Method for improving oxygen enrichment ablation resistance of additive manufacturing high-temperature alloy

Abstract

The invention belongs to the technical field of high-temperature alloy and additive manufacturing, and particularly relates to a method for improving oxygen enrichment ablation resistance of an additive manufacturing high-temperature alloy. The method comprises the following steps: (1) mixing high-temperature alloy micron powder with nano ceramic particles to obtain composite powder; (2) processing the composite powder by adopting a laser powder bed melting additive manufacturing process to obtain an additive manufacturing sample; and (3) carrying out solution treatment and aging treatment on the additive manufacturing sample. According to the method, the oxygen-enriched ablation resistance of the alloy can be remarkably improved, and the method is compatible with an additive manufacturing process, high in universality and suitable for preparing high-temperature alloy components for liquid rocket engine hot end components.

Description

Technical Field

[0001] This invention belongs to the field of high-temperature alloys and additive manufacturing technology, and specifically relates to a method for improving the resistance of additive-manufactured high-temperature alloys to oxygen-rich ablation. Background Technology

[0002] High-temperature alloys, as core materials in high-end equipment fields such as aerospace and energy, possess excellent oxidation resistance, creep resistance, and structural stability under high-temperature conditions, making them a crucial support for breaking through the upper limit of equipment service temperature and ensuring long-term reliable operation. Additive manufacturing technology's core advantage lies in its ability to rapidly and integrally form complex components without traditional molds, significantly improving material utilization and shortening the R&D cycle. Specifically in the field of high-temperature alloys, additive manufacturing is particularly suitable for manufacturing key high-performance high-temperature alloy components for aerospace applications.

[0003] However, with the improvement of thrust-to-weight ratio in new-generation aero-engines and breakthroughs in thrust levels of liquid rocket engines, the service environment of hot-end components is becoming increasingly extreme. In particular, the widespread application of the oxygen-enriched staged combustion cycle technology in liquid rocket engines requires these hot-end components to withstand long-term exposure to high-temperature, high-pressure, and high-dynamic-load oxygen-enriched gas erosion. This can easily induce severe oxidation and combustion reactions in the high-temperature alloy materials used, leading to rapid heat release, structural failure, and even serious accidents. Therefore, in addition to excellent high-temperature strength and creep resistance, the resistance to oxygen-enriched gas ablation has become a core indicator determining the reliability and operational limits of liquid rocket engines.

[0004] However, the oxygen-enriched ablation resistance of current mainstream high-temperature alloys (such as GH4169) is no longer sufficient to meet the technical requirements of next-generation equipment. Current traditional methods for improving the ablation resistance of high-temperature alloys have significant limitations: First, surface coating methods, while able to isolate the oxygen-enriched environment to some extent, are prone to cracking and peeling during thermal cycling due to the difference in thermal expansion coefficients between the coating and the substrate. Furthermore, the coating preparation process is complex, contradicting the integrated forming advantages of additive manufacturing. Second, traditional composition control methods often optimize oxygen-enriched ablation resistance by controlling the content of high-heat-of-combustion elements (such as Al and Ti) in the alloy. However, these methods have long development cycles, and the newly developed high-temperature alloys often fail to simultaneously achieve high-temperature strength and toughness. Therefore, developing a high-temperature alloy modification method that balances additive manufacturing process compatibility with oxygen-enriched ablation resistance has become a critical technical bottleneck that the industry urgently needs to overcome.

[0005] In view of this, this invention is hereby proposed. Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention provides a method for improving the resistance of additively manufactured high-temperature alloys to oxygen-rich ablation, the method comprising the following steps: (1) High-temperature alloy micron powder is mixed with nano-ceramic particles to obtain composite powder; (2) The composite powder is processed using laser powder bed fusion additive manufacturing process to obtain an additive manufacturing sample; (3) The additive manufacturing sample is subjected to solution treatment and aging treatment, and then it is ready.

[0007] Preferably, in step (1), the high-temperature alloy micron powder is spherical or near-spherical with a particle size of 15-53 μm.

[0008] Preferably, in step (1), the high-temperature alloy comprises matrix elements, solid solution strengthening elements, precipitation strengthening elements, grain boundary toughening elements, other trace elements, and unavoidable impurity elements; wherein, by weight percentage: The matrix element is Ni, with Ni ≥ 50%; The solid solution strengthening element is one or more of Co, Cr, Fe, W, and Mo, with 0.1%≤Co≤30%, 0.1%≤Cr≤25%, 0.1%≤Fe≤25%, 0.1%≤W≤10%, and 0.1%≤Mo≤10%. The precipitation strengthening element is one or more of Al, Ti, and Nb, with 0.1%≤Al≤5%, 0.1%≤Ti≤5%, and 0.1%≤Nb≤6%. The grain boundary strengthening element is one or more of C, B, and Zr, with 0.01%≤C≤0.1%, 0.001%≤B≤0.01%, and 0.01%≤Zr≤0.05%. The other trace elements are one or more of Cu, V, and Ce; The unavoidable impurity element is one or a combination of two or more of Mn, Si, P, S, O, N, and H.

