CN115821116A - Additive manufacturing nickel-based high-temperature alloy and preparation method thereof - Google Patents
Additive manufacturing nickel-based high-temperature alloy and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention relates to an additive manufacturing nickel-based high-temperature alloy and a preparation method thereof, and relates to the technical field of additive manufacturing nickel-based high-temperature alloys. The main technical scheme adopted is as follows: an additive manufacturing nickel-base superalloy having a chemical composition, in weight percent, as follows: 6.5 to 9.5 weight percent of Cr, 6.5 to 9.5 weight percent of Co, 6.5 to 9.5 weight percent of W, 1.0 to 2.5 weight percent of Mo1, 4.0 to 5.5 weight percent of Al, 0.5 to 1.5 weight percent of Ti, 4.5 to 6.0 weight percent of Ta, 0.01 to 0.1 weight percent of C, 0.01 to 0.1 weight percent of B and the balance of Ni. The invention is mainly used for providing and preparing the additive manufacturing nickel-based superalloy which has excellent high-temperature performance, good structural stability, low crack sensitivity and low hole defects. The strength of the additive manufactured nickel-based high-temperature alloy is superior to that of an ABD-850M alloy, is close to that of a typical CM247LC alloy, and is particularly suitable for additive manufacturing of long-life and high-reliability hot-end high-temperature components in the fields of aviation, aerospace, energy and the like.
Description
Technical Field
The invention relates to the technical field of additive manufacturing of nickel-based high-temperature alloys, in particular to an additive manufacturing nickel-based high-temperature alloy and a preparation method thereof.
Background
The nickel-based high-temperature alloy is the first choice material of the key hot end component which bears the highest temperature and the most complicated stress load in the advanced high thrust-weight ratio aircraft engine at present and in a long period of time in the future due to the excellent high-temperature stability and mechanical property.
The additive manufacturing technology has the advantages of high preparation freedom, short period, capability of realizing integrated forming and the like, so that the requirement of additive manufacturing of high-temperature alloy precision components is more urgent. However, due to the high alloying of the superalloy and the high volume fraction of the gamma prime phase, cracks, holes, and other defects may occur during printing. At present, the process optimization (regulating and controlling the scanning speed, the laser power and the like) mainly adopted at home and abroad can not thoroughly eliminate cracks, and the design optimization of components can effectively solve the defect problem.
There are studies showing that: when Al + Ti is more than or equal to 6.5wt%, the additive manufacturing superalloy is easy to generate low-melting-point phase and gamma' -phase volume fraction is high, and the weldability is poor (such as IN738, CM247, CMSX-4 alloy and the like); however, the reduction of the content of the gamma 'phase forming elements such as Al, ti and the like will reduce the volume fraction of the gamma' phase of the high-temperature strengthening phase in the alloy, and influence the high-temperature mechanical property of the alloy. Ta element is used as a main gamma ' phase forming element, has the characteristics of large atomic radius, low diffusion coefficient and the like, can replace partial Al atoms to form and strengthen the gamma ' phase, thereby reducing the addition of Al, ti and other elements, inhibiting the formation of low-melting-point phase, controlling the content of the gamma ' phase and reducing the crack sensitivity of the alloy. However, the excessive contents of Al, ti and Ta still cause the increase of the contents of low melting point phase, carbide and gamma' phase and the solidification range, the crack sensitivity of the alloy is rapidly increased, and the structure stability is deteriorated.
Accordingly, the inventors of the present invention considered that: to ensure sufficient gamma prime phase content to obtain excellent high temperature mechanical properties while maintaining good structural stability and low crack sensitivity, the contents of Al, ti and Ta must be controlled within appropriate ranges, and the determination of the ranges is a current problem.
Disclosure of Invention
In view of the above, the present invention provides an additive manufacturing nickel-based superalloy and a preparation method thereof, and mainly aims to provide and prepare an additive manufacturing nickel-based superalloy having excellent high temperature performance, good structural stability, low crack sensitivity, and low void defects.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide an additive manufactured nickel-base superalloy, wherein the additive manufactured nickel-base superalloy has a chemical composition, in weight percent, as follows:
Cr 6.5-9.5wt％；
Co 6.5-9.5wt％；
W 6.5-9.5wt％；
Mo 1.0-2.5wt％；
Al 4.0-5.5wt％；
Ti 0.5-1.5wt％；
Ta 4.5-6.0wt％；
C 0.01-0.1wt％；
B 0.01-0.1wt％；
the balance being Ni.
Preferably, if the additive manufacturing nickel-based superalloy is in a laser metal deposition printing state, the volume fraction of a gamma' phase in the additive manufacturing nickel-based superalloy is 40-50%; after the laser metal deposition printing state is subjected to heat treatment, the volume fraction of the gamma' phase is 50-60%.
Preferably, if the additive manufactured nickel-base superalloy is in a selective laser melting printed state (having little or no gamma prime phase in the printed state), the selective laser melting printed state has a volume fraction of gamma prime phase of 50-60% after heat treatment.
Preferably, if the additive manufacturing nickel-base superalloy is in a laser metal deposition printing state, then: the microstructure of the additive manufacturing nickel-based superalloy presents columnar crystals growing along the construction direction; the inside of the columnar crystal is provided with fine gamma' phases among dendrites and dendrites which grow in parallel (the parallel refers to the growth which is parallel to the construction direction and is parallel to each other); wherein, the primary dendrite spacing of the dendrite is 30-50 μm, preferably 30-40 μm; the size of the gamma 'phase is 0.05-0.1 μm, and the shape of the gamma' phase has a certain cubic degree; preferably, the gamma prime phase is distributed in the dendrite trunk and interdendritic region of the dendrite; preferably, the size of carbides in the microstructure of the additive manufacturing nickel-base superalloy is less than or equal to 150nm, preferably less than or equal to 100nm; the carbide is dispersedly distributed in the dendrite trunk and interdendritic region of the dendrite. Preferably, the average size of the crystal grains of the columnar crystals is 250 to 300 μm.
