CN114425624A - Method for improving comprehensive performance of additive manufacturing nickel-based superalloy and nickel-based superalloy powder - Google Patents
Method for improving comprehensive performance of additive manufacturing nickel-based superalloy and nickel-based superalloy powder Download PDFInfo
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0073—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only borides
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- B22F9/02—Making metallic powder or suspensions thereof using physical processes
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Abstract
The invention discloses a method for improving the comprehensive performance of additive manufacturing nickel-based superalloy and nickel-based superalloy powder6、YB6、CeB6Or ErB6Wherein the rare earth boride is present in a mass fraction of 0.5 to 2%. The invention provides a method for preparing the compound by adding proper amountThe rare earth element boride is subjected to grain boundary strengthening, and the rare earth element boride is subjected to segregation at grain boundaries and phase boundaries after decomposition, so that the form and distribution of carbide are improved, the crack sensitivity factor of the additive manufacturing nickel-based high-temperature alloy is reduced, the formation of formed cracks is inhibited, and the comprehensive mechanical property of the additive manufacturing nickel-based high-temperature alloy is greatly improved.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a method for improving the comprehensive performance of additive manufacturing nickel-based superalloy and nickel-based superalloy powder.
Background
As a typical solid solution strengthening type nickel-based high-temperature alloy, the GH3536 alloy has good oxidation resistance and corrosion resistance, has moderate endurance and creep strength below 900 ℃, and is mainly used for preparing aeroengine combustor parts used for a long time at 900 ℃ and other parts in service in a high-temperature environment. The GH3536 alloy has the advantages of increasing the iron content, reducing the Mo content, and only containing a small amount of strategic alloy elements such as Co, and the like, so the cost is low. Meanwhile, the GH3536 alloy has good oxidation resistance and can be easily processed into plates, wires, bars, pipes and the like with various sizes, so that the GH3536 alloy is widely applied and is one of high-temperature alloys with large using amount. For the purpose of light weight, the complexity of the structure of the parts of the high-performance aircraft engine is required to be higher and higher, which brings great difficulty to the traditional manufacturing process.
Because the SLM forming process takes a high-energy laser beam as a heat source, metal powder is selectively melted, and the SLM forming process is formed by stacking layer by layer, the forming principle is different from the traditional processes of casting, forging, welding and the like, and the SLM forming material usually has a finer structure and more excellent mechanical properties. However, in the SLM forming process, the temperature gradient is large, the cooling speed is fast, cracks are easily formed in the member, and the cracks cannot be completely eliminated by the conventional methods such as optimizing process parameters. Therefore, eliminating cracks in SLM construction and improving overall performance is a problem to be solved urgently in the field of additive manufacturing.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
In view of the above and/or the problems that selective laser melting forming nickel-based superalloy in the prior art is easy to crack and has low comprehensive performance and the like, the method for improving the comprehensive performance of additive manufacturing nickel-based superalloy by using rare earth element boride is provided.
One of the purposes of the invention is to provide an application of a rare earth element boride in improving the comprehensive performance of additive manufacturing nickel-based high-temperature alloy, which is different from other inventions in that heterogeneous nucleation points are directly added for fine grain strengthening, and the rare earth element boride is added.
In order to solve the technical problems, the invention provides the following technical scheme: application of rare earth element boride to improvement of comprehensive performance of additive manufacturing nickel-based high-temperature alloy, wherein the rare earth element boride is LaB6、YB6、CeB6Or ErB6Wherein the rare earth boride is present in a mass fraction of 0.5 to 2%.
It is another object of the present invention to provide a method for improving the overall properties of an additive manufactured nickel-base superalloy, comprising,
taking nickel-based superalloy powder as a raw material, mechanically mixing rare earth boride, and forming by an additive manufacturing technology;
wherein the rare earth boride is LaB6、YB6、CeB6Or ErB6One of (a) and (b);
the mass fraction ratio of the nickel-based superalloy powder to the rare earth boride is 98-99.5%: 0.5 to 2 percent.
As a preferred scheme of the method for improving the comprehensive performance of the additive manufacturing nickel-based superalloy, the method comprises the following steps: the powder is formed by an additive manufacturing technology, a selective laser melting forming technology is selected, the laser power is 150-250 MPa, the scanning speed is 700-1100 mm/s, the scanning interval is 0.05-0.1 mm, the thickness of the powder layer is 0.03-0.05 mm, and the scanning mode is that the layers rotate by 67-90 degrees or the powder layer rotates by 67 degrees in a partition mode.
