CN114686731B - Single crystal high temperature alloy and preparation method and application thereof - Google Patents
Single crystal high temperature alloy and preparation method and application thereof Download PDFInfo
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- CN114686731B CN114686731B CN202210377785.9A CN202210377785A CN114686731B CN 114686731 B CN114686731 B CN 114686731B CN 202210377785 A CN202210377785 A CN 202210377785A CN 114686731 B CN114686731 B CN 114686731B
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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%
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- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
- B22D27/045—Directionally solidified castings
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- 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
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
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Abstract
The invention relates to the technical field of single crystal high-temperature alloy, in particular to Ni 3 Al-based single crystal high-temperature alloy and a preparation method and application thereof. The invention provides Ni 3 Al-based single crystal superalloy, said Ni 3 The main bearing crystal orientation of the Al-based single crystal high-temperature alloy is [111]]Orientation; by mass percent, the Ni 3 The Al-based single crystal superalloy comprises the following elements: 7 to 8.5 percent of Al, less than or equal to 5 percent of Re + W, 7.1 to 7.5 percent of Mo7, 5.7 to 6.1 percent of Co, 4.8 to 5.3 percent of Ta4, 1.1 to 1.5 percent of Cr, less than or equal to 0.05 percent of Zr, less than or equal to 0.01 percent of C, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Hf, and the balance of Ni. The Ni 3 The Al-based single crystal high-temperature alloy has higher high-temperature creep property.
Description
Technical Field
The invention relates to the technical field of single crystal high-temperature alloys, in particular to a single crystal high-temperature alloy and a preparation method and application thereof.
Background
Ni 3 The Al-based single crystal high-temperature alloy is a key material for preparing a high-pressure turbine blade of an aircraft engine, and the high-temperature creep property of the Al-based single crystal high-temperature alloy is one of core indexes for ensuring the long-term stable service of the blade under the temperature-stress-environmental condition. By adding refractory elements Re and Ru, many generations of single crystal high temperature alloys have been developed]The orientation is in the main bearing direction, the high-temperature creep property is obviously improved, and the development of an aeroengine is greatly supported. Excessive refractory elements result in high cost and high densityThe problems of overlarge structure, poor structure stability and the like are solved, the high-temperature performance of the alloy is difficult to further improve, and the development of novel single crystal high-temperature alloy which can meet the requirements of high heat intensity and light weight of the turbine blade of an advanced high thrust-weight ratio engine becomes a hotspot and a difficult point.
By controlling the crystal orientation, the dominant orientation of the single crystal superalloy under anisotropy is selected as the main bearing direction, which is one of feasible ways. [111] The Schmid factor of the oriented octahedral slip system is 0.27, which is obviously lower than the Schmid factor of 0.41 under the [001] orientation, and is beneficial to improving the performance, so that the [111] oriented single crystal alloy has more excellent medium and low temperature creep resistance, durability and fatigue performance than the traditional [001] oriented alloy. The result shows that the [111] oriented single crystal superalloy has very excellent comprehensive mechanical properties and is a very potential advanced aeroengine turbine blade candidate material. However, the research on single crystal high temperature alloys such as SRR99, CMSX-4, DD15, DD6 and DD33 shows that the [111] orientation high temperature creep property is basically equivalent to the [001] orientation under the traditional alloying design and microstructure regulation, and the property advantage of the [111] crystal orientation is not exerted. That is, the components and structure of the conventional [001] oriented single crystal superalloy are not suitable for the [111] orientation performance, and the high temperature creep performance of the [111] oriented single crystal superalloy cannot be sufficiently exploited.
Disclosure of Invention
The invention aims to provide a single crystal high-temperature alloy, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides Ni 3 Al-based single crystal superalloy, said Ni 3 The main bearing crystal orientation of the Al-based single crystal high-temperature alloy is [111]]Orientation;
by mass percent, the Ni 3 The Al-based single crystal superalloy comprises the following elements: 7 to 8.5 percent of Al, less than or equal to 5 percent of Re + W, 7.1 to 7.5 percent of Mo7, 5.7 to 6.1 percent of Co5, 4.8 to 5.3 percent of Ta4, 1.1 to 1.5 percent of Cr1, less than or equal to 0.05 percent of Zr, less than or equal to 0.01 percent of C, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Hf, and the balance of Ni.