Preferably, if the additive manufacturing nickel-base superalloy is in a laser metal deposition printing state, the instantaneous tensile properties of the nickel-base superalloy are as follows: sigma of the additive manufacturing nickel-base superalloy at room temperature b ≥1320MPa，σ 0.2 Not less than 970MPa, A not less than 19%; sigma of the additive manufacturing nickel-base superalloy at a temperature of 760 ℃ b ≥1170MPa，σ 0.2 More than or equal to 925MPa, A more than or equal to 35 percent; sigma of the additive manufacturing nickel-base superalloy at a temperature of 1000 ℃ b ≥450MPa,σ 0.2 ≥350MPa，A≥50％。
Preferably, if the additive manufacturing nickel-base superalloy is in a selective laser melting printing state, then: the microstructure of the nickel-based superalloy presents columnar crystals growing along the construction direction; the columnar crystals have a cell structure inside. Preferably, the average size of the crystal grains of the columnar crystals is 60 to 100 μm.
Preferably, if the additive manufacturing nickel-base superalloy is in a selective laser melting printing state, the instantaneous tensile properties of the nickel-base superalloy are as follows: sigma of the additive manufacturing nickel-based superalloy at room temperature b ≥1100MPa，σ 0.2 850MPa or more and A is or more than 19 percent; sigma of the additive manufacturing nickel-base superalloy at a temperature of 760 ℃ b ≥1100MPa，σ 0.2 Not less than 900900MPa, A not less than 12%; sigma of the additive manufacturing nickel-base superalloy at a temperature of 1000 ℃ b ≥558MPa,σ 0.2 ≥370MPa，A≥10％。
On the other hand, an embodiment of the present invention further provides a preparation method of any one of the foregoing additive manufacturing nickel-based superalloys, where the preparation method of the additive manufacturing nickel-based superalloy includes the following steps:
preparing a master alloy: carrying out vacuum smelting on the raw materials and casting the raw materials into a master alloy meeting the chemical components;
preparing alloy powder: atomizing the master alloy into alloy powder;
preparing the nickel-based superalloy: and printing the alloy powder into the additive manufacturing nickel-based superalloy by utilizing a laser metal deposition process or a selective laser melting process.
Preferably, in the step of preparing a master alloy:
the vacuum smelting comprises the following steps: refining at 1500-1600 deg.C for 5-10min; and/or
The casting temperature is 1420-1480 ℃; and/or
After the casting, polishing and sand blowing treatment are carried out; and/or
The content of impurity elements in the master alloy is less than 5ppm; wherein the impurity element includes N, P, and S.
Preferably, in the step of preparing the alloy powder: preparing the master alloy into alloy powder by using argon atomization equipment under the conditions that the pressure is 5-8MPa and the temperature is 1350-1450 ℃; wherein the sphericity of the alloy powder is 87-89%, preferably 88%, and the alloy powder with D50 of 90-100 μm is screened for use in the step of preparing the nickel-base superalloy.
Preferably, in the step of preparing the nickel-base superalloy:
if the laser metal deposition process is selected, the laser metal deposition process parameters are set as follows: the power is set to be 1500-2000W, the scanning speed is set to be 800-1500mm/min, the powder feeding speed is set to be 8-12g/min, and the laser diameter is 1-3mm, preferably 2mm;
if the selective laser melting process is selected, the parameters of the selective laser melting process are set as follows: the power is set to be 300-400W, the scanning speed is set to be 800-1000mm/s, the layer thickness is set to be 30-50 mu m, the laser diameter is set to be 100-200 mu m, and the lap ratio is 30-40%.
Compared with the prior art, the additive manufacturing nickel-based high-temperature alloy and the preparation method thereof have the following beneficial effects:
on one hand, the chemical composition design of the additive manufacturing nickel-based superalloy provided by the embodiment of the invention is as follows: 6.5 to 9.5 weight percent of Cr, 6.5 to 9.5 weight percent of Co, 6.5 to 9.5 weight percent of W, 1.0 to 2.5 weight percent of Mo1, 4.0 to 5.5 weight percent of Al, 0.5 to 1.5 weight percent of Ti, 4.5 to 6.0 weight percent of Ta, 0.01 to 0.1 weight percent of C, 0.01 to 0.1 weight percent of B and the balance of Ni. The invention controls the volume fraction (40-60%) of the gamma ' phase by adopting a higher Ta/Al ratio so as to strengthen the gamma and gamma ' phases while ensuring high-temperature performance, effectively inhibit the formation of gamma/gamma ' low-melting-point eutectic, and add higher content of solid solution strengthening elements such as W, mo, cr, co and the like to strengthen the intrinsic strength of a matrix and trace crystal boundary elements such as C and B to strengthen crystal boundaries. The formation of liquefied cracks, solidified cracks and solid cracks is inhibited as far as possible through the regulation and control of the components, the high-temperature mechanical properties in the alloy are improved by exerting the effects of precipitation strengthening, solid solution strengthening and grain boundary strengthening of alloy elements, the high-temperature structure stability is kept, and the alloy reaches the level of high-performance additive manufacturing of high-temperature alloys.
Further, the alloy of the above chemical composition of the present invention contains only one noble metal of the Ta element, and therefore, the cost is low as a whole. On the other hand, the invention ensures the forming efficiency of the gamma 'phase by improving the Ta/Al ratio and adding a small amount of Ti element, ensures that the high content (40-60%) of the gamma' phase can be met firstly, and ensures the high-temperature performance. Second, the inventors of the present invention found that: the high Ta/Al ratio can inhibit the interdendritic segregation, such as the segregation of Al, ti, C and other elements, reduce the size of the carbide to a certain extent, and enable the carbide to be in a dispersion distribution form, so that the problem that the performance is affected due to the large-size carbide caused by the high Ta can be avoided (namely, the high Ta/Al ratio designed by the application can avoid the interdendritic segregation and reduce the formation of harmful phases).