As a preferred scheme of the method for improving the comprehensive performance of the additive manufacturing nickel-based superalloy, the method comprises the following steps: the additive manufacturing nickel-based superalloy is formed under the protection of inert gas, and the inert gas is one of high-purity argon or high-purity nitrogen.
It is another object of the present invention to provide a nickel-base superalloy obtained by the method as described above, comprising, in mass percent: 20.5 to 23 percent of Cr, 17 to 20 percent of Fe, 8 to 10 percent of Mo, 0.5 to 2.5 percent of Co, 0.2 to 1 percent of W, less than or equal to 0.5 percent of Al, 0.05 to 0.15 percent of C, less than or equal to 0.15 percent of Ti, and XB60.5-2%, and the balance of Ni;
wherein X is selected from one of La, Y, Ce or Er.
As a preferable embodiment of the nickel-base superalloy of the present invention, wherein: the relative density of the additive manufacturing nickel-based high-temperature alloy is 99.0-99.8%, the yield strength is 680-750 MPa, the ultimate tensile strength is 850-960 MPa, and the elongation after fracture is 20-45%.
As a preferable embodiment of the nickel-base superalloy of the present invention, wherein: the composite material comprises the following components in percentage by mass: 22.27% of Cr, 18.73% of Fe, 9.33% of Mo, 1.61% of Co, 0.55% of W, 0.1% of Al, 0.066% of C, 0.02% of Ti and XB60.5 percent of Ni and the balance of Ni;
wherein X is selected from one of La, Y, Ce or Er.
Another object of the present invention is to provide a nickel-base superalloy powder for additive manufacturing, comprising a nickel-base superalloy powder and a rare earth boride, the rare earth boride being LaB6、YB6、CeB6Or ErB6One of (1);
the mass fraction ratio of the nickel-based superalloy powder to the rare earth boride is 98-99.5%: 0.5 to 2 percent.
As a preferred embodiment of the nickel-base superalloy powder for additive manufacturing according to the present invention, wherein: the particle size of the nickel-based superalloy powder is 15-53 mu m, and the particle size of the rare earth element boride is smaller than 1 mu m.
As a preferred embodiment of the nickel-base superalloy powder for additive manufacturing according to the present invention, wherein: the nickel-based high-temperature alloy powder comprises, by mass, 20.5-23% of Cr, 17-20% of Fe, 8-10% of Mo, 0.5-2.5% of Co, 0.2-1% of W, less than or equal to 0.5% of Al, and 0.05-0.15% of C.
As a preferred embodiment of the nickel-base superalloy powder for additive manufacturing according to the present invention, wherein: the nickel-based superalloy powder is one of raw material powders of GH3536 alloy, Hastelloy X alloy, NC22FeD alloy, NiCr22FeMo alloy or Nimonic PE13 alloy.
It is another object of the invention to provide a method for preparing a nickel-base superalloy powder for additive manufacturing, comprising,
selecting GH3536 alloy powder with the granularity of 15-53 mu m and rare earth boride powder with the granularity of less than 1 mu m, and weighing the two powders according to the mass percentage of 98-99.5% and 0.5-2%;
putting the weighed powder into a ball milling tank, then putting zirconia balls with the mass ratio of 1:1 to the powder, wherein the ball milling rotation speed is 50rad/min, the ball milling mode is wet milling, the ball milling medium is ethanol, the mass ratio of the ethanol to the nickel-based high-temperature alloy powder is 1:1, and the ball milling time is 15 hours;
and taking out the ball-milled mixed powder, placing the ball-milled mixed powder in a beaker, drying the ball-milled mixed powder in a vacuum drying oven for 8 hours at the drying temperature of 80 ℃, and then carrying out vacuum packaging on the dried powder.
As a preferable aspect of the method for preparing the nickel-based superalloy powder for additive manufacturing of the present invention, wherein: the purity of the protective atmosphere argon during sieving was higher than 99.999%.
As a preferable aspect of the method for preparing the nickel-based superalloy powder for additive manufacturing of the present invention, wherein: the nickel-base superalloy powder has an oxygen content of less than 10ppm, a nitrogen content of less than 10ppm, a hydrogen content of less than 10ppm, and a sulfur content of less than 150 ppm.
