Mo) = 1-1.1, the strength of a gamma ' phase in the alloy is high, the gamma ' phase morphology with good cubic degree can be obtained through high-temperature aging, and the alloy has low mismatching degree in a service temperature interval, so that the degradation rate of the gamma ' phase is low. Therefore, ta/(W +2 Mo) =1 to 1.1 is required for a long-life, high-strength, hot-corrosion-resistant single crystal alloy.
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 Co content of the high-strength heat-corrosion-resistant single crystal alloy is controlled to be 4-6%.
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 Na 2 SO 4 The protective properties of (a) are extremely poor. Therefore, the Al content of the high-strength hot corrosion resistant single crystal alloy is 3.5-4.5%.
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. Meanwhile, ti can also obviously improve the hot corrosion resistance of the alloy. However, the Ti content is too high, the structural stability of the alloy is poor, the eutectic content is high, the heat treatment of the alloy is extremely difficult, and the Ti content is controlled to be 3.5-4.5% by combining the factors.
The addition of a proper amount of C can improve the processing property and the defect tolerance of the alloy. 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 improve 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 nickel-based single crystal superalloy provided by the invention is prepared by smelting pure Ni, co, cr, W, mo, ta, ti, al, C, hf and other elements in a vacuum induction furnace (refining temperature: 1530 +/-10 ℃, refining time 30min, refining period vacuum degree less than or equal to 3 Pa), casting into a mother alloy with chemical components meeting requirements, remelting by a directional solidification device (high-speed solidification method or liquid metal cooling method, casting at 1550 ℃, directional solidification drawing rate of 4 mm/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: 1290 ℃/2h/AC +1315 ℃/6h/AC +1140 ℃/4h/AC +870 ℃/20h/AC (AC: air cooled).
Aiming at the background of the prior art, the invention develops the long-life high-strength hot corrosion resistant single crystal superalloy, the hot corrosion resistant performance of the long-life high-strength hot corrosion resistant single crystal superalloy is equivalent to that of the PWA1483 alloy, the mechanical property of the long-life high-strength hot corrosion resistant single crystal superalloy is obviously superior to that of the PWA1483 single crystal superalloy, and the alloy has excellent static and dynamic structure stability.
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 PWA1483 alloy.
(2) The alloy does not contain a noble element Re, but the durability of the alloy is obviously superior to PWA1483 single-crystal high-temperature alloy. The durable life is more than 120h under 980 ℃/248MPa and 70h under 1000 ℃/235MPa, and the alloy is a high-strength hot-corrosion-resistant single crystal superalloy.
(4) The alloy of the invention has stable structure after long-term thermal exposure at 900-1000 ℃, and the mechanical property of the alloy is not deteriorated but obviously improved after long-term thermal exposure.
Drawings
FIG. 1 shows the 900 ℃ hot corrosion performance of the alloy of the present invention;
FIG. 2 is a graph comparing the Larson-Miller curves for the alloy of the present invention and a first generation single crystal superalloy PWA1483 of the prior art;
FIG. 3 is a graph showing creep performance of alloys of the present invention after various long term thermal exposures at 900 ℃.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The following examples alloy specific preparation method requirements: smelting in a vacuum induction furnace, casting into a master alloy with chemical components meeting requirements, then preparing a single crystal test rod, and carrying out heat treatment before use.
Examples 1 to 5:
the chemical compositions of the nickel-based single crystal superalloy samples of the present invention are shown in table 1. For ease of comparison, the chemical composition of a typical first generation nickel-based single crystal superalloy PWA1483 is also listed in table 1.
TABLE 1 tabulation of chemical composition (wt.%) of inventive alloys (examples 1-5) and DD413
| Alloy (I) | Cr | Co | W | Mo | Ta | Al | Ti | C | Hf | Ni |
| Example 1 | 11.4 | 5.5 | 5.9 | 0.4 | 6.8 | 3.9 | 4.1 | 0.07 | 0.09 | Surplus |
| Example 2 | 12 | 5.8 | 6.8 | 0.4 | 7.3 | 4.2 | 4.1 | 0.07 | 0.08 | Surplus |
| Example 3 | 10.2 | 4.3 | 5.2 | 0.3 | 6.1 | 3.6 | 3.8 | 0.05 | 0.08 | Surplus |
| Example 4 | 11.5 | 5.1 | 6 | 0.4 | 6.8 | 4.4 | 4.2 | 0.08 | 0.07 | Surplus |
| Example 5 | 11.3 | 5.3 | 6.1 | 0.1 | 6.4 | 4.2 | 4.2 | 0.05 | 0.09 | Surplus |
| PWA1483 | 12.0 | 9.0 | 4.0 | 1.9 | 5.0 | 3.4 | 4.0 | 0.06 | - | Surplus |
Note: the "remainder" in the column of Ni content in the table means "remainder".