[0009] Preferably, in step (1), the particle size of the nano-ceramic particles is 20-1000 nm.

[0010] Preferably, in step (1), the nano-ceramic particles are 0.3-3% of the mixed raw materials by weight percentage.

[0011] Preferably, in step (1), the nano-ceramic particles are one or a combination of oxide nano-ceramic particles and carbide nano-ceramic particles.

[0012] Preferably, in step (2), additive manufacturing is performed under vacuum or a protective atmosphere.

[0013] Preferably, in step (2), the parameters of the additive manufacturing process are: single layer thickness of 20-40μm, scanning spacing of 60-100μm, laser power of 150-350W, laser scanning rate of 800-1300mm / s, and laser spot diameter of 60-100μm.

[0014] Preferably, in step (3), the solution treatment is performed by holding the solution at 980-1000℃ for 1-2 hours and then cooling it.

[0015] Preferably, in step (3), the aging process is as follows: first, heat treatment at 730-750℃ for 15-17 hours, then cool, then heat treatment at 650-670℃ for 10-12 hours, and then cool again.

[0016] The beneficial effects of this invention are as follows: 1. Targeted solutions to pain points in extreme service environments: The method of this invention can significantly improve the oxygen-enriched ablation resistance of additively manufactured high-temperature alloys. As shown in the verification data, after introducing nano-ceramic particles, the actual burning length of the alloy is greatly reduced from 96.48 mm to a minimum of 6.34 mm. This can effectively resist the extreme service environment of hot-end components of oxygen-enriched combustion cycle engines, avoid component failure due to severe oxidation and combustion, and ensure the operational reliability and working limits of the equipment.

[0017] 2. Compatible with additive manufacturing process characteristics: By precisely controlling the type and amount of nano-ceramic particles (0.3-3wt%), this invention does not compromise the compatibility of high-temperature alloys with additive manufacturing processes, and can achieve integrated forming of complex components by relying on laser powder bed fusion additive manufacturing technology.

[0018] 3. Overcoming the limitations of traditional modification methods: Compared with traditional coating methods, this invention uniformly disperses nanoscale ceramic particles inside the high-temperature alloy matrix, significantly reducing the risk of cracking caused by the difference in thermal expansion coefficients between the high-temperature alloy and ceramic. Compared with traditional composition control methods, this method does not require adjustment of the alloy matrix composition. It can achieve a leap in oxygen-rich ablation resistance simply by introducing a small amount of nano-ceramic particles, avoiding the negative impact of traditional composition adjustment on the high-temperature strength and creep resistance of the alloy.

[0019] 4. Strong process versatility: The method of this invention has been verified to be effective in a variety of high-temperature alloy systems (Examples 1, 6 and 8). After introducing suitable nano-ceramic particles, the resistance to oxygen-rich ablation can be significantly improved. It can also be flexibly matched with different additive manufacturing process parameter ranges, making it suitable for the preparation of different types of high-temperature alloy components in the aerospace field and possessing broad engineering application prospects. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a SEM image of the composite powder from Example 2 of the present invention.

[0022] Figure 2 This is a SEM image of the composite powder from Example 3 of the present invention.

[0023] Figure 3 This is a SEM image of the composite powder from Example 4 of the present invention.

[0024] Figure 4 This is a SEM image of the composite powder from Example 5 of the present invention.

[0025] Figure 5 This is a SEM image of the composite powder from Example 7 of the present invention.

[0026] Figure 6 This is a SEM image of the composite powder from Example 9 of the present invention. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0028] Example 1 This embodiment provides a method for improving the resistance of additively manufactured high-temperature alloys to oxygen-rich ablation, the method comprising the following steps: (1) Determine the composition of the high-temperature alloy, including the following components by mass percentage: Fe: 14.25%, Cr: 17.20%, Mo: 3.98%, Al: 0.95%, Ti: 0.72%, Nb: 5.1%, Mn: 0.005%, Si: 0.041%, Cu: 0.38%, V: 0.44%, C: 0.012%, B: 0.0062%, Zr: 0.036%, Ce: 0.0025%, balance Ni and unavoidable impurities.