Further, if the additive manufacturing nickel-base superalloy is in a laser metal deposition printing state, the microstructure thereof is as follows: exhibit columnar crystals growing in the build direction (the crystal grains of the columnar crystals of the present invention are well oriented, see (a) diagram in fig. 9); the inside of the columnar crystal is provided with dendrites which grow in parallel and fine gamma' phases among the dendrites; wherein, the primary dendrite spacing of the dendrite is 30-40 μm, the spacing is smaller, and the smaller the primary dendrite spacing is, the better the performance is (the high Ta/Al ratio designed by the invention can strengthen the strength of the dendrite); the size of the gamma ' phase is 0.05-0.1 mu m (note: the chemical composition design of the nickel-based superalloy of the invention is matched with a laser metal deposition printing process, so that a better gamma ' phase can be precipitated in a printing state, and the printing state has excellent performance, in the prior art, the high-content gamma ' phase can be precipitated only by carrying out subsequent heat treatment on the printing state, and the shape of the gamma ' phase has certain cubic degree (the good-shape gamma ' phase can be obtained due to the high Ta/Al ratio of the invention); the gamma' phase is distributed in the dendrite trunk and interdendritic region of the dendrite; the size of carbide in the microstructure of the additive manufacturing nickel-based superalloy is less than or equal to 150nm, preferably less than or equal to 100nm; the carbide is dispersedly distributed in the dendrite trunk and interdendritic region of the dendrite. The nickel-based superalloy with the chemical composition has excellent performance after heat treatment compared with the existing partial alloy without subsequent heat treatment in a laser metal deposition printing state.
Further, if the additive manufacturing nickel-base superalloy of the present invention is in the selective laser melting printing state, it is superior to the selective laser melting printing state nickel-base superalloy of the prior art.
On the other hand, the embodiment of the invention provides the preparation method for the additive manufacturing nickel-based superalloy, which improves the laser density in a specific process so as to overcome the defects caused by refractory elements W, mo and Ta and enable the defects to exert respective advantages.
In summary, the additive manufacturing nickel-based superalloy and the preparation method thereof provided by the embodiment of the invention enable the additive manufacturing nickel-based superalloy to have low crack sensitivity, excellent formability, strong process adaptability and good structure stability. Compared with the existing alloy, the additive manufactured nickel-based high-temperature alloy has better room temperature, medium temperature, high temperature strength and plasticity.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a metallographic and scanned microstructure representation of as-printed samples of laser metal deposition prepared in accordance with example 1 of the present invention; wherein, the diagram (a) in FIG. 1 is a gold phase diagram; FIG. 1 (b) is a scanned microstructure view;
FIG. 2 is a macroscopic fracture morphology after room temperature, medium temperature, high temperature tensile fracture of a laser metal deposition as-printed sample prepared in example 1 of the present invention; wherein, the graph (a) is the macro fracture morphology after room temperature tensile fracture, (b) is the macro fracture morphology after medium temperature (760 ℃) tensile fracture, and (c) is the macro fracture morphology after high temperature (1000 ℃) tensile fracture;
FIG. 3 is a graph comparing tensile properties at room temperature, medium temperature (760 deg.C), and high temperature (1000 deg.C) of laser metal deposition as-printed samples prepared in example 1 of the present invention, ABD-850AM alloy, and CM247LC alloy;
FIG. 4 is a graph showing the plastic properties of the laser metal deposition as-printed sample prepared in example 1 of the present invention, ABD-850AM alloy, and CM247LC alloy at room temperature, medium temperature (760 ℃) and high temperature (1000 ℃);
FIG. 5 is a metallographic and scanned microstructure image of a laser metal deposition as-printed sample prepared in example 2 of the present invention; wherein, the diagram (a) in FIG. 2 is a gold phase diagram; FIG. 2 (b) is a scanned microstructure view;
FIG. 6 is a macroscopic fracture morphology after room temperature, medium temperature, high temperature tensile fracture of a laser as-deposited metal print prepared in example 2 of the present invention; wherein, the graph (a) is the macro fracture morphology after room temperature tensile fracture, (b) is the macro fracture morphology after medium temperature (760 ℃) tensile fracture, and (c) is the macro fracture morphology after high temperature (1000 ℃) tensile fracture;
FIG. 7 is a graph comparing tensile properties at room temperature, medium temperature (760 deg.C), and high temperature (1000 deg.C) of laser metal deposition as-printed samples, ABD-850AM alloy, and CM247LC alloy prepared in example 2 of the present invention;
FIG. 8 is a comparison plot of plasticity of the laser metal deposition as-printed sample prepared in example 2 of the present invention, ABD-850AM alloy, CM247LC alloy at room temperature, medium temperature (760 deg.C), and high temperature (1000 deg.C).
FIG. 9 is an EBSD picture alignment comparison of columnar grains in ABD-850AM alloy and laser as-deposited metal samples prepared in example 1 of the present invention. Wherein, the picture (a) in fig. 9 is an EBSD picture of columnar crystals of the as-printed sample of laser metal deposition prepared in example 1; (b) The figure is an EBSD picture of columnar grains in the ABD-850AM alloy.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The invention aims to provide an additive manufacturing nickel-based high-temperature alloy and a preparation method thereof, so that the additive manufacturing nickel-based high-temperature alloy has excellent tensile strength and plasticity at room temperature, medium temperature and high temperature, reaches the level of the conventional additive manufacturing high-temperature alloy, maintains excellent high-temperature strength and good high-temperature structure stability, and has low-level defects such as cracks, holes and the like. The technical problems of poor formability, difficult defect control and the like of the existing additive manufacturing high-temperature alloy are solved.
The technical scheme of the invention is as follows:
in one aspect, an embodiment of the present invention provides an additive manufacturing nickel-based superalloy, where the additive manufacturing nickel-based superalloy has a chemical composition, in weight percent, as follows: 6.5 to 9.5 weight percent of Cr, 6.5 to 9.5 weight percent of Co, 6.5 to 9.5 weight percent of W, 1.0 to 2.5 weight percent of Mo, 4.0 to 5.5 weight percent of Al, 0.5 to 1.5 weight percent of Ti, 4.5 to 6.0 weight percent of Ta, 0.01 to 0.1 weight percent of C, 0.01 to 0.1 weight percent of B and the balance of Ni.
The chemical composition of the additive manufacturing nickel-base superalloy is designed as follows:
(1) In the prior art, the content of Ta in the nickel-based high-temperature alloy manufactured by additive manufacturing is low; the reason for this is that: the formation efficiency of the Ta element on the gamma 'phase is low, and a large amount of Ta is required to form the gamma' phase. Ta can form carbide, increase the content of carbide, and is unfavorable for performance, and the cost of c.Ta is high. Therefore, the Ta content is generally designed to be low. Therefore, the prior art mainly uses Al and Ti elements and can efficiently form a gamma' phase.