As a preferable aspect of the method for preparing the nickel-based superalloy powder for additive manufacturing of the present invention, wherein: also comprises the step of putting the nickel-based superalloy powder into a vacuum drying oven for drying for 8 hours, wherein the drying temperature is 80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for improving the comprehensive performance of additive manufacturing nickel-based high-temperature alloy by using rare earth element boride, aiming at the problems that selective laser melting forming nickel-based high-temperature alloy is easy to crack and the comprehensive performance is low and the like, and different from other inventions in which heterogeneous nucleation points are directly added to carry out fine grain strengthening.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
fig. 1 is a metallographic structure picture comparison of additive manufactured nickel-base superalloys prepared in example 1 of the present invention and comparative example 1.
FIG. 2 is a comparison of room temperature stress-strain curves for additive manufactured nickel-base superalloys prepared in example 1 of the present invention and comparative example 1.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Weighing 497.5g of GH3536 powder and 2.5g of LaB according to the mass percent of 99.5: 0.5%6Powder;
(2) mixing the two kinds of powder, putting the mixture into a 500ml ball milling tank, putting 500g of zirconia balls with the diameter of 5mm, then putting 500g of ethanol solution, and ball milling at the rotation speed of 50rad/min for 15 h;
(3) taking out the ball-milled mixed powder, placing the ball-milled mixed powder in a beaker, drying the ball-milled mixed powder in a vacuum drying oven for 8 hours at the drying temperature of 80 ℃, and then carrying out vacuum packaging on the dried powder;
(4) placing the screened powder into SLM forming equipment, introducing protective atmosphere argon or nitrogen, preheating the substrate at 100 ℃, and carrying out SLM forming, wherein selective laser melting forming parameters are as follows: the laser power is 200W; the scanning speed is 1000 mm/s; the scanning interval is 0.08 mm; the thickness of the powder layer is 0.03 mm; and the scanning mode is that the sample is rotated in a partition way at 67 degrees, the printed sample piece is cut from the substrate and subjected to surface treatment to obtain an SLM-formed nickel-based superalloy sample bottle, and the sample is subjected to mechanical property test and metallographic phase detection.
Comparative example 1
Placing 500g of GH3536 powder used for powder mixing in SLM forming equipment, introducing protective atmosphere argon or nitrogen, and carrying out SLM forming at the substrate preheating temperature of 100 ℃, wherein the substrate is made of a nickel-based high-temperature alloy material;
the selective laser melting forming parameters are as follows: the laser power is 200W; the scanning speed is 1000 mm/s; the scanning interval is 0.08 mm; the thickness of the powder layer is 0.03 mm; and the scanning mode is that the sample piece is rotated in a partition way at 67 degrees, the printed sample piece is cut from the substrate and subjected to surface treatment to obtain the SLM-formed nickel-based high-temperature alloy sample piece, and the sample is subjected to mechanical property test and metallographic detection.
FIG. 1 is a metallographic comparison of the samples obtained in example 1 and comparative example 1, and it can be seen that the samples obtained in comparative example 1 (FIG. 1b) and comparative example 1 (FIG. 1a) were prepared using LaB addition under the same process parameters6The internal cracks and air holes of a sample formed by selective laser melting of powdered GH3536 nickel-based superalloy powder are obviously reduced.
FIG. 2 is a stress-strain curve at room temperature for the samples obtained in example 1 and comparative example 1, and it can be seen that LaB was measured6The laser selective melting forming GH3536 nickel-base high-temperature alloy prepared from the strengthened GH3536 powder has better comprehensive mechanical properties, the tensile strength is 960 +/-10 MPa, the elongation is 45 +/-2%, and the alloy is far better than the GH3536 nickel-base high-temperature alloy obtained by direct selective laser melting forming in comparative example 1.