[0029] (2) The above-mentioned high-temperature alloy spherical powder (particle size 15-53μm) was used to prepare samples by laser powder bed melting additive manufacturing process. The additive manufacturing process parameters included: laser spot diameter of 80μm, single layer thickness of 40μm, scanning spacing of 80μm, laser power of 240W, and laser scanning rate of 1000mm / s.

[0030] (3) The obtained additive manufacturing sample was subjected to solution treatment and aging treatment. The solution treatment method was: heat treatment at 980℃ for 1 hour, followed by air cooling. The aging treatment method was: heat treatment at 730℃ for 15 hours, followed by air cooling, then heat treatment at 650℃ for 10 hours, followed by air cooling.

[0031] Example 2 The difference between Example 2 and Example 1 is only that: 1.3% by mass of Y2O3 nano-ceramic particles are introduced on the basis of the high-temperature alloy spherical powder described in Example 1. That is, 1677.9g of high-temperature alloy powder and 22.1g of Y2O3 nano-ceramic particles are placed in an acoustic resonance powder mixer. The powder mixing process parameters include: acceleration 65g and mixing time 30min.

[0032] Example 3 The difference between Example 3 and Example 1 is only that: 1.3% by mass of TiC nano-ceramic particles are introduced on the basis of the high-temperature alloy spherical powder described in Example 1. That is, 1677.9g of high-temperature alloy powder and 22.1g of TiC nano-ceramic particles are placed in an acoustic resonance powder mixer. The powder mixing process parameters include: acceleration 65g and mixing time 30min.

[0033] Example 4 The difference between Example 4 and Example 1 is only that: 1.3% by mass of WC nano-ceramic particles are introduced on the basis of the high-temperature alloy spherical powder described in Example 1. That is, 1677.9g of high-temperature alloy powder and 22.1g of WC nano-ceramic particles are placed in an acoustic resonance powder mixer. The powder mixing process parameters include: acceleration 65g and mixing time 30min.

[0034] Example 5 The difference between Example 5 and Example 1 is only that: 1.3% by mass ZrC nano-ceramic particles are introduced on the basis of the high-temperature alloy spherical powder described in Example 1. That is, 1677.9g of high-temperature alloy powder and 22.1g of ZrC nano-ceramic particles are placed in an acoustic resonance powder mixer. The powder mixing process parameters include: acceleration 65g and mixing time 30min.

[0035] Example 6 The only difference between Example 6 and Example 1 is the chemical composition of the high-temperature alloy. The high-temperature alloy in this example comprises the following components by mass percentage: Co: 16.8%, Cr: 7.9%, Al: 1.5%, Ti: 3.4%, Mn: 0.0024%, Si: 0.021%, C: 0.05%, B: 0.003%, Zr: 0.01%, with the balance being Ni and unavoidable impurities.

[0036] Example 7 The difference between Example 7 and Example 6 is only that: 2.0% by mass of TiC nano-ceramic particles are introduced on the basis of the high-temperature alloy spherical powder described in Example 6, that is, 1666g of high-temperature alloy powder and 34g of TiC nano-ceramic particles are placed in an acoustic resonance powder mixer, and the powder mixing process parameters include: acceleration 65g and mixing time 30min.

[0037] Example 8 The only difference between Example 8 and Example 1 is the chemical composition of the high-temperature alloy. The high-temperature alloy in this example comprises the following components by mass percentage: Co: 16.7%, Cr: 8.0%, W: 2.1%, Mo: 0.3%, Al: 1.6%, Ti: 3.5%, Mn: 0.0034%, Si: 0.021%, C: 0.07%, B: 0.003%, Zr: 0.02%, with the balance being Ni and unavoidable impurities.

[0038] Example 9 The difference between Example 9 and Example 8 is only that: 2.0% by mass of TiC nano-ceramic particles are introduced on the basis of the high-temperature alloy spherical powder described in Example 8, that is, 1666g of high-temperature alloy powder and 34g of TiC nano-ceramic particles are placed in an acoustic resonance powder mixer, and the powder mixing process parameters include: acceleration 65g and mixing time 30min.

[0039] Verification Example Oxygen-enriched combustion samples were prepared for the additively manufactured high-temperature alloys of Examples 1-9. The samples had a diameter of φ3.2×120mm, a bright, oil-free surface, and were then tested for resistance to oxygen-enriched ablation. The test conditions for Examples 1-5 were room temperature, 3.5MPa, and pure oxygen; the test conditions for Examples 6-9 were room temperature, 13MPa, and pure oxygen. Al strips were used as ignition aids in all tests, and the actual burning length of each sample was measured. The test results are shown in Table 1.