Here, the alloy of the present invention contains only one noble metal of Ta element, and therefore, the cost is low as a whole. On the other hand, the invention ensures the forming efficiency of the gamma 'phase by improving the Ta/Al ratio and adding a small amount of Ti element, ensures that the high content (40-60%) of the gamma' phase can be satisfied firstly, and ensures the high-temperature performance. Second, the inventors of the present invention found that: the high Ta/Al ratio can inhibit the interdendritic segregation, such as the segregation of Al, ti, C and other elements, and reduce the size of the carbide to a certain extent, but the carbide is in a dispersion distribution form, so that the problem that the performance is affected due to the large-size carbide caused by the high Ta (the high Ta/Al ratio can avoid the interdendritic segregation and reduce the formation of harmful phases) can be avoided.
In the invention, the control of the volume fraction, the solidification range and the harmful phase content of the gamma 'phase of the alloy is realized by optimizing the content ranges of the gamma' phase forming elements Al, ti and Ta. A design method of an alloy with high Ta/Al ratio and low Ti content is provided, which is obviously different from the reported design methods of a nickel-based alloy ABD-850AM and a cobalt-based alloy SB-CoNi-10. On the basis, the invention designs the solid solution strengthening alloy matrix with high content ranges of solid solution strengthening elements W, mo, co and Cr, and adds trace crystal boundary elements C and B to strengthen the crystal boundary. And then, preliminarily optimizing the alloy composition range according to the design concept by utilizing thermodynamic calculation software and an electronic space number calculation method, and screening and optimizing suitable alloy compositions from the alloy composition range.
In summary, the design of the alloy components of the additive manufacturing nickel-base superalloy of the present invention is as follows: the volume fraction (40-60%) of the gamma ' phase is controlled by adopting a higher Ta/Al ratio to ensure high-temperature performance, the gamma and gamma ' phases are strengthened, the formation of gamma/gamma ' low-melting-point eutectic is effectively inhibited, in addition, solid solution strengthening elements such as W, mo, cr, co and the like with higher content are added to strengthen the intrinsic strength of a matrix, and trace grain boundary elements C and B strengthen a grain boundary. The formation of liquefied cracks, solidified cracks and solid cracks is inhibited as far as possible through the regulation and control of the components, the high-temperature mechanical properties in the alloy are improved by exerting the effects of precipitation strengthening, solid solution strengthening and grain boundary strengthening of alloy elements, the high-temperature structure stability is kept, and the alloy reaches the level of high-performance additive manufacturing of high-temperature alloys.
In addition, the chemical composition of the additive manufacturing nickel-base superalloy of the present invention is designed mainly for the following reasons:
the main function of the Cr element is to improve the high-temperature corrosion resistance of the alloy, so that the content of the Cr element is as high as possible, but the content of the Cr element should be controlled so that the matrix can dissolve high-content refractory elements such as W, mo and the like to obtain excellent creep property. The Cr content in nickel based single crystal superalloys is typically 5.0-9.0wt.%.
Co element can reduce the stacking fault energy of a matrix, promote the precipitation of an alloy gamma' phase, stabilize the alloy and enlarge a heat treatment window, and Erickson limits Co to be 3.0 wt% in CMSX-10, which is called to reduce the tendency of forming a TCP phase; but also have been shown to reduce the fracture strength and oxidation resistance. The alloys of the present invention show that Co contributes to the stability of the structure, so the selected Co content is in the range of 6.0-10.0wt.%.
Mo is a solid solution strengthening element and can increase the mismatching degree of gamma/gamma', enable a mismatching dislocation network to be dense, effectively block dislocation movement and improve performance, but Mo has a bad influence on the hot corrosion performance of the alloy, so that the content of Mo is 0.1-3.0wt.%.
The W element is a strong solid solution strengthening element, can improve the interatomic bonding force and the diffusion activation energy, fully exerts the strengthening effect of W and Ta, and can effectively improve the high-temperature performance, but the excessive addition of W can cause the instability of a microstructure, and easily forms a TCP brittle phase such as a mu phase and a P phase. Thus, in the alloy of the invention, the W content is 6.5-9.5wt%.
Al element is a strengthening phase gamma' phase (Ni) formed in the nickel-base superalloy 3 Al), the content of which plays an important role in the high-temperature performance, and the content of Al is also important for the oxidation resistance of the high-temperature alloy, so that a certain amount of Al must be added into the high-temperature alloy, but excessive Al can reduce the structural stability of the high-temperature alloy, cause the precipitation of harmful phases (such as the promotion of the formation of carbides), promote the formation of an intercrystalline low-melting-point eutectic phase and improve the crack sensitivity of the alloy. Therefore, the invention controls the Al content in the alloy to be 4.0-5.5wt%.
Ti is also the basic element for forming gamma 'phase, and after Ti is added into the alloy, the gamma' phase is formed by Ni 3 Al to Ni 3 (Al, ti). Ti also has a beneficial effect on the hot corrosion resistance of the alloy. However, excessive Ti is easy to form a large amount of carbide, which causes the poor stability of alloy structure, and the content of Ti in the high-generation secondary high-temperature alloy is controlled to be very low or even completely removed, therefore, the content of Ti in the alloy is controlled to be 0.5-1.5wt%
The Ta element has the advantages that: the high-temperature strength of the alloy is improved mainly by increasing the number of gamma ' phases and improving the strength and the thermal stability of the gamma ' phases, and meanwhile, the gamma ' phase alloy also has a solid solution strengthening effect. The Ta has large atomic radius and low self-diffusion rate, can influence the diffusion behavior of other elements in the alloy, inhibit the formation of eutectic with low melting point among dendrites to a certain extent, and reduce the crack sensitivity of the alloy. In addition, ta also has a beneficial effect on the oxidation resistance, hot corrosion resistance and durability of the alloy and does not cause the formation of TCP phases, so that 4.0 to 6.0 wt.% Ta is added to the alloy. The invention improves the Ta/Al ratio to make Ta element exert its advantages and avoid its disadvantages.