Example 2
(1) According to the mass percent of 99.8 percent to 0.2 percent, 499g of GH3536 powder and 1g of LaB are weighed6Powder;
(2) mixing the two kinds of powder, putting the mixture into a 500ml ball milling tank, putting 500g of zirconia balls with the diameter of 5mm, then putting 500g of ethanol solution, and ball milling at the rotation speed of 50rad/min for 15 h;
(3) taking out the ball-milled mixed powder, placing the ball-milled mixed powder in a beaker, drying the ball-milled mixed powder in a vacuum drying oven for 8 hours at the drying temperature of 80 ℃, and then carrying out vacuum packaging on the dried powder;
(4) putting the sieved powder into SLM forming equipment, introducing protective atmosphere argon or nitrogen, preheating the substrate at 100 ℃, and performing SLM forming, wherein selective laser melting forming parameters are as follows: the laser power is 200W; the scanning speed is 1000 mm/s; the scanning interval is 0.08 mm; the thickness of the powder layer is 0.03 mm; and the scanning mode is that the sample piece is rotated in a partition way at 67 degrees, the printed sample piece is cut from the substrate and subjected to surface treatment to obtain the SLM-formed nickel-based superalloy sample piece, and a mechanical property test is performed on the sample.
Example 3
(1) Weighing 496g of GH3536 powder and 4g of LaB according to the mass percentage of 99.2 percent to 0.8 percent6Powder;
(2) mixing the two kinds of powder, putting the mixture into a 500ml ball milling tank, putting 500g of zirconia balls with the diameter of 5mm, then putting 500g of ethanol solution, and ball milling at the rotation speed of 50rad/min for 15 h;
(3) taking out the ball-milled mixed powder, placing the ball-milled mixed powder in a beaker, drying the ball-milled mixed powder in a vacuum drying oven for 8 hours at the drying temperature of 80 ℃, and then carrying out vacuum packaging on the dried powder;
(4) placing the screened powder into SLM forming equipment, introducing protective atmosphere argon or nitrogen, preheating the substrate at 100 ℃, and carrying out SLM forming, wherein selective laser melting forming parameters are as follows: the laser power is 200W; the scanning speed is 1000 mm/s; the scanning interval is 0.08 mm; the thickness of the powder layer is 0.03 mm; and the scanning mode is that the sample piece is rotated in a partition way at 67 degrees, the printed sample piece is cut from the substrate and subjected to surface treatment to obtain the SLM-formed nickel-based superalloy sample piece, and a mechanical property test is performed on the sample.
Example 4
The procedure of example 4 is the same as example 1 except that the GH3536 alloy powder of example 1 is replaced with Hastelloy X alloy powder and the sample is subjected to mechanical property testing.
The results of the tensile strength, yield strength, elongation and porosity tests on the nickel-based superalloy samples prepared in examples 1-3 and comparative example 1 are shown in table 1.
TABLE 1
| Tensile strength (MPa) | Yield strength (MPa) | Elongation (%) | Porosity (%) | |
| EXAMPLE 1 | 960 | 752 | 45 | 0.8 |
| Example 2 | 852 | 690 | 20 | 1.1 |
| Example 3 | 884 | 725 | 38 | 2.1 |
| Example 4 | 955 | 745 | 41 | 0.9 |
| Comparative example 1 | 911 | 720 | 19 | 1.8 |
As can be seen from the comparison of the data in Table 1, LaB6Should not be too small or too large, LaB6When the amount of (b) is 0.8%, the tensile strength, yield strength and elongation are rather decreased, and the porosity is greatly increased.
As can be seen by comparing example 1 with example 4, Hastelloy X alloy and GH3536 alloy are nickel-base superalloys with similar properties, and thus, LaB6The grain boundary strengthening can be carried out on the additive manufacturing nickel-base superalloy.
Aiming at the problem that the nickel-based high-temperature alloy is easy to crack in the additive manufacturing process, the invention firstly carries out grain boundary strengthening on the nickel-based high-temperature alloy in the additive manufacturing process by adding the rare earth element boride, the rare earth element boride can be decomposed into the rare earth element and the boron element in the laser-powder interaction, the rare earth element can react with oxygen and other impurity elements in the powder to generate rare earth oxide to purify a grain boundary, the boron element can form boride with strong carbide forming elements such as Ti, Cr or Mo and the like or the boron carbide can change the carbide form and distribution state at the grain boundary, and the grain boundary strengthening effect is also achieved.