[0040] Table 1. Test results of oxygen-enriched ablation resistance of different additive manufacturing samples

[0041] As shown in Table 1, the additively manufactured high-temperature alloy sample rod in Example 1 exhibited a large burning length, reaching 96.48 mm. In Examples 2-5, after introducing 1.3% by mass of Y₂O₃, TiC, WC, and ZrC nano-ceramic particles into the high-temperature alloy described in Example 1, the actual burning lengths were significantly reduced to 38.62 mm, 6.34 mm, 10.41 mm, and 14.74 mm, respectively, indicating a substantial improvement in the material's resistance to oxygen-enriched ablation. In Examples 6 and 8, two other high-temperature alloy compositions were used, and due to the differences in alloy composition, their resistance to oxygen-enriched ablation was significantly better than that of the high-temperature alloy in Example 1. Based on Examples 6 and 8, the introduction of 2% by mass of TiC further enhanced the material's resistance to oxygen-enriched ablation.

[0042] Figures 1-6 The composite powders used in Examples 2-5, 7, and 9 are respectively. It can be seen that the composite powders used in Examples 2-5 respectively introduced Y2O3, TiC, WC, and ZrC nano-ceramic particles, which adhered to the surface of the high-temperature alloy micron powder; the composite powders used in Examples 7 and 9 respectively introduced TiC nano-ceramic particles.

[0043] As can be seen from the above, this invention significantly improves the alloy's resistance to oxygen-enriched ablation by introducing appropriate amounts of carbide, oxide, and other nano-ceramic particles into the high-temperature alloy without compromising its additive manufacturing processability. Furthermore, the method disclosed in this invention has been successfully verified in various high-temperature alloy systems, demonstrating a certain degree of universality. The method provided by this invention can ensure the compatibility of high-temperature alloy materials with additive manufacturing processes while improving their resistance to oxygen-enriched ablation, thus meeting the stringent requirements of key components such as liquid rocket engines.

[0044] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys, characterized in that, The method includes the following steps: (1) High-temperature alloy micron powder is mixed with nano-ceramic particles to obtain composite powder; (2) The composite powder is processed using laser powder bed fusion additive manufacturing process to obtain an additive manufacturing sample; (3) The additive manufacturing sample is subjected to solution treatment and aging treatment, and then it is ready.

2. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (1), the high-temperature alloy micron powder is spherical or near-spherical with a particle size of 15-53 μm.

3. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (1), the high-temperature alloy includes matrix elements, solid solution strengthening elements, precipitation strengthening elements, grain boundary toughening elements, other trace elements, and unavoidable impurity elements; wherein, by weight percentage: The matrix element is Ni, with Ni ≥ 50%; The solid solution strengthening element is one or more of Co, Cr, Fe, W, and Mo, with 0.1%≤Co≤30%, 0.1%≤Cr≤25%, 0.1%≤Fe≤25%, 0.1%≤W≤10%, and 0.1%≤Mo≤10%. The precipitation strengthening element is one or more of Al, Ti, and Nb, with 0.1%≤Al≤5%, 0.1%≤Ti≤5%, and 0.1%≤Nb≤6%. The grain boundary strengthening element is one or more of C, B, and Zr, with 0.01%≤C≤0.1%, 0.001%≤B≤0.01%, and 0.01%≤Zr≤0.05%. The other trace elements are one or more of Cu, V, and Ce; The unavoidable impurity element is one or a combination of two or more of Mn, Si, P, S, O, N, and H.

4. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (1), the particle size of the nano-ceramic particles is 20-1000 nm.

5. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (1), the nano-ceramic particles are 0.3-3% of the composite powder by weight percentage.

6. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (1), the nano-ceramic particles are one or a combination of two of oxide nano-ceramic particles and carbide nano-ceramic particles.

7. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (2), additive manufacturing is performed under vacuum or a protective atmosphere.

8. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (2), the parameters of the additive manufacturing process are: single layer thickness of 20-40μm, scanning spacing of 60-100μm, laser power of 150-350W, laser scanning rate of 800-1300mm / s, and laser spot diameter of 60-100μm.

9. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (3), the solution treatment is performed by holding the solution at 980-1000℃ for 1-2 hours and then cooling it.

10. The method for improving the resistance to oxygen-rich ablation of additively manufactured high-temperature alloys according to claim 1, characterized in that, In step (3), the aging process is as follows: first, keep warm at 730-750℃ for 15-17 hours, then cool down, and then keep warm at 650-670℃ for 10-12 hours, and then cool down again.

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