C. The trace elements such as B and the like are mainly crystal boundary strengthening elements and can form discontinuous fine carbides on crystal boundary to improve the strength of the crystal boundary, but hard, brittle and continuous chain carbides can be formed when the content is too high, and the hard, brittle and continuous chain carbides become crack initiation and expansion areas and are not favorable for the performance of the alloy, so that the content of C and B added into the alloy is 0.01-0.1wt%.
Here, if the additive manufacturing nickel-base superalloy is a laser metal deposition printed sample, its microstructure is as follows: exhibit columnar crystals growing along the build direction (z-axis) (the crystal grain orientation of the columnar crystals of the present invention is good); the inside of the columnar crystal is provided with dendrites which grow in parallel and fine gamma' phases among the dendrites; wherein, the primary dendrite spacing of the dendrite is 30-50 μm, preferably about 30-40 μm, the spacing is smaller, and the smaller the primary dendrite spacing is, the better the performance is (the designed high Ta/Al ratio can strengthen the strength of the dendrite); the size of the gamma ' phase is 0.05-0.1 mu m (note: the chemical composition design of the nickel-based superalloy of the invention is matched with a laser metal deposition printing process, so that a better gamma ' phase can be precipitated in a printing state, and the printing state has excellent performance, in the prior art, the high-content gamma ' phase can be precipitated only by carrying out subsequent heat treatment on the printing state, and the shape of the gamma ' phase has certain cubic degree (the good-shape gamma ' phase can be obtained due to the high Ta/Al ratio of the invention); the gamma' phase is distributed in the dendrite trunk and interdendritic region of the dendrite; the size of carbide in the microstructure of the additive manufacturing nickel-based superalloy is less than or equal to 150nm, preferably less than or equal to 100nm; the carbide is dispersedly distributed in the dendrite trunk and interdendritic region of the dendrite. The nickel-based superalloy with the chemical composition has excellent performance after heat treatment compared with the existing partial alloy without subsequent heat treatment in a laser metal deposition printing state.
Here, it should be noted that: in the prior art, the performance of the nickel-based superalloy prepared by the selective laser melting process is superior to that of the nickel-based superalloy prepared by the laser metal deposition printing process. However, the alloy with the chemical components is designed, and the performance of the alloy prepared by adopting the laser metal deposition printing process is superior to or close to that of the existing alloys ABD-850AM and CM247LC. The conventional alloys ABD-850AM and CM247LC are prepared by adopting a selective laser melting printing process, and are obtained by performing heat treatment on a printing state (wherein the heat treatment is to further treat the printing state to precipitate a gamma' phase so as to improve the performance; the printing state performance of the laser metal deposition process is excellent, and the performance of the conventional alloys ABD-850AM and CM247LC after heat treatment can be achieved without performing heat treatment).
In addition, the transient tensile properties for the as-printed sample of laser metal deposition were as follows:
sigma of the nickel-base superalloy at room temperature b ≥1320MPa，σ 0.2 ≥970MPa，A≥19％；
Sigma of the nickel-base superalloy at a temperature of 760 DEG C b ≥1170MPa，σ 0.2 ≥925MPa，A≥35％；
Sigma of the nickel-base superalloy at a temperature of 1000 DEG C b ≥450MPa,σ 0.2 ≥350MPa，A≥50％。
It can be seen that the additive manufacturing nickel-based superalloy provided by the invention has particularly excellent performance in a laser metal deposition printing state, and not only is excellent compared with the alloy in the printing state in the prior art, but also is excellent compared with the performance after heat treatment. See the data comparison of the examples specifically.
Here, if the additive manufacturing nickel-base superalloy is in a selective laser melting printing state, then: the microstructure of the nickel-based superalloy presents columnar crystals growing along the construction direction; the columnar crystals have a cell structure inside.
The instantaneous tensile properties for the selected laser-melted printed state are as follows:
sigma of the nickel-base superalloy at room temperature b ≥1100MPa，σ 0.2 ≥850MPa，A≥19％；
Sigma of the nickel-base superalloy at a temperature of 760 DEG C b ≥1100MPa，σ 0.2 ≥900MPa，A≥12％；
At a temperature of 1000 ℃, the nickel base is highSigma of warm alloys b ≥558MPa，σ 0.2 ≥370MPa，A≥10％。
It can be seen that the additive manufacturing nickel-based superalloy provided by the invention is superior to the selective laser melting printing nickel-based superalloy in the prior art in the selective laser melting printing state.
On the other hand, the embodiment of the present invention further provides a preparation method of the additive manufacturing nickel-based superalloy, where the preparation method of the additive manufacturing nickel-based superalloy includes the following steps:
1) Preparing a master alloy: and carrying out vacuum smelting on the raw materials and casting the raw materials into a master alloy according with the chemical composition.
The vacuum smelting process comprises the following steps: refining at 1580 deg.C for 5min; casting at 1460 deg.C, and polishing and blowing to obtain mother alloy with impurity element (N, P, S, etc.) less than 5 ppm.
2) Preparing alloy powder: and atomizing the master alloy into alloy powder.
Preparing alloy powder by argon atomization equipment under the powder spraying parameters of pressure of 7MPa and temperature of 1400 ℃, wherein the powder sphericity reaches 88%, the fluidity is good, and screening out the alloy powder with the particle size D50 of 90-100 mu m.
3) Preparing the nickel-based superalloy: and printing the alloy powder into the additive manufacturing nickel-based superalloy by utilizing a laser metal deposition process or a selective laser melting process.
Wherein, the laser metal deposition process parameters are as follows: the power is 1700W, the scanning speed is 1100mm/min, the powder feeding speed is 10.5g/min, and the laser diameter is 2mm. Rectangular column samples having a length, width and height of 16mm × 16mm × 60mm were printed.
Wherein the selective laser melting parameter is power of 380W, scanning speed of 800-1000mm/s, layer thickness of 50 μm, laser diameter of 180 μm, and overlapping rate of 30%. Rectangular column samples having a length, width and height of 16mm × 16mm × 60mm were printed.
Here, it should be noted that: in the two processes, because the chemical components of the alloy of the invention contain a large amount of refractory elements W, mo, ta and the like, the laser energy density (power, scanning speed, powder feeding speed and laser diameter) of the two processes is set to be larger so as to overcome the defects brought by the refractory elements W, mo and Ta.