Preferably, the following elements are included: 8.1 to 8.2 percent of All, 1.4 to 1.5 percent of Re1, 1.8 to 2.0 percent of W, 7.4 to 7.5 percent of Mo7, 5.7 to 6.1 percent of Co5.0 to 5.1 percent of Ta5, 1.1 to 1.3 percent of Cr1, 0.01 percent of Zrl, less than or equal to 0.01 percent of C, less than or equal to 0.005 percent of B, 0.11 to 0.12 percent of Hf0 and the balance of Ni.
Preferably, the Ni 3 The matrix of the Al-based single crystal high-temperature alloy is Ni 3 An Al phase;
at room temperature, the Ni 3 The volume percentage content of the Al phase is more than or equal to 75 percent;
in service temperature, the Ni 3 The volume percentage content of the Al phase is more than or equal to 65 percent.
Preferably, the Ni 3 The density of the Al-based single crystal high-temperature alloy is 8.152-8.443 g/cm 3 。
The invention also provides Ni in the technical scheme 3 The preparation method of the Al-based single crystal superalloy comprises the following steps:
according to Ni 3 Preparing a mother alloy ingot by using the element composition of the Al-based single crystal high-temperature alloy;
taking the [111] oriented seed crystal as a seed crystal, melting the mother alloy ingot, and performing directional solidification to obtain a [111] oriented single crystal alloy;
mixing the [111]]Sequentially carrying out solid solution treatment and isothermal transformation heat treatment on the oriented single crystal alloy to obtain the Ni 3 Al-based single crystal superalloy.
Preferably, the drawing rate of the directional solidification is 150-250 μm/s.
Preferably, the melting temperature is 1600 to 1800 ℃.
Preferably, the temperature of the solution treatment is 1335-1345 ℃, and the holding time is 20-24 h.
Preferably, the temperature of the isothermal transformation heat treatment is 1045-1060 ℃, and the holding time is 82-106 h.
The invention also provides Ni in the technical scheme 3 Al-based single crystal superalloy or Ni prepared by the preparation method of the technical scheme 3 Use of an Al-based single crystal superalloy in a turbine blade.
The invention providesSeed Ni 3 Al-based single crystal superalloy, said Ni 3 The main bearing crystal orientation of the Al-based single crystal high-temperature alloy is [111]]Orientation; by mass percent, the Ni 3 The Al-based single crystal superalloy comprises the following elements: 7 to 8.5 percent of Al, less than or equal to 5 percent of Re + W, 7.1 to 7.5 percent of Mo7, 5.7 to 6.1 percent of Co5, 4.8 to 5.3 percent of Ta4, 1.1 to 1.5 percent of Cr1, less than or equal to 0.05 percent of Zr, less than or equal to 0.01 percent of C, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Hf, and the balance of Ni. The invention can ensure the Ni by controlling the Al within the range of 7-8.5 percent 3 Ni in Al-based single crystal superalloy 3 The Al phase is easier to be subjected to base conversion; at the same time due to [111]]Crystal orientation intrinsic elastic modulus up to [001]]Three times the orientation. The too high elastic modulus can cause the problems of too high casting residual stress and service thermal stress, induced dimensional deformation or recrystallization and the like, so that the total addition of the Young modulus strengthening element Re + W is reduced as much as possible in the developed alloy, and the mass percent of the Young modulus strengthening element Re + W is controlled to be less than 5%. Meanwhile, the invention further uses the Ni by synergistically controlling the using amount of other alloy elements 3 The density of the Al-based single crystal high temperature alloy is further reduced, the creep life at 1100 ℃ and 137MPa can reach 1274h, and the novel single crystal high temperature alloy meets the requirements of high heat intensity and light weight, and is an ideal substitute material for the turbine blade of the engine.
Drawings
FIG. 1 shows Ni prepared in example 1 3 SEM picture of Al-based single crystal superalloy;
FIG. 2 shows Ni prepared in example 1 3 A two-phase volume fraction statistical chart of the Al-based single crystal superalloy;
FIG. 3 shows Ni prepared in example 1 3 TEM image of Al-based single crystal superalloy after creep treatment at 1100 deg.C and 137 MPa;
FIG. 4 is a schematic view of dislocation motion for a conventional nickel-based single crystal superalloy;
FIG. 5 shows Ni as described in examples 1 to 5 3 Dislocation motion schematic diagram of Al-based single crystal superalloy;
FIG. 6 Ni produced in examples 1 to 5 3 The change curve of the density of the Al-based single crystal superalloy along with the temperature;
FIG. 7 shows Ni prepared in examples 1 to 5 and comparative examples 1 to 5 3 The elastic modulus curve of the Al-based single crystal superalloy at different temperatures;
FIG. 8 shows Ni prepared in examples 1 to 3 3 Creep curve of Al-based single crystal superalloy at 1100 deg.C and 137 MPa.