The Larson-Miller curves of examples 1, 2 and 3 of the present invention and a typical first generation hot corrosion resistant nickel based single crystal superalloy PWA1483 are shown in FIG. 1. The durability of the alloy of the invention is obviously higher than that of PWA1483 alloy.
The 900 ℃ hot corrosion performance of the alloy of example 4 of the invention is compared with that of the hot corrosion resistant alloy PWA1483 shown in FIG. 2. The hot corrosion performance of the alloy of the invention is equivalent to that of the hot corrosion resistant alloy PWA1483 alloy.
The creep performance of the alloy of example 5 of the invention after different long-term thermal exposures at 900 c (figure 3). It was found that the performance of the alloy did not deteriorate after long term heat exposure, and the alloy had the best creep performance after 2000h heat exposure.
Claims (2)
1. A long-life high-strength hot corrosion resistant single crystal superalloy is characterized in that: the alloy comprises the following chemical components in percentage by weight:
cr:11.2 to 11.8%, co: 4.5-5.5%, mo:0.1 to 0.4%, W:5.7 to 6.3%, ta:6.7 to 7.3%, al:3.8 to 4.2 percent, ti:3.8 to 4.2%, C:0.04 to 0.08%, hf:0.05 to 0.15 percent, and the balance of Ni; ta/(W +2 Mo) = 1-1.1, N v ≤2.4；
The alloy has the following durable performance: the lasting life is more than 120h at 980 ℃ and 248MPa and more than 70h at 1000 ℃ and 235 MPa; the alloy has stable structure after long-term thermal exposure at 900-1000 ℃, and the mechanical property of the alloy is not deteriorated but obviously improved after long-term thermal exposure.
2. A long life, high strength, hot corrosion resistant single crystal superalloy as in claim 1, wherein: in the chemical components of the alloy, the weight percentage content of impurity elements meets 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 equal to 0.00003, and Sn is less than or equal to 0.0015.
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| US4459160A (en) * | 1980-03-13 | 1984-07-10 | Rolls-Royce Limited | Single crystal castings |
| US4402772A (en) * | 1981-09-14 | 1983-09-06 | United Technologies Corporation | Superalloy single crystal articles |
| JP3402603B2 (en) * | 1986-03-27 | 2003-05-06 | ゼネラル・エレクトリック・カンパニイ | Nickel-base-superalloy with improved low angle grain boundary resistance for producing single crystal products |
| JP2546324B2 (en) * | 1988-03-14 | 1996-10-23 | 三菱マテリアル株式会社 | Ni-based single crystal superalloy with excellent high temperature corrosion resistance |
| FR2686902B1 (en) * | 1992-02-05 | 1994-07-29 | Onera (Off Nat Aerospatiale) | SINGLE-CRYSTAL NICKEL-BASED SUPERALLOY WITH IMPROVED OXIDATION RESISTANCE AND PREPARATION METHOD. |
| JP3679973B2 (en) * | 2000-04-17 | 2005-08-03 | 三菱重工業株式会社 | Single crystal Ni-base heat-resistant alloy, turbine blade and gas turbine |
| EP1536026A1 (en) * | 2003-11-27 | 2005-06-01 | Siemens Aktiengesellschaft | High temperature resistant article |
| US8353444B2 (en) * | 2005-10-28 | 2013-01-15 | United Technologies Corporation | Low temperature diffusion braze repair of single crystal components |
| JP6267890B2 (en) * | 2013-08-07 | 2018-01-24 | 三菱日立パワーシステムズ株式会社 | Ni-base cast superalloy and casting made of the Ni-base cast superalloy |
| CN103966671A (en) * | 2014-03-31 | 2014-08-06 | 中国科学院金属研究所 | High-strength hot-corrosion-resistant Ni-based single crystal superalloy and preparation method |
| CN105200521B (en) * | 2014-05-28 | 2018-05-25 | 中国科学院金属研究所 | A kind of no rhenium low density and high performance nickel-base high-temperature single crystal alloy and its heat treatment process |
| JP6460336B2 (en) * | 2015-07-09 | 2019-01-30 | 三菱日立パワーシステムズ株式会社 | Ni-based high-strength heat-resistant alloy member, method for producing the same, and gas turbine blade |
| CN107675026A (en) * | 2017-09-30 | 2018-02-09 | 东方电气集团东方汽轮机有限公司 | A kind of low cost, the nickel-base high-temperature single crystal alloy of high comprehensive performance |
| CN111440967B (en) * | 2020-05-08 | 2021-12-31 | 中国科学院金属研究所 | High-thermal-stability high-strength Re-free nickel-based single crystal superalloy and preparation process thereof |
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