The resulting additively manufactured nickel-base superalloys have a high volume fraction γ' strengthening phase and a low crack sensitivity microstructure characteristic.
The invention is further illustrated below by means of specific examples:
example 1
This example prepares an additive-fabricated nickel-base superalloy with the chemical composition shown in table 1:
TABLE 1
| Alloy (I) | W | Co | Cr | Mo | Al | Ti | Ta | C | B | Ni |
| Example 1 | 8.0 | 8.0 | 8.0 | 2.0 | 4.1 | 1.2 | 5.5 | 0.01 | 0.015 | Allowance of |
The preparation method comprises the following specific steps:
1) Preparing a master alloy: and carrying out vacuum smelting on the raw materials and casting the raw materials into a master alloy according with the chemical composition. Wherein the vacuum smelting process comprises the following steps: refining at 1580 deg.C for 5min; casting at 1460 deg.C, and polishing and blowing to obtain mother alloy with impurity element (N, P, S, etc.) less than 5 ppm.
2) Preparing alloy powder: and atomizing the master alloy into alloy powder. Wherein, the alloy powder is prepared by argon atomization equipment under the powder spraying parameters of pressure of 7MPa and temperature of 1400 ℃, wherein, the powder sphericity reaches 88 percent, the fluidity is good, and the alloy powder with the grain diameter D50 of 90-100 μm is screened out.
3) Preparing the nickel-based superalloy: the alloy powder is printed into an additive manufacturing nickel-base superalloy (i.e., laser metal deposition as-printed) using a laser metal deposition process. Wherein, the laser metal deposition process parameters are as follows: the power is 1700W, the scanning speed is 1100mm/min, the powder feeding speed is 10.5g/min, and the laser diameter is 2mm. Rectangular column samples having a length, width and height of 16mm × 16mm × 60mm were printed.
Here, the metallographic and scanned microstructure of the additive manufactured nickel-base superalloy prepared in this example (as printed by laser metal deposition without heat treatment) is shown in fig. 1. As can be seen from fig. 1, the laser metal deposition printed state prepared by this embodiment has the following structural features:
no significant cracks were observed in the microstructure, which exhibited typical columnar grains (average grain size 250-300 μm) growing in the build direction, parallel growing dendrites within the grains (primary dendrite crystallization 30-40 μm), and rapid solidification (10) due to additive manufacturing 3- 10 5 K/s), high temperature gradient, and limited dendrite arm growth. A fine gamma 'phase (0.05-0.1 μm) was observed in the dendrite trunk and interdendritic region, the shape tended to be cubic, and the volume fraction was 40-48%, and the formation of low melting gamma/gamma' eutectic was not observed. In addition, as can be seen from fig. 1: no harmful phase is separated out, which shows that the microstructure is consistent and the tissue stability is excellent.
The instantaneous tensile properties at different temperatures of the additive manufactured nickel-base superalloy prepared in this example (as-laser metal deposition printing, without heat treatment) are shown in table 2.
TABLE 2
As can be seen from table 2: from room temperature to 760 ℃, the yield strength of the additive manufacturing nickel-based superalloy of the embodiment is basically unchanged, the tensile strength is slightly reduced, but the plasticity is obviously increased, particularly 760 ℃, the additive manufacturing nickel-based superalloy still maintains good plasticity in a classic intermediate-temperature brittle region, and shows good comprehensive performance of both strength and plasticity, after the temperature exceeds 760 ℃, the strength is rapidly reduced, but the tensile strength at 1000 ℃ still reaches 457MPa, and it is known that the additive manufacturing nickel-based superalloy prepared by the embodiment has better intermediate-temperature and high-temperature strength and plasticity.
The macro fracture morphology of the additive manufacturing nickel-based superalloy prepared in this example (laser metal deposition printed state, without heat treatment) after tensile fracture at room temperature, medium temperature, and high temperature is shown in fig. 2. As can be seen from fig. 2: has obvious river patterns for cleavage and fracture at room temperature; the material is cleavage and micropore aggregation type fracture at 760 ℃, and shows better plasticity; typical micropore aggregation type fracture is realized at 1000 ℃, and obvious micropores and dimples are formed.
Example 2
This example prepares an additive-fabricated nickel-base superalloy with the chemical composition shown in table 1:
TABLE 3
| Alloy (I) | W | Co | Cr | Mo | Al | Ti | Ta | C | B | Ni |
| Example 1 | 8.0 | 8.0 | 8.0 | 2.0 | 5.0 | 1.2 | 4.5 | 0.01 | 0.015 | Balance of |
The preparation method comprises the following specific steps:
1) Preparing a master alloy: and carrying out vacuum smelting on the raw materials and casting the raw materials into a master alloy according with the chemical composition. Wherein, the vacuum smelting process comprises the following steps: refining at 1580 deg.C for 5min; casting at 1460 deg.C, and polishing and blowing to obtain mother alloy with impurity element (N, P, S, etc.) less than 5 ppm.
2) Preparing alloy powder: and atomizing the master alloy into alloy powder. Wherein, the alloy powder is prepared by argon atomization equipment under the powder spraying parameters of pressure of 7MPa and temperature of 1400 ℃, wherein, the powder sphericity reaches 88 percent, the fluidity is good, and the alloy powder with the grain diameter D50 of 90-100 μm is screened out.
3) Preparing the nickel-based superalloy: the alloy powder is printed into an additive manufacturing nickel-base superalloy (i.e., laser metal deposition as-printed) using a laser metal deposition process. The laser metal deposition process parameters are as follows: the power is 1700W, the scanning speed is 1100mm/min, the powder feeding speed is 10.5g/min, and the laser diameter is 2mm. Rectangular column samples having a length, width and height of 16mm × 16mm × 60mm were printed.
The metallographic and scanned microstructure of the additive manufactured nickel-base superalloy prepared in this example (as printed by laser metal deposition without heat treatment) is shown in fig. 5. As can be seen from fig. 5, the laser metal deposition printed state prepared by this embodiment has the following structural features:
the microstructure has a low level of microcracks (very small (crack area percentage of about 0.1-0.2%; compared to the prior art reported crack area percentage of about 0.4-0.8%), much smaller than the conventional printed state), the microstructure exhibits typical columnar grains (average grain size of 250-300 μm) growing in the direction of the build, parallel dendrites in the grains, dendrite arms growing favourably due to increased interdendritic elements (due to increased content of Al, ti elements in example 2), primary interdendritic spacing of about 40-50 μm, but still smaller than conventional cast alloys. A fine gamma' phase (0.05-0.1 mu m) is observed in the dendritic crystal stem and interdendritic region, the shape of the phase tends to be cubic, and the volume fraction is 45-50%; no formation of low melting γ/γ' eutectic was observed.