The GH3536 nickel-based high-temperature alloy formed by the method has no obvious cracks, the relative density of a sample piece reaches over 99.5 percent, the yield strength and the ultimate tensile strength reach 750MPa and 960MPa, and the elongation after fracture can reach about 45 percent.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. The application of the rare earth element boride in improving the comprehensive performance of the additive manufacturing nickel-based high-temperature alloy is characterized in that: the rare earth boride is LaB6、YB6、CeB6Or ErB6Wherein the rare earth boride is present in a mass fraction of 0.5 to 2%.
2. A method for improving the comprehensive performance of additive manufacturing nickel-based high-temperature alloy is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
taking nickel-based superalloy powder as a raw material, mechanically mixing rare earth boride, and forming by an additive manufacturing technology;
wherein the rare earth boride is LaB6、YB6、CeB6Or ErB6One of (1);
the mass fraction ratio of the nickel-based superalloy powder to the rare earth boride is 98-99.5%: 0.5 to 2 percent.
3. The method for improving the overall performance of an additive manufactured nickel-base superalloy as in claim 2, wherein: the powder is formed by an additive manufacturing technology, a selective laser melting forming technology is selected, the laser power is 150-250 MPa, the scanning speed is 700-1100 mm/s, the scanning interval is 0.05-0.1 mm, the thickness of the powder layer is 0.03-0.05 mm, and the scanning mode is that the layers rotate by 67-90 degrees or the powder layer rotates by 67 degrees in a partition mode.
4. Nickel-base-superalloy obtainable by the process according to claim 2 or 3, wherein: the nickel-based superalloy comprises the following components in percentage by mass: 20.5 to 23 percent of Cr, 17 to 20 percent of Fe, 8 to 10 percent of Mo, 0.5 to 2.5 percent of Co, 0.2 to 1 percent of W, less than or equal to 0.5 percent of Al, 0.05 to 0.15 percent of C, less than or equal to 0.15 percent of Ti, and XB60.5-2%, and the balance of Ni;
wherein X is selected from one of La, Y, Ce or Er.
5. The nickel-base superalloy according to claim 4, wherein: the composite material comprises the following components in percentage by mass:Cr:22.27％、Fe:18.73％、Mo:9.33％、Co:1.61％、W:0.55％、Al:0.1％、C:0.066％、Ti:0.02％、XB60.5 percent of Ni and the balance of Ni;
wherein, X is selected from one of La, Y, Ce or Er.
6. A nickel-base superalloy powder for additive manufacturing, comprising: comprises nickel-based superalloy powder and a rare earth boride, wherein the rare earth boride is LaB6、YB6、CeB6Or ErB6One of (1);
the mass fraction ratio of the nickel-based superalloy powder to the rare earth boride is 98-99.5%: 0.5 to 2 percent.
7. The nickel-base superalloy powder for additive manufacturing of claim 6, wherein: the particle size of the nickel-based superalloy powder is 15-53 mu m, and the particle size of the rare earth element boride is smaller than 1 mu m.
8. The nickel-base superalloy powder for additive manufacturing of claim 6 or 7, wherein: the nickel-based high-temperature alloy powder comprises, by mass, 20.5-23% of Cr, 17-20% of Fe, 8-10% of Mo, 0.5-2.5% of Co, 0.2-1% of W, less than or equal to 0.5% of Al, and 0.05-0.15% of C.
9. The nickel-base superalloy powder for additive manufacturing of claim 8, wherein: the nickel-based superalloy powder is selected from one of raw material powders of GH3536 alloy, Hastelloy X alloy, NC22FeD alloy, NiCr22FeMo alloy or Nimonic PE13 alloy.
10. A preparation method of nickel-based superalloy powder for additive manufacturing is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
selecting GH3536 alloy powder with the granularity of 15-53 mu m and rare earth boride powder with the granularity of less than 1 mu m, and weighing the two powders according to the mass percentage of 98-99.5% and 0.5-2%;
putting the weighed powder into a ball milling tank, then putting zirconia balls with the mass ratio of 1:1 to the powder, wherein the ball milling rotation speed is 50rad/min, the ball milling mode is wet milling, the ball milling medium is ethanol, the mass ratio of the ethanol to the nickel-based high-temperature alloy powder is 1:1, and the ball milling time is 15 hours;
and taking out the ball-milled mixed powder, placing the ball-milled mixed powder in a beaker, drying the ball-milled mixed powder in a vacuum drying oven for 8 hours at the drying temperature of 80 ℃, and then carrying out vacuum packaging on the dried powder.
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