High-temperature alloy powder for additive manufacturing and preparation method thereof

Abstract

The invention relates to high-temperature alloy powder for additive manufacturing and a preparation method thereof, and the preparation method comprises the following steps: selecting raw materials; the raw materials comprise matrix high-temperature alloy powder and nano-particle powder; the matrix high-temperature alloy powder is subjected to corrosion treatment, and a nanometer pit structure is formed in the surface of the matrix high-temperature alloy powder; then cleaning and drying treatment are carried out, and matrix high-temperature alloy powder subjected to corrosion treatment is obtained; the nano-particle powder and the matrix high-temperature alloy powder obtained after corrosion treatment are mixed so that nano-particles can be loaded on the matrix high-temperature alloy powder obtained after corrosion treatment, and powder obtained after mixing treatment is obtained; and the powder obtained after mixing treatment is subjected to free-state nano-particle removal treatment, and the high-temperature alloy powder for additive manufacturing is obtained. The method is mainly used for improving the laser absorptivity of the high-temperature alloy powder for additive manufacturing.

Description

Technical Field

[0001] This invention relates to the field of high-temperature alloy materials and additive manufacturing technology, and in particular to a high-temperature alloy powder for additive manufacturing and its preparation method. Background Technology

[0002] In laser additive manufacturing, the particle size distribution, morphology, and surface condition of metal powder significantly affect laser absorption rate, thus determining the microstructure density and mechanical properties of the formed component. To improve raw material utilization and reduce costs, the repeated recycling of metal powder is commonly used in actual manufacturing processes (some high-temperature alloy powder is not printed into components during additive manufacturing and is recycled). However, the surface condition, morphological integrity, and physical properties of recycled powder change, leading to a decrease in laser absorption rate. This affects the stability of the molten pool and the compaction of the forming process, reducing the stability and forming consistency of the high-temperature alloy additive manufacturing process, which is detrimental to its large-scale and engineering applications.

[0003] In existing technologies, laser absorption rate is often improved by increasing powder sphericity and optimizing particle size distribution. However, these methods have high production costs, and sphericity is easily damaged during actual additive manufacturing, leading to a decrease in powder laser absorption performance and making long-term stable use difficult. Meanwhile, laser absorption rate directly affects the one-time forming quality and printing efficiency of components. For metal materials with high laser reflectivity, such as aluminum alloys, high laser power and low scanning rates are required, resulting in low efficiency. Conversely, for steel and high-temperature alloys with superior laser absorption performance, further improving their laser absorption rate would help improve processing efficiency and forming quality.

[0004] In summary, there is an urgent need for a novel method for preparing high-temperature alloy powders for additive manufacturing to improve the powder laser absorption rate. Summary of the Invention

[0005] In view of this, the present invention provides a high-temperature alloy powder for additive manufacturing and a method for preparing the same, the main purpose of which is to improve the laser absorption rate of the high-temperature alloy powder for additive manufacturing.

[0006] To achieve the above objectives, the present invention mainly provides the following technical solutions:

[0007] On one hand, embodiments of the present invention provide a method for preparing high-temperature alloy powder for additive manufacturing, which includes the following steps:

[0008] Raw material preparation: Select raw materials; wherein, the raw materials include matrix high-temperature alloy powder and nanoparticle powder;

[0009] Corrosion treatment: The base high-temperature alloy powder is subjected to corrosion treatment to form a nano-pit structure on the surface of the base high-temperature alloy powder; then it is cleaned and dried to obtain the corrosion-treated base high-temperature alloy powder.

[0010] Mixing treatment: The nanoparticle powder and the corrosion-treated matrix high-temperature alloy powder are mixed to load the nanoparticles onto the corrosion-treated matrix high-temperature alloy powder, resulting in a mixed powder.

[0011] Treatment to remove free nanoparticles: The powder after the mixed treatment is subjected to treatment to remove free nanoparticles to obtain high-temperature alloy powder for additive manufacturing.

[0012] Preferably, in the step of preparing raw materials:

[0013] The raw materials comprise, by mass fraction, 96-99 wt.% matrix high-temperature alloy powder and 1-4 wt.% nanoparticle powder.

[0014] Preferably, in the step of preparing raw materials:

[0015] The nanoparticle powder comprises one or more of ceramic particles, graphene particles, and rare earth particles; preferably, the ceramic particles are one or more of Y₂O₃ particles, ZrO₂ particles, and Al₂O₃ particles; the rare earth elements are one or more of La, Sc, and Ce particles; and / or

[0016] The primary particle size range of the nanoparticle powder is 50-200 nm.

[0017] Preferably, in the step of preparing raw materials:

[0018] In the matrix high-temperature alloy powder: the mass percentage of Cr is 27.0-31.0 wt.%; the mass percentage of Co is 30.0-33.0 wt.%; the mass percentage of Re is 1.0-3.0 wt.%; the mass percentage of W is 1.0-4.0 wt.%; the mass percentage of Al is 0.1-1.0 wt.%; the mass percentage of Ti is 0.1-1.0 wt.%; the mass percentage of Nb is 0.1-1.0 wt.%; the mass percentage of C is 0.01-0.2 wt.%, and the balance is Ni;

[0019] The particle size of the matrix high-temperature alloy powder is 15-53 μm.

[0020] Preferably, in the corrosion treatment step: the base high-temperature alloy powder is placed in aqua regia and chemically corroded for 10-60 seconds to etch nano-pits on the surface of the base high-temperature alloy powder.

[0021] Preferably, after chemical etching, the powder after chemical etching is ultrasonically cleaned with a volatile cleaning solvent, then after sedimentation, the cleaning solution is removed and vacuum drying is performed to obtain the etched high-temperature alloy matrix powder; preferably, the volatile cleaning solvent is alcohol.

[0022] More preferably, during the ultrasonic cleaning process: the ultrasonic vibration frequency is 15-35 kHz, the vibration mode is continuous vibration mode or pulse vibration mode, the ultrasonic cleaning time is 30-60 min, and the mechanical stirring speed is 50-150 r / min.

[0023] Preferably, in the mixing process step:

[0024] The corroded matrix high-temperature alloy powder and nanoparticle powder are placed in an acoustic resonance device for acoustic resonance mixing treatment, so as to load the nanoparticles on the corroded matrix high-temperature alloy powder to obtain the mixed powder.

[0025] Preferably, the parameters of the acoustic resonance mixing process are as follows: the filling ratio is 80%-90%; first, vibrate for 5-10 minutes under an acceleration of 10-30g, and then vibrate for 50-70 minutes under an acceleration of 70-90g;

[0026] Preferably, a cooling process is required during the acoustic resonance mixing process; preferably, the cooling process is a circulating water cooling process.

[0027] Preferably, in the step of removing free nanoparticles: the mixed powder is placed in a volatile solvent, ultrasonically stirred, and then settled. After the solution is discarded, the powder is dried to obtain a composite powder.

[0028] Preferably, the volatile solvent is alcohol;

[0029] Preferably, the drying process is vacuum drying; wherein the temperature of the vacuum drying process is 200-300℃ and the time of the vacuum drying process is 1-4 hours.

[0030] Preferably, the method for preparing the high-temperature alloy powder for additive manufacturing further includes:

[0031] Sieving process: The high-temperature alloy powder for additive manufacturing is sieved to obtain high-temperature alloy powder for additive manufacturing with the required particle size;

[0032] Preferably, the required particle size is 15-53 μm.

[0033] On the other hand, embodiments of the present invention provide a high-temperature alloy powder for additive manufacturing, characterized in that the high-temperature alloy powder for additive manufacturing is prepared by the preparation method of the high-temperature alloy powder for additive manufacturing described in any one of the above claims.

[0034] Preferably, the high-temperature alloy powder for additive manufacturing comprises: a matrix high-temperature alloy powder having a nanoscale pit structure on its surface and nanoparticles; wherein the nanoparticles are loaded on the surface of the pit structure and the matrix high-temperature alloy powder;

[0035] Preferably, the diameter of the pit structure is 50-200 nm and the depth is 20-100 nm;

[0036] Preferably, the size of the nanoparticles is 50-150 nm;

[0037] Preferably, the high-temperature alloy powder for additive manufacturing has an absorption rate of 75-85% at a 1064nm laser wavelength.

[0038] Compared with the prior art, the high-temperature alloy powder for additive manufacturing and its preparation method according to embodiments of the present invention have at least the following beneficial effects:

[0039] This invention provides a method for preparing high-temperature alloy powder for additive manufacturing. The method involves selecting raw materials, including a matrix high-temperature alloy powder and nanoparticle powder. The matrix high-temperature alloy powder is subjected to etching treatment to create nano-pits on its surface. After cleaning and drying, the etched matrix high-temperature alloy powder is obtained. The nanoparticle powder and the etched matrix high-temperature alloy powder are then mixed to load the nanoparticles onto the etched matrix high-temperature alloy powder, resulting in a mixed powder. The mixed powder is then subjected to a process to remove free nanoparticles, yielding the high-temperature alloy powder for additive manufacturing. It should be noted that, compared to existing technologies (e.g., comparative examples), the surface of the etched matrix powder in the high-temperature alloy powder for additive manufacturing prepared in this invention has a nanoscale pit structure, causing multiple reflections and scattering of the incident laser on the powder surface, significantly extending the optical path and increasing the absorbed light energy per unit time. Meanwhile, the nanoparticles (such as Y2O3) loaded on the substrate possess high refractive index and localized surface plasmon effects, further enhancing the local electromagnetic field strength and improving the coupling efficiency between laser energy and the metal substrate. Furthermore, the roughening of the substrate powder surface after etching enhances the contact area between powder particles and the micropore light absorption effect, which helps reduce reflection loss. This results in a 10-25% increase in the absorption rate of the high-temperature alloy powder for additive manufacturing prepared in this embodiment at a 1064nm laser wavelength, effectively improving the energy utilization rate and forming stability of the laser molten pool.

[0040] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings. Attached Figure Description

[0041] Figure 1 This is a schematic flowchart illustrating a method for preparing high-temperature alloy powder for additive manufacturing, provided as an example.

[0042] Figure 2 The typical morphology and elemental distribution characteristics of the additive manufacturing high-temperature alloy composite powder prepared in Example 1 are shown in Figure 1. (a) Figure 1 is a low-magnification SEM image of the additive manufacturing high-temperature alloy powder, (b) Figure 2 is a high-magnification SEM image of the additive manufacturing high-temperature alloy powder, and (c) Figure 3 is an EDS elemental surface scan image of the additive manufacturing high-temperature alloy powder.

[0043] Figure 3The typical morphology and elemental distribution characteristics of the additive manufacturing high-temperature alloy composite powder prepared in Example 2 are shown in Figure 2. (a) Figure 2 shows a low-magnification SEM image of the additive manufacturing high-temperature alloy powder, (b) Figure 2 shows a high-magnification SEM image of the additive manufacturing high-temperature alloy powder, and (c) Figure 3 shows an EDS elemental surface scan of the additive manufacturing high-temperature alloy powder.

[0044] Figure 4 The typical morphology and elemental distribution characteristics of the additive manufacturing high-temperature alloy composite powder prepared in Comparative Example 1 are shown in Figure 1. (a) Figure 1 is a low-magnification SEM image of the additive manufacturing high-temperature alloy powder, (b) Figure 2 is a high-magnification SEM image of the additive manufacturing high-temperature alloy powder, and (c) Figure 3 is an EDS elemental surface scan image of the additive manufacturing high-temperature alloy powder.

[0045] Figure 5 The images show the morphology of the high-temperature alloy powder for additive manufacturing prepared in Comparative Example 2; (a) is a low-magnification SEM image of the high-temperature alloy powder for additive manufacturing, (b) is a high-magnification SEM image of the high-temperature alloy powder for additive manufacturing, and (c) is an EDS elemental surface scan image of the high-temperature alloy powder for additive manufacturing.

[0046] Figure 6 The images show the morphology of the high-temperature alloy powder for additive manufacturing prepared in Comparative Example 3; (a) is a low-magnification SEM image of the high-temperature alloy powder for additive manufacturing, (b) is a high-magnification SEM image of the high-temperature alloy powder for additive manufacturing, and (c) is an EDS elemental surface scan image of the high-temperature alloy powder for additive manufacturing.

[0047] Figure 7 The image shows a comparison of the laser absorption rates of the additive manufacturing high-temperature alloy composite powders prepared in Examples 1 and 2 and Comparative Examples 1-3 of this invention. Detailed Implementation

[0048] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the specific embodiments, structures, features, and effects according to the present invention will be described in detail below with reference to the accompanying drawings and preferred embodiments. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.

[0049] This invention provides a high-temperature alloy powder for additive manufacturing and its preparation method. The method involves etching the base high-temperature alloy powder to construct a nanoscale pit structure on the particle surface, and simultaneously using physical composite technology to load a layer of high-absorption nanoparticles onto the powder surface. This method not only enhances the adhesion stability of the nanoparticles on the powder surface but also significantly improves the powder's absorption capacity for laser energy, thereby increasing the energy coupling efficiency of the laser molten pool and improving the forming density and processing efficiency.

[0050] The method of this invention has advantages such as process controllability, moderate cost, and applicability to cyclic powder modification. It can be widely applied to the additive manufacturing process of high-temperature alloys such as nickel-based and cobalt-based alloys, providing raw material guarantee for the stable and efficient preparation of high-performance complex structural components.

[0051] The specific solution of the present invention is as follows:

[0052] On one hand, embodiments of the present invention provide a method for preparing high-temperature alloy powder for additive manufacturing, such as... Figure 1 As shown, it includes the following steps:

[0053] Raw material preparation: Select raw materials; wherein, the raw materials include matrix high-temperature alloy powder and nanoparticle powder.

[0054] The raw materials, by mass fraction, comprise 96-99 wt.% matrix high-temperature alloy powder and 1-4 wt.% nanoparticle powder.

[0055] The nanoparticle powder includes one or more of ceramic particles, graphene particles, and rare earth particles. The ceramic particles are one or more of Y2O3 particles, ZrO2 particles, and Al2O3 particles; the rare earth elements are one or more of La, Sc, and Ce particles.

[0056] The primary particle size range of the nanoparticle powder is 50-200 nm.

[0057] In the matrix high-temperature alloy powder: the mass percentage of Cr is 27.0-31.0 wt.%; the mass percentage of Co is 30.0-33.0 wt.%; the mass percentage of Re is 1.0-3.0 wt.%; the mass percentage of W is 1.0-4.0 wt.%; the mass percentage of Al is 0.1-1.0 wt.%; the mass percentage of Ti is 0.1-1.0 wt.%; the mass percentage of Nb is 0.1-1.0 wt.%; the mass percentage of C is 0.01-0.2 wt.%, and the balance is Ni.

[0058] The particle size of the matrix high-temperature alloy powder is 15-53 μm.

[0059] Corrosion treatment: The base high-temperature alloy powder is subjected to corrosion treatment to form nano-pits on the surface of the base high-temperature alloy powder; then it is cleaned and dried to obtain the corrosion-treated base high-temperature alloy powder (i.e., lightly corroded powder).

[0060] Preferably, in this step, the base high-temperature alloy powder is placed in aqua regia (concentrated hydrochloric acid: concentrated nitric acid = 3:1) and chemically etched for 10-60 seconds to etch nano-pits on the surface of the base high-temperature alloy powder.

[0061] The process involves several steps. After chemical etching, the powder is ultrasonically cleaned with alcohol, followed by a sedimentation process. (After ultrasonic stirring, the powder suspension is placed in a beaker and allowed to stand for 10-30 minutes, allowing larger particles to settle first, while free nanoparticles remain suspended in the upper liquid layer.) The cleaning solution is then removed, and the powder is vacuum-dried (the upper clear liquid is carefully discarded, and the settled powder layer is retained and vacuum-dried. The vacuum drying temperature is 200-300℃, and the drying time is 1-4 hours). This yields the etched high-temperature alloy matrix powder. This sedimentation process effectively removes unbonded free nanoparticles, ensuring uniform surface loading and strong adhesion of the composite powder.

[0062] Preferably, during the ultrasonic cleaning process: the ultrasonic vibration frequency is 15-35kHz, the vibration mode is continuous vibration mode or pulse vibration mode, the ultrasonic cleaning time is 30-60min, and the mechanical stirring speed is 50-150r / min.

[0063] Mixing treatment: The nanoparticle powder and the corrosion-treated matrix high-temperature alloy powder are mixed to load the nanoparticles onto the corrosion-treated matrix high-temperature alloy powder, resulting in a mixed powder (i.e., acoustic resonance composite powder).

[0064] In this process, the corroded high-temperature alloy matrix powder and nanoparticle powder are placed in an acoustic resonance device for acoustic resonance mixing treatment, so as to load the nanoparticles onto the corroded high-temperature alloy matrix powder to obtain the mixed powder.

[0065] Preferably, the parameters of the acoustic resonance mixing process are as follows: the filling ratio is 80%-90% (wherein, the filling ratio refers to the volume ratio of the mixed powder to the entire mixing chamber); first, vibrate for 5-10 minutes under an acceleration of 20g, and then vibrate for 50-70 minutes under an acceleration of 80g (the unit of acceleration of the mixing equipment is g, which represents gravitational acceleration).

[0066] Preferably, a cooling process is required during the acoustic resonance mixing process; preferably, the cooling process is a circulating water cooling process.

[0067] Treatment to remove free nanoparticles: The powder after the mixed treatment is subjected to treatment to remove free nanoparticles (i.e., to remove excess nanoparticles that are not loaded on the matrix high-temperature alloy powder) to obtain high-temperature alloy powder for additive manufacturing.

[0068] The mixed powder is placed in alcohol and subjected to ultrasonic stirring and sedimentation (after ultrasonic stirring, sedimentation is performed by placing the powder suspension in a beaker and letting it stand for 10-30 minutes to allow larger particles to settle first, while free nanoparticles remain suspended in the upper liquid layer). The solution is then discarded and dried (the upper clear liquid is carefully discarded, the lower settled powder layer is retained, and vacuum drying is performed) to obtain the composite powder. Preferably, the drying process is vacuum drying. The temperature of the vacuum drying process is 200-300℃, and the time is 1-4 hours.

[0069] Sieving process: The high-temperature alloy powder for additive manufacturing is sieved to obtain high-temperature alloy powder for additive manufacturing with the required particle size.

[0070] Among them, the composite powder is sieved to obtain high-temperature alloy powder for additive manufacturing with a particle size of 15-53μm.

[0071] Preferably, a sieve of 270-800 mesh is used for sieving (selecting 270 mesh and 800 mesh sieves for secondary sieving) to remove large and small composite powders, thereby obtaining high-temperature alloy composite powder with a size of 15-53μm.

[0072] On the other hand, embodiments of the present invention provide a high-temperature alloy powder for additive manufacturing, wherein the high-temperature alloy powder for additive manufacturing is prepared by the preparation method of the high-temperature alloy powder for additive manufacturing described in any of the above claims.

[0073] Preferably, the high-temperature alloy powder for additive manufacturing comprises: a matrix high-temperature alloy powder with a nanoscale pit structure on its surface and nanoparticles; wherein the nanoparticles are loaded on the surface of the pit structure and the matrix high-temperature alloy powder. The pit structure has a diameter of 50-200 nm and a depth of 20-100 nm; the nanoparticles have a size of 50-150 nm; and the high-temperature alloy powder for additive manufacturing has an absorption rate of 75-85% at a 1064 nm laser wavelength. It should be noted that the nanoparticles are uniformly loaded on the pit and powder surface, forming a "pit-particle-matrix" composite interface structure. Compared with powder that has only undergone physical mixing, the surface area of ​​this composite interface structure is increased by approximately 15-30%, which can effectively enhance the multiple scattering and light-trapping effect of the powder on laser energy. Preferably, the matrix high-temperature alloy powder particles in the additive manufacturing high-temperature alloy powder prepared in this embodiment have an absorption rate of 75-85% at a laser wavelength of 1064nm after chemical etching, which is about 10-25% higher than that of the comparative powder (55-65%).

[0074] It should be noted that the above technical solution, by incorporating a specific proportion of nanoparticles into the high-temperature alloy matrix powder for additive manufacturing, and through a process of corrosion, acoustic resonance mixing, ultrasonic cleaning to remove free nanoparticles, and sieving, yields a composite powder with excellent adhesion, meeting the requirements for additive manufacturing. Simultaneously, the surface roughness of the high-temperature alloy powder modified with nanoparticles is significantly increased, allowing laser rays to be reflected multiple times within the powder rather than in the atmosphere, greatly improving the laser absorption rate of the high-temperature alloy composite powder. Furthermore, nanoparticles can also act as a reinforcing phase, improving the performance of the raw materials. This invention overcomes the technical problems of existing methods that alter laser absorption rate by increasing powder sphericity and improve forming efficiency using multi-laser equipment.

[0075] The present invention will be further illustrated below through examples:

[0076] Example 1

[0077] This embodiment prepares a high-temperature alloy powder for additive manufacturing, mainly including the following steps:

[0078] Raw material preparation: Select raw materials; wherein, by mass fraction, the raw materials include 99 wt.% matrix high-temperature alloy powder and 1 wt.% nanoparticle powder. The matrix high-temperature alloy powder has a particle size of 15-53 μm; the nanoparticle powder is selected from Y2O3 ceramic particles with a particle size of 100 nm.

[0079] The chemical composition of the matrix high-temperature alloy powder is as follows: Cr 28.3 wt.%; Co 33.0 wt.%; Re 1.40 wt.%; W 3.0 wt.%; Al 0.28 wt.%; Ti 0.25 wt.%; Nb 0.73 wt.%; C 0.05 wt.%; with the balance being Ni.

[0080] Corrosion treatment: The base high-temperature alloy powder was placed in aqua regia (concentrated hydrochloric acid: concentrated nitric acid = 3:1) for chemical corrosion treatment for 30 seconds. Then the solution was discarded, and the chemically corroded powder was ultrasonically cleaned with alcohol (ultrasonic stirring for 60 minutes). Then the powder was settled, and the cleaning solution was removed and vacuum dried. The vacuum drying temperature was 200℃ and the vacuum drying time was 2 hours to obtain the corrosion-treated base high-temperature alloy powder (i.e., lightly corroded powder).

[0081] Mixing treatment: Nanoparticle powder and corrosion-treated high-temperature alloy matrix powder are added to an acoustic resonance device for acoustic resonance mixing treatment; the powder filling ratio is 90%, and the device is first vibrated for 5 minutes under an acceleration of 20g, and then vibrated for 50 minutes under an acceleration of 80g. The entire process is cooled by circulating water to obtain the mixed powder (i.e., acoustic resonance composite powder).

[0082] Removal of free nanoparticles: The mixed powder was ultrasonically stirred in alcohol for 30 minutes. After ultrasonic stirring, a sedimentation process was performed (the powder suspension was placed in a beaker and allowed to stand for 10-30 minutes, allowing larger particles to settle first, while free nanoparticles remained suspended in the upper liquid). The supernatant was then carefully discarded, and the settled powder was retained and vacuum dried. The vacuum drying temperature was 200-300℃, and the drying time was 1-4 hours. The powder was then sieved through 270-mesh and 800-mesh sieves to obtain a high-temperature alloy powder for additive manufacturing with good adhesion.

[0083] Figure 2 The figures show the typical morphology and elemental distribution characteristics of the high-temperature alloy powder for additive manufacturing prepared in Example 1; wherein, (a) is a low-magnification SEM image of the high-temperature alloy powder for additive manufacturing, (b) is a high-magnification SEM image of the high-temperature alloy powder for additive manufacturing, and (c) is an EDS elemental surface scan image of the high-temperature alloy powder for additive manufacturing. Figure 2Figure (a) shows that the powder as a whole has good sphericity and particle size distribution. The surface of the powder after corrosion has a large number of fine particles attached, indicating that the effective composite of nanoparticles was achieved during the acoustic resonance treatment. Figure 2 Figure (b) shows a high-magnification SEM image of a single powder particle, which reveals a certain degree of roughness and irregular microstructure on its surface. This indicates that yttrium oxide particles are deposited in a relatively uniform manner and tightly adhered to the surface of the corroded matrix powder, providing a structural basis for enhancing laser absorption performance. Figure 2 Figure (c) shows the EDS elemental surface scan of the corresponding region. The results indicate that the Y element is uniformly dispersed on the powder surface, demonstrating that the acoustic resonance technology can achieve effective loading and uniform surface coverage of yttrium oxide nanoparticles. This composite powder structure helps improve laser absorption rate and molten pool stability, making it suitable for enhancing powder laser response performance in high-temperature alloy additive manufacturing.

[0084] Example 2

[0085] This embodiment prepares a high-temperature alloy powder for additive manufacturing, mainly including the following steps:

[0086] Raw material preparation: Select raw materials; wherein, by mass fraction, the raw materials include 98 wt.% matrix high-temperature alloy powder and 2 wt.% nanoparticle powder. The matrix high-temperature alloy powder has a particle size of 15-53 μm; the nanoparticle powder is selected from Y2O3 ceramic particles with a particle size of 100 nm.

[0087] The chemical composition of the matrix superalloy powder is as follows: Cr 28.3 wt.%; Co 33.0 wt.%; Re 1.40 wt.%; W 3.0 wt.%; Al 0.28 wt.%; Ti 0.25 wt.%; Nb 0.73 wt.%; C 0.05 wt.%; with the balance being Ni.

[0088] Corrosion treatment: The base high-temperature alloy powder was placed in aqua regia (concentrated hydrochloric acid: concentrated nitric acid = 3:1) for chemical corrosion treatment for 30 seconds. Then the solution was discarded, and the chemically corroded powder was ultrasonically cleaned with alcohol (ultrasonic stirring for 60 minutes). Then the powder was settled, and the cleaning solution was removed and vacuum dried. The vacuum drying temperature was 200℃ and the vacuum drying time was 2 hours to obtain the corrosion-treated base high-temperature alloy powder (i.e., lightly corroded powder).

[0089] Mixing treatment: Nanoparticle powder and corrosion-treated high-temperature alloy matrix powder are added to an acoustic resonance device for acoustic resonance mixing treatment; the powder filling ratio is 90%, and the device is first vibrated for 5 minutes under an acceleration of 20g, and then vibrated for 50 minutes under an acceleration of 80g. The entire process is cooled by circulating water to obtain the mixed powder (i.e., acoustic resonance composite powder).

[0090] Removal of free nanoparticles: The mixed powder is ultrasonically stirred in alcohol for 30 minutes, followed by sedimentation (after ultrasonic stirring, the powder suspension is placed in a beaker and allowed to stand for 10-30 minutes, allowing larger particles to settle first, while free nanoparticles remain suspended in the upper liquid). The supernatant is then carefully discarded, and the settled powder is retained and vacuum dried. The vacuum drying temperature is 200-300℃, and the drying time is 1-4 hours. This process effectively removes unbound free nanoparticles, ensuring uniform surface loading and strong adhesion of the composite powder. After sieving through 270-mesh and 800-mesh sieves, a high-temperature alloy powder for additive manufacturing with good adhesion is obtained.

[0091] Figure 3 The figures show the typical morphology and elemental distribution characteristics of the high-temperature alloy powder for additive manufacturing prepared in Example 2; wherein, (a) is a low-magnification SEM image of the high-temperature alloy powder for additive manufacturing, (b) is a high-magnification SEM image of the high-temperature alloy powder for additive manufacturing, and (c) is an EDS elemental surface scan image of the high-temperature alloy powder for additive manufacturing. Figure 3 Figure (a) shows that the powder as a whole has good sphericity and particle size distribution. The surface of the powder after corrosion has a large number of fine particles attached, indicating that the effective composite of nanoparticles was achieved during the acoustic resonance treatment. Figure 3 Figure (b) shows a high-magnification SEM image of a single powder particle, which reveals a certain degree of roughness and irregular microstructure on its surface. This indicates that yttrium oxide particles are deposited in a relatively uniform manner and tightly adhered to the surface of the corroded matrix powder, providing a structural basis for enhancing laser absorption performance. Figure 3 Figure (c) shows the EDS elemental surface scan of the corresponding region. The results indicate that the Y element is uniformly dispersed on the powder surface, demonstrating that the acoustic resonance technology can achieve effective loading and uniform surface coverage of yttrium oxide nanoparticles. This composite powder structure helps improve laser absorption rate and molten pool stability, making it suitable for enhancing powder laser response performance in high-temperature alloy additive manufacturing.

[0092] Comparative Example 1

[0093] Comparative Example 1 describes the preparation of a high-temperature alloy powder for additive manufacturing, which mainly includes the following steps:

[0094] Raw material preparation: Select raw materials; wherein, by mass fraction, the raw materials include 99 wt.% matrix high-temperature alloy powder and 1 wt.% nanoparticle powder. The matrix high-temperature alloy powder has a particle size of 15-53 μm; the nanoparticle powder is selected from Y2O3 ceramic particles with a particle size of 100 nm.

[0095] The chemical composition of the matrix high-temperature alloy powder is as follows: Cr 28.3 wt.%; Co 33.0 wt.%; Re 1.40 wt.%; W 3.0 wt.%; Al 0.28 wt.%; Ti 0.25 wt.%; Nb 0.