The instantaneous tensile properties at different temperatures of the additive manufactured nickel-base superalloys prepared in this example (as laser metal deposition prints, without heat treatment) are shown in table 4.
TABLE 4
From table 4, it can be seen that, from room temperature to 760 ℃, the yield strength of the additive manufacturing nickel-based superalloy prepared in the embodiment is basically unchanged, the tensile strength is improved to some extent, but the plasticity is slightly reduced, especially 760 ℃, the elongation of the classical medium-temperature brittle region of the superalloy is still more than or equal to 15%, the alloy still has good strength and certain plasticity, the strength is rapidly reduced after the temperature exceeds 760 ℃, but the tensile strength at 1000 ℃ still reaches 470MPa, and the yield reaches 390MPa, so that the alloy of the invention has better medium-high temperature strength and plasticity.
The macro fracture morphology of the additive manufacturing nickel-based superalloy prepared in this example (in the laser metal deposition printing state, without heat treatment) after tensile fracture at room temperature, medium temperature and high temperature is shown in fig. 6. As can be seen from fig. 6: it can be seen that the cleavage fracture at room temperature has obvious river patterns; cleavage fracture at 760 ℃, and certain brittleness is shown; typical micropore aggregation type fracture is realized at 1000 ℃, and obvious micropores and dimples are formed.
Here, the chemical composition of example 2 differs from that of example 1 in that: example 2 increased the Al content and decreased the Ta/Al ratio, distinguishing the microstructure and properties of example 2 from example 1. Most notably, the segregation increase of elements such as Al, ti and the like is beneficial to the growth of dendrites, the primary dendrite spacing is increased, and slight cracking occurs at the same time. In addition, because Al and Ti are gamma' phase forming elements, the volume fraction of the Al and Ti is also improved, which is beneficial to improving the high-temperature performance of the alloy. Finally, the crack sensitivity of the alloy of example 2 is higher than that of example 1, but the high temperature tensile properties are slightly better than that of example 1 due to the presence of higher content of the gamma' phase of the high temperature strengthening phase.
Comparative example
The comparative examples provide two prior art alloys: ABD-850AM and CM247LC alloys (both printed by the selective laser melting process and heat treated) had the following alloy compositions:
TABLE 3
The additive manufacturing nickel-based superalloy prepared in example 1 (as laser metal deposition printing, without heat treatment) and ABD-850AM and CM247LC alloys have tensile properties and plasticity pairs at room temperature, medium temperature and high temperature as shown in fig. 3 and 4. As can be seen from FIGS. 3 and 4, the tensile strength of the alloy of example 1 is superior to that of the ABD-850AM and CM247LC alloy in both the room temperature region and the middle temperature region, and especially the strength and plasticity are compatible in the middle temperature region; the tensile strength of the alloy of example 1 is slightly lower than that of the CM247LC alloy and still higher than that of the ABD-850AM alloy at 1000 ℃, which shows that the strength and plasticity of the alloy in a printing state prepared by the embodiment reach the level of the special high-temperature alloy for typical medium-high temperature additive manufacturing, and the alloy has low crack sensitivity and good formability.
Referring to the IPF plot shown in fig. 9, it can be seen that the columnar grains of the additive manufactured nickel-base superalloy prepared in example 1 of the present invention (as-laser metal deposition printing, without heat treatment) have a much more pronounced [001] texture, i.e., along the build direction, than the ABD-850AM alloy.
In addition, as shown in fig. 7 and 8, the tensile strength of the additive manufacturing nickel-based superalloy prepared in example 2 (in a laser metal deposition printing state, without heat treatment) and the tensile strength of ABD-850AM and CM247LC at room temperature, medium temperature and high temperature are superior to or close to that of the ABD-850AM and CM247LC alloys at the room temperature and the medium temperature, and particularly, the strength is remarkably improved at the medium temperature, and the plasticity is not lower than those of the two novel alloys; the tensile strength of the example 2 alloy was slightly lower than the CM247LC alloy but still higher than the ABD-850AM alloy at 1000 ℃, indicating that: the strength and plasticity of the additive manufacturing nickel-based superalloy prepared in example 2 (as-printed by laser metal deposition without heat treatment) reach the level of typical medium-high temperature additive manufacturing special-purpose superalloys, and has low crack sensitivity and good formability.
The experimental result shows that the strength of the additive manufacturing nickel-based high-temperature alloy is superior to that of ABD-850M alloy, is close to that of typical CM247LC alloy, and is particularly suitable for additive manufacturing of long-life and high-reliability hot-end high-temperature components in the fields of aviation, aerospace, energy and the like.
In summary, the two alloys of the comparative example are in the alloy state after the heat treatment of the printed state (the heat treatment is to homogenize the structure and precipitate high-content cubic γ' phase to improve the performance), while the additive manufacturing nickel-based high-temperature alloys of the examples 1 and 2 belong to the printed state, and the comparison shows that the additive manufacturing nickel-based high-temperature alloys prepared by the examples of the invention have excellent performance in the printed state.
In conclusion, the additive manufacturing nickel-based superalloy provided by the embodiment of the invention has the advantages of low crack sensitivity, good tensile strength and plasticity at room temperature, medium temperature and high temperature, low cost and the like, is a special additive manufacturing nickel-based superalloy with high performance and stable structure, and has wide popularization and application prospects.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. An additive manufacturing nickel-base superalloy, characterized in that the additive manufacturing nickel-base superalloy has the following chemical composition in weight percent:
Cr 6.5-9.5wt％；
Co 6.5-9.5wt％；
W 6.5-9.5wt％；
Mo 1.0-2.5wt％；
Al 4.0-5.5wt％；
Ti 0.5-1.5wt％；
Ta 4.5-6.0wt％；
C 0.01-0.1wt％；
B 0.01-0.1wt％；
the balance being Ni.