Detailed Description
The invention provides Ni 3 Al-based single crystal superalloy, said Ni 3 The main bearing crystal orientation of the Al-based single crystal high-temperature alloy is [111]]Orientation;
by mass percent, the Ni 3 The Al-based single crystal superalloy comprises the following elements: 7 to 8.5 percent of Al, less than or equal to 5 percent of Re + W, 7.1 to 7.5 percent of Mo7, 5.7 to 6.1 percent of Co5, 4.8 to 5.3 percent of Ta4, 1.1 to 1.5 percent of Cr1, less than or equal to 0.05 percent of Zr, less than or equal to 0.01 percent of C, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Hf, and the balance of Ni.
In the present invention, the Ni 3 The substrate of the Al-based single crystal superalloy is preferably Ni 3 An Al phase; at room temperature, the Ni 3 The volume percentage content of the Al phase is preferably more than or equal to 75 percent; in service temperature, the Ni 3 The volume percentage content of the Al phase is preferably more than or equal to 65 percent.
In the invention, the service temperature is preferably 1020-1060 ℃.
In the present invention, the Ni is controlled 3 The volume percentage content of the Al phase at room temperature and service temperature can better ensure Ni 3 Formation of Al-based composition, facilitating the formation of Ni 3 Conversion of Al phase into a matrix, and further increase of [111]]High temperature mechanical properties of crystal orientation.
In the present invention, the Ni 3 The density of the Al-based single crystal superalloy is preferably 8.152 to 8.443g/cm 3 。
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy contains 7 to 8.5% Al, preferably 8.1 to 8.2%.
In the present invention, the Al element is controlled within the above range to satisfy "in room temperature, the Ni 3 The volume percentage content of the Al phase is more than or equal to 75 percent; in service temperature, the Ni 3 The volume percentage content of the Al phase is more than or equal to 65 percent.
Based on the mass percentage, the Ni is 3 The Al-based single crystal high-temperature alloy comprises Re + W less than or equal to 5 percent; the preferable mass percentage of Re is 1.4-1.5%, and the preferable mass percentage of W is 1.8-2.0%.
In the invention, the addition of Re and W can improve the elastic modulus of the alloy, and the intrinsic elastic modulus of the [111] crystal orientation is three times of that of the [001] orientation, and too high elastic modulus can cause too high casting residual stress and service thermal stress; therefore, the addition ratio of Re and W in the range can be controlled to maintain the alloy in a more proper elastic modulus range, and the problems of excessive residual stress and service thermal stress, induced dimensional deformation or recrystallization and the like can be reduced or even avoided.
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy comprises Mo7.1 to 7.5%, preferably 7.4 to 7.5%.
In the invention, the Mo has the function of enabling the lattice mismatching degree of two phases to become more negative by being enriched in the matrix phase, thereby increasing the interface dislocation network density and being beneficial to improving the creep property. Meanwhile, mo can inhibit the formation of a Secondary Reaction Zone (SRZ).
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy comprises Co5.7 to 6.1%, preferably 5.8 to 6.0%.
In the invention, the Co plays a role of solid solution strengthening, the strength is improved, the fault energy of an alloy matrix can be reduced, and the endurance strength and the creep resistance of the alloy are obviously improved. Co can reduce the solid solution temperature of the gamma' phase, expand the heat treatment window and improve the phase stability. In addition, co can also improve the plasticity and hot workability of the alloy.
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy comprises Ta4.8-5.3%, preferably 5.0-5.1%.
In the invention, the Ta is enriched in a gamma ' phase, promotes the precipitation of the gamma ' phase and improves the stability of the gamma ' phase. Meanwhile, ta can improve the strength and the solid solution temperature of a gamma' phase and can effectively improve the oxidation resistance and the corrosion resistance of the alloy.
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy comprises Cr1.1-1.5%, preferably 1.1-1.3%.
In the invention, the Cr is enriched in the gamma matrix, thereby improving the oxidation resistance and hot corrosion resistance of the alloy and simultaneously playing a role in solid solution strengthening.
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy contains Zr less than or equal to 0.05 percent, and preferably 0.01 percent.
In the invention, the Zr is enriched in dendrites to strengthen the dendrite intercrystals.
Based on the mass percentage, the Ni is 3 The Al-based single crystal high-temperature alloy comprises less than or equal to 0.01 percent of C, and preferably 0.002 to 0.008 percent.
In the present invention, C functions as an important interdendritic strengthening element to strengthen interdendritic dendrites, stabilize the structure, and suppress the precipitation of a harmful TCP phase. The C element is also an important alloy refining agent, and plays a role of a deoxidizer in the alloy smelting process and simultaneously increases the casting performance of the alloy.
Based on the mass percentage, the Ni is 3 The Al-based single crystal high-temperature alloy comprises less than or equal to 0.005 percent of B, and preferably 0.002 to 0.003 percent of B.
In the invention, the B plays a role of enriching in grain boundaries and increasing the bonding force of the grain boundaries. B can form boride with alloy elements, and the boride is distributed in a grain boundary in a granular or block form, so that grain boundary slippage is prevented, and connection and expansion of grain boundary cavities are inhibited. Meanwhile, the precipitation of harmful phases at the grain boundary can be eliminated, and the content of harmful elements at the grain boundary is reduced.
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy comprises Hf less than or equal to 0.15%, and preferably 0.11-0.12%.
In the invention, the Hf is enriched in the gamma ' phase, so that the content of the gamma ' phase is increased, the antiphase domain boundary energy of the gamma ' phase can be improved, and dislocation is prevented from passing through the gamma ' phase by a cutting mechanism, thereby improving the strength of the gamma ' phase. Meanwhile, the Hf atom has larger radius, so that the mismatching degree of two phases of lattices can be increased, and the creep property of the alloy is improved.
Based on the mass percentage, the Ni is 3 The Al-based single crystal superalloy includes Ni as a balance.
In the present invention, the Ni is synergistically acted by controlling the amounts of Mo, co, ta, cr, zr, C, B and Hf to be within the above ranges 3 The density of the Al-based single crystal high-temperature alloy is further reduced, and the light single crystal high-temperature alloy is favorably obtained.
The invention also provides Ni in the technical scheme 3 The preparation method of the Al-based single crystal superalloy comprises the following steps:
according to Ni 3 Preparing a mother alloy ingot by using the element composition of the Al-based single crystal high-temperature alloy;
taking the [111] oriented seed crystal as a seed crystal, melting the mother alloy ingot, and performing directional solidification to obtain a [111] oriented single crystal alloy;
will be described in [111]]Sequentially carrying out solid solution treatment and isothermal transformation heat treatment on the oriented single crystal alloy to obtain the Ni 3 Al-based single crystal superalloy.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
Ni according to the technical scheme of the invention 3 And (3) preparing the Al-based single crystal high-temperature alloy to obtain a master alloy ingot.
In the invention, the method for preparing the master alloy ingot is preferably vacuum arc melting; the vacuum arc melting process is not limited in any way, and can be carried out by adopting a process well known to a person skilled in the art.
After a mother alloy ingot is obtained, the method takes [111] oriented seed crystals as seed crystals, and after the mother alloy ingot is melted, the directional solidification is carried out to obtain the [111] oriented single crystal alloy.
After obtaining the master alloy ingot, the invention also preferably comprises the step of pretreating the master alloy ingot, wherein the pretreatment is preferably to process the master alloy ingot into a metal cylinder with the diameter of 15mm and the length of 70mm, then to machine and polish oxide skin, and then to clean the metal cylinder with acetone and then to dry the metal cylinder.
In the present invention, the melting temperature is preferably 1600 to 1800 ℃, more preferably 1650 to 1750 ℃. The present invention does not have any particular limitation on the temperature increase rate for the melting, and the temperature increase rate known to those skilled in the art may be used. In an embodiment of the present invention, the thawing process specifically includes: firstly, the temperature is raised from room temperature to 1000 ℃ at a heating rate of 15 ℃/min, and then the temperature is raised to 1600 ℃ at a heating rate of 5 ℃/min.
In the present invention, the drawing rate of the directional solidification is preferably 150 to 250. Mu.m/s, more preferably 200. Mu.m/s.
In the invention, the process of directional solidification is preferably carried out in an LMC directional solidification furnace, and the specific process is preferably as follows: the mould of the LMC directional solidification furnace is a hollow alumina ceramic tube, the inner diameter is about 15mm generally, the diameters of a mother alloy test bar and seed crystals are consistent with the inner diameter of the mould, then the seed crystals are placed at the bottom, then the mother alloy test bar is placed, and then the mother alloy part is melted and drawn.
To obtain [111]]After the single crystal alloy is oriented, the invention uses the [111]]Sequentially carrying out solid solution treatment and isothermal transformation heat treatment on the oriented single crystal alloy to obtain the Ni 3 Al-based single crystal superalloy.
In the present invention, the temperature of the solution treatment is preferably 1335 to 1345 ℃, more preferably 1338 to 1342 ℃; the holding time is preferably 20 to 24 hours, more preferably 22 to 23 hours.
In the present invention, the temperature of the isothermal transformation heat treatment is preferably 1045 to 1060 ℃, more preferably 1050 to 1055 ℃; the heat preservation time is preferably 82 to 106 hours, and more preferably 90 to 100 hours; in the invention, the isothermal transformation thermal treatment process specifically comprises the steps of putting the solid solution alloy obtained after the solid solution treatment into a salt bath at 1045-1060 ℃ and preserving heat.
In the invention, the process of isothermal transformation thermal treatment can realize the Ni 3 And (4) conversion of Al phase into a matrix.
The invention also provides Ni in the technical scheme 3 Al-based single crystal superalloy or Ni prepared by the preparation method of the technical scheme 3 The application of Al-based single crystal superalloy in the preparation of turbine blades. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
Ni provided by the present invention is described in connection with examples 3 Al-based single crystal superalloys, methods of making and using the same are described in detail, but they are not to be construed as limiting the scope of the invention.
Examples 1 to 5
Ni described in examples 1 to 5 3 The elemental compositions of the Al-based single crystal superalloys (corresponding to alloys 1-5) are shown in table 1:
TABLE 1 Ni described in examples 1 to 5 3 Elemental composition (wt%) of Al-based single crystal superalloy
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Ni | 68.325 | 73.590 | 68.625 | 69.194 | 68.78 |
| Al | 8 | 8 | 8.2 | 7.5 | 8.5 |
| Co | 6 | 6 | 6 | 5.7 | 6.1 |
| Cr | 1.5 | 1.5 | 1.2 | 1.1 | 1.2 |
| Hf | 0.15 | 0 | 0.15 | 0.1 | 0.1 |
| Mo | 7.4 | 7.4 | 7.3 | 7.1 | 7.1 |
| Re | 1.5 | 1.5 | 1.5 | 2 | 1.5 |
| Ta | 5.1 | 0 | 5.1 | 5.3 | 5.2 |
| W | 2 | 2 | 1.9 | 2 | 1.5 |
| Zr | 0.01 | 0 | 0.01 | 0 | 0.01 |
| B | 0.005 | 0 | 0.005 | 0.001 | 0.005 |
| C | 0.01 | 0.01 | 0.01 | 0.005 | 0.005 |
The preparation method comprises the following steps:
preparing a master alloy ingot by adopting a vacuum arc melting method according to the element composition ratio;
processing the master alloy ingot into a metal cylinder with the diameter of 15mm and the length of 70mm, polishing oxide skin, cleaning with acetone, and drying to obtain a cylindrical master alloy ingot;
placing the [111] oriented seed crystal at the bottom of a ceramic mold, then placing the ceramic mold into a cylindrical master alloy ingot, fixing the cylindrical master alloy ingot in the LMC oriented solidification furnace, firstly heating the alloy ingot to 1600 ℃ (the heating process is that the temperature is firstly increased from room temperature to 1000 ℃ at the heating rate of 15 ℃/min, and then is increased to 1600 ℃ at the heating rate of 5 ℃/min, and then carrying out oriented solidification (the drawing rate of the oriented solidification is 200 mu m/s) to obtain the [111] oriented single crystal alloy;
mixing the [111]]Sequentially carrying out solid solution treatment (the temperature is 1345 ℃ and the time is 20 h) and isothermal transformation thermal treatment (the solid solution alloy is put into a salt bath at 1060 ℃ and is kept warm for 82 h) on the oriented single crystal alloy to obtain the Ni 3 Al-based single crystal superalloy.
Comparative examples 1 to 5
Ni as described in comparative examples 1 to 5 3 The elemental composition of the Al-based single crystal superalloy (corresponding to the alloy 1-5001 orientation) is shown in table 2:
TABLE 2 Ni as described in comparative examples 1 to 5 3 Elemental composition (wt%) of Al-based single crystal superalloy
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Ni | 68.325 | 73.590 | 68.625 | 69.194 | 68.78 |
| Al | 8 | 8 | 8.2 | 7.5 | 8.5 |
| Co | 6 | 6 | 6 | 5.7 | 6.1 |
| Cr | 1.5 | 1.5 | 1.2 | 1.1 | 1.2 |
| Hf | 0.15 | 0 | 0.15 | 0.1 | 0.1 |
| Mo | 7.4 | 7.4 | 7.3 | 7.1 | 7.1 |
| Re | 1.5 | 1.5 | 1.5 | 2 | 1.5 |
| Ta | 5.1 | 0 | 5.1 | 5.3 | 5.2 |
| W | 2 | 2 | 1.9 | 2 | 1.5 |
| Zr | 0.01 | 0 | 0.01 | 0 | 0.01 |
| B | 0.005 | 0 | 0.005 | 0.001 | 0.005 |
| C | 0.01 | 0.01 | 0.01 | 0.005 | 0.005 |
The preparation method was referenced to examples 1 to 5, except that the seed crystal was a [001] oriented seed.
Test example
Ni prepared in example 1 3 SEM test of the Al-based single crystal superalloy, the test result is shown in figure 1, and as can be seen from figure 1, after isothermal transformation heat treatment, the Ni is 3 Ni in Al-based single crystal superalloy 3 Al phases (gamma' phases) are mutually communicated, and Ni solid solution phases (gamma phases) form mutually independent irregular island-shaped structures;
FIG. 2 shows Ni prepared in example 1 3 A two-phase volume fraction statistical chart of the Al-based single crystal superalloy, wherein regions 1-24 represent gamma-phase, and region 25 represents the whole of FIG. 2; as shown in Table 3, the statistical results of the sum of the relative areas of the regions 1 to 24 and the relative area of the region 25 were found to be 10.278 and 46.081, respectively, and the calculated gamma phase fraction was 22.3% and the calculated gamma' phase fraction was 77.7%, indicating that Ni is present in the alloy 3 The volume fraction of the Al phase is more than 75%;
table 3 Ni prepared in example 1 3 Area ratio of each region in Al-based single crystal superalloy
Ni prepared in example 1 3 The Al-based single crystal superalloy was subjected to TEM test after creeping at 1100 ℃ under 137MPa, and the test results are shown in FIG. 3, from FIG. 3, it can be seen that Ni after creeping 3 Ni in Al-based single crystal high-temperature alloy 3 The Al phases are mutually communicated, and the gamma phases are mutually independent and have small size;
FIG. 4 is a schematic view showing dislocation movement of a conventional nickel-based single crystal superalloy (CMSX-4, renen5, DD6, or PWA 1497), wherein a is<001>Schematic diagram of the movement of orientation dislocation, b and c are<111>Schematic view of orientation dislocation motion. FIG. 5 shows Ni as described in examples 1 to 5 3 Dislocation motion schematic of Al-based single crystal superalloys. As can be seen from FIG. 4, the conventional Ni-based single crystal superalloy germinates in the gamma phase during creep, and as creep progresses, dislocations proliferate and form a dense dislocation network at the interface of two phases, which prevents dislocation movement and dislocation cutting of the gamma 'phase, and only a small amount of dislocations cut the gamma' phase before entering the third phase of creep. The nickel-based single crystal superalloy generates tissue raft in the creep process<111>Orientation, the included angle between raft tissue and stress axis is about 55 deg., dislocation moves along raft surface by sliding and climbing mixture and crosses gamma' phase at raft tissue surface (namely two-phase interface), equivalent to<110>The {001} hexahedral glide series starts with a Schmid factor of about 0.47. As can be seen from FIG. 5, with respect to Ni 3 The Al-based single crystal high-temperature alloy has mutually independent gamma phases, limited dislocation motion range and incapability of climbing over the gamma' phase at the interface of two phases, and cannot be equivalent to a complete hexahedral sliding system, namely only<110>The {111} glide line starts, with a Schmid factor of about 0.27. Thus, ni 3 The Al-based single crystal high-temperature alloy can obviously improve the [111]]Crystal orientation high-temperature mechanical properties;
FIG. 6 example1 to 5 of prepared Ni 3 The change curve of the density of the Al-based single crystal superalloy along with the temperature, the Ni of the invention 3 The density of the Al-based single crystal high-temperature alloy is 8.152-8.443 g/cm 3 ；
FIG. 7 shows Ni prepared in examples 1 to 5 and comparative examples 1 to 5 3 The elastic modulus curve of the Al-based single crystal superalloy at different temperatures is determined according to the Schmid law,<001>the octahedral slip system in the oriented single crystal alloy starts at 2/3, and the corresponding Schmid factor is 0.41; and then<111>The octahedral slip system in the oriented single crystal alloy is 1/2 of the movement, and the corresponding Schmid factor is 0.27, so that<111>Modulus of elasticity of orientation of about<001>Twice (as shown in table 4); as can be seen from the elastic modulus curve shown in fig. 7, the elastic modulus of the 111 orientation is twice as high as 001, and even if the elastic modulus of 001 is within the normal range, the elastic modulus of 111 may be too high to cause residual stress. For example, an elastic modulus of more than 300MPa induces residual stress, and if an elastic modulus of 001 is 200MPa, the elastic modulus of 111 orientation reaches 400MPa, exceeding the threshold inducing residual stress. It is necessary to reduce the 111 orientation elastic modulus to a range not inducing residual stress by controlling the contents of Re and W. Therefore, the contents of Re and W are reasonably controlled to be below 5 percent;
TABLE 4 octahedral slip system in different oriented alloys
| Sliding system | <001> | <111> |
| (111)[1-10] | 0 | 0 |
| (111)[-101] | 0.408 | 0 |
| (111)[01-1] | 0.408 | 0 |
| (-111)[101] | 0.408 | 0.272 |
| (-111)[110] | 0 | 0.272 |
| (-111)[01-1] | 0.408 | 0 |
| (1-11)[-101] | 0.408 | 0 |
| (1-11)[011] | 0.408 | 0.272 |
| (1-11)[110] | 0 | 0.272 |
| (11-1)[011] | 0.408 | 0.272 |
| (11-1)[101] | 0.408 | 0.272 |
| (11-1)[-110] | 0 | 0 |
Ni prepared in examples 1 to 3 3 The creep test of the Al-based single crystal superalloy was carried out at 1100 ℃ and 137MPa, and the test results are shown in FIG. 8, from which it can be seen that Ni prepared in examples 1 to 3 is shown in FIG. 8 3 The creep life of the Al-based single crystal superalloy is 1274h, 1212h and 1143h respectively, and exceeds that of the fourth generation nickel-based single crystal superalloy TMS-138<001>Oriented creep life 423h.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. Ni 3 Al-based single crystal superalloy, characterized in that Ni is as defined above 3 The main bearing crystal orientation of the Al-based single crystal high-temperature alloy is [111]]Orientation;
by mass percent, the Ni 3 The Al-based single crystal superalloy comprises the following elements: 7 to 8.5 percent of Al, less than or equal to 5 percent of Re + W, 7.1 to 7.5 percent of Mo, 5.7 to 6.1 percent of Co, 4.8 to 5.3 percent of Ta4, 1.1 to 1.5 percent of Cr, less than or equal to 0.05 percent of Zr, less than or equal to 0.01 percent of C, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Hf, and the balance of Ni;
the Ni 3 The preparation method of the Al-based single crystal superalloy comprises the following steps:
according to Ni 3 Preparing a mother alloy ingot by using the element composition of the Al-based single crystal high-temperature alloy;
taking the [111] oriented seed crystal as a seed crystal, melting the mother alloy cast ingot, and then performing directional solidification to obtain a [111] oriented single crystal alloy;
mixing the [111]]Sequentially carrying out solid solution treatment and isothermal transformation heat treatment on the oriented single crystal alloy to obtain the Ni 3 Al-based single crystal superalloy;
the temperature of the isothermal transformation heat treatment is 1045-1060 ℃, and the heat preservation time is 82-106 h.
2. The Ni of claim 1 3 The Al-based single crystal superalloy is characterized by comprising the following elements: 8.1 to 8.2 percent of Al, 1.4 to 1.5 percent of Re, 1.8 to 2.0 percent of W, 7.4 to 7.5 percent of Mo, 5.7 to 6.1 percent of Co, 5.0 to 5.1 percent of Ta5, 1.1 to 1.3 percent of Cr, 0.01 percent of Zr, less than or equal to 0.01 percent of C, less than or equal to 0.005 percent of B, 0.11 to 0.12 percent of Hf0 and the balance of Ni.
3. Ni according to claim 1 or 2 3 Al-based single crystal superalloy, characterized in that Ni is as defined above 3 The matrix of the Al-based single crystal superalloy is Ni 3 An Al phase;
at room temperature, the Ni 3 The volume percentage content of the Al phase is more than or equal to 75 percent;
in service temperature, the Ni 3 The volume percentage content of the Al phase is more than or equal to 65 percent.
4. Ni according to claim 3 3 Al-based single crystal superalloy, characterized in that Ni is as defined above 3 The density of the Al-based single crystal high-temperature alloy is 8.152-8.443 g/cm 3 。
5. Ni according to any one of claims 1 to 4 3 The preparation method of the Al-based single crystal superalloy is characterized by comprising the following steps:
according to Ni 3 Preparing a mother alloy ingot by using the element composition of the Al-based single crystal high-temperature alloy;
taking the [111] oriented seed crystal as a seed crystal, melting the mother alloy ingot, and performing directional solidification to obtain a [111] oriented single crystal alloy;
will be described in [111]]Sequentially carrying out solid solution treatment and isothermal transformation heat treatment on the oriented single crystal alloy to obtain the Ni 3 Al-based single crystal superalloy;
the temperature of the isothermal transformation heat treatment is 1045-1060 ℃, and the heat preservation time is 82-106 h.
6. The process according to claim 5, wherein the drawing rate of the directional solidification is from 150 to 250 μm/s.
7. The method of claim 5, wherein the melting temperature is 1600 to 1800 ℃.
8. The method according to claim 5, wherein the solution treatment temperature is 1335-1345 ℃ and the holding time is 20-24 h.
9. Ni according to any one of claims 1 to 4 3 Al-based single crystal superalloy or Ni prepared by the method of any of claims 5 to 8 3 The Al-based single crystal superalloy is applied to the turbine blade of an engine.
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| CN101289018A (en) * | 2007-04-18 | 2008-10-22 | 株式会社日立制作所 | Heat-resistant component with heat insulation coating |
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| CN113564717A (en) * | 2021-07-27 | 2021-10-29 | 北航（四川）西部国际创新港科技有限公司 | Ni3Al-based single crystal high-temperature alloy and preparation method thereof |
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| US7338259B2 (en) * | 2004-03-02 | 2008-03-04 | United Technologies Corporation | High modulus metallic component for high vibratory operation |
| CN100587134C (en) * | 2007-12-17 | 2010-02-03 | 北京航空航天大学 | Method for preparing Ni3Al based single-crystal high-temperature alloy by employing seed crystal |
| EP2465957B1 (en) * | 2009-08-10 | 2018-11-07 | IHI Corporation | Ni-BASED MONOCRYSTALLINE SUPERALLOY AND TURBINE BLADE |
| JP5296046B2 (en) * | 2010-12-28 | 2013-09-25 | 株式会社日立製作所 | Ni-based alloy and turbine moving / stator blade of gas turbine using the same |
| CN106521244A (en) * | 2016-12-16 | 2017-03-22 | 北京航空航天大学 | High-Mo Ni3Al-based monocrystal high-temperature alloy modified by rare earth and preparation method of high-Mo Ni3Al-based monocrystal high-temperature alloy |
| CN112899786B (en) * | 2021-01-15 | 2022-02-08 | 北京航空航天大学 | Component design method of nickel-based single-crystal superalloy seed alloy and nickel-based single-crystal superalloy seed alloy |
| CN114686731B (en) * | 2022-04-12 | 2022-11-22 | 北航（四川）西部国际创新港科技有限公司 | Single crystal high temperature alloy and preparation method and application thereof |
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| CN101087894A (en) * | 2004-12-23 | 2007-12-12 | 西门子公司 | A Ni based alloy, a component, a gas turbine arrangement and use of pd in connection with such an alloy |
| CN101289018A (en) * | 2007-04-18 | 2008-10-22 | 株式会社日立制作所 | Heat-resistant component with heat insulation coating |
| CN112176225A (en) * | 2020-09-24 | 2021-01-05 | 中国科学院金属研究所 | Nickel-based single crystal superalloy and preparation method thereof |
| CN113529172A (en) * | 2021-07-20 | 2021-10-22 | 广西科技大学 | Single crystal alloy for ultrahigh temperature creep clamp and preparation method thereof |
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