2. The additive manufactured nickel-base superalloy according to claim 1,
if the additive manufacturing nickel-based superalloy is in a laser metal deposition printing state, the volume fraction of a gamma' phase in the additive manufacturing nickel-based superalloy is 40-50%; after the laser metal deposition printing state is subjected to heat treatment, the volume fraction of a gamma' phase is 50-60%;
if the additive manufacturing nickel-based superalloy is in a selective laser melting printing state, the volume fraction of a gamma' phase in the selective laser melting printing state is 50-60% after the selective laser melting printing state is subjected to heat treatment.
3. Additive-manufacturing nickel-base superalloy according to claim 1 or 2, wherein if the additive-manufacturing nickel-base superalloy is in a laser metal deposition print state:
the microstructure of the additive manufacturing nickel-based superalloy presents columnar crystals growing along the construction direction; the inside of the columnar crystal is provided with dendrite growing in parallel and gamma' phase among dendrites; wherein, the primary dendrite spacing of the dendrite is 30-50 μm, preferably 30-40 μm; the size of the gamma 'phase is 0.05 to 0.1 μm, and the shape of the gamma' phase has a cubic degree;
preferably, the gamma-prime phase is distributed in the dendrite trunk and interdendritic region of the dendrite;
preferably, the average size of crystal grains of the columnar crystal is 250-300 μm;
preferably, the size of carbides in the microstructure of the additive manufacturing nickel-base superalloy is less than or equal to 150nm, preferably less than or equal to 100nm; the carbide is dispersedly distributed in the dendrite trunk and interdendritic region of the dendrite.
4. Additive-manufactured nickel-base superalloy according to any of claims 1 to 3, wherein, if the additive-manufactured nickel-base superalloy is in the laser metal deposition print state, the instantaneous tensile properties of the nickel-base superalloy are as follows:
sigma of the additive manufacturing nickel-base superalloy at room temperature b ≥1320MPa，σ 0.2 ≥970MPa，A≥19％；
Sigma of the additive manufacturing nickel-base superalloy at a temperature of 760 ℃ b ≥1170MPa，σ 0.2 ≥925MPa，A≥35％；
Sigma of the additive manufacturing nickel-base superalloy at a temperature of 1000 ℃ b ≥450MPa,σ 0.2 ≥350MPa，A≥50％。
5. Additive-manufactured nickel-base superalloy according to claim 1 or 2, wherein if the additive-manufactured nickel-base superalloy is in a selective laser melting printing state:
the microstructure of the nickel-based superalloy presents columnar crystals growing along the construction direction; a cell structure in the columnar crystal;
preferably, the average size of the crystal grains of the columnar crystals is 60 to 100 μm.
6. The additive manufactured nickel-base superalloy according to any of claims 1-2, 5, wherein if the additive manufactured nickel-base superalloy is in a selective laser melting as-printed state, the instantaneous tensile properties of the nickel-base superalloy are as follows:
sigma of the additive manufacturing nickel-base superalloy at room temperature b ≥1100MPa，σ 0.2 ≥850MPa，A≥19％；
Sigma of the additive manufacturing nickel-base superalloy at a temperature of 760 ℃ b ≥1100MPa，σ 0.2 ≥900MPa，A≥12％；
Sigma of the additive manufacturing nickel-base superalloy at a temperature of 1000 ℃ b ≥558MPa,σ 0.2 ≥370MPa，A≥10％。
7. The method of preparing an additive manufactured nickel-base superalloy according to any of claims 1 to 6, wherein the method of preparing an additive manufactured nickel-base superalloy comprises the steps of:
preparing a master alloy: carrying out vacuum smelting on the raw materials and casting the raw materials into a master alloy which accords with the chemical components;
preparing alloy powder: atomizing the master alloy into alloy powder;
preparing the nickel-based superalloy: and printing the alloy powder into the additive manufacturing nickel-based superalloy by utilizing a laser metal deposition process or a selective laser melting process.
8. The method of making an additive-manufactured nickel-base superalloy as in claim 7, wherein in the step of making a master alloy:
the vacuum smelting comprises the following steps: refining at 1500-1600 deg.C for 5-10min; and/or
The casting temperature is 1420-1480 ℃; and/or
After the casting, polishing and sand blowing treatment are carried out; and/or
The content of impurity elements in the master alloy is less than 5ppm; wherein the impurity element includes N, P, and S.
9. The method of making an additive-manufactured nickel-base superalloy as in claim 7, wherein in the step of making the alloy powder:
preparing the master alloy into alloy powder by using argon atomization equipment under the conditions that the pressure is 5-8MPa and the temperature is 1350-1450 ℃; wherein the sphericity of the alloy powder is 87-89%, preferably 88%, and the alloy powder with D50 of 90-100 μm is screened for use in the step of preparing the nickel-base superalloy.
10. The method of making an additive-manufactured nickel-base superalloy as in claim 7, wherein in the step of making the nickel-base superalloy:
if the laser metal deposition process is selected, the laser metal deposition process parameters are set as follows: the power is set to be 1500-2000W, the scanning speed is set to be 800-1500mm/min, the powder feeding speed is set to be 8-12g/min, and the laser diameter is 1-3mm, preferably 2mm;
if the selective laser melting process is selected, the parameters of the selective laser melting process are set as follows: the power is set to be 300-400W, the scanning speed is set to be 800-1000mm/s, the layer thickness is set to be 30-50 mu m, the laser diameter is set to be 100-200 mu m, and the lap ratio is 30-40%.
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| CN114606413A (en) * | 2022-03-17 | 2022-06-10 | 广州赛隆增材制造有限责任公司 | High-temperature alloy for additive manufacturing and application thereof |
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| US20220341003A1 (en) * | 2019-09-13 | 2022-10-27 | Siemens Energy Global GmbH & Co. KG | Nickel-based alloy for additive manufacturing, method and product |
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| GB202212512D0 (en) * | 2019-06-07 | 2022-10-12 | Alloyed Ltd | A nickel-based alloy |
| US20220341003A1 (en) * | 2019-09-13 | 2022-10-27 | Siemens Energy Global GmbH & Co. KG | Nickel-based alloy for additive manufacturing, method and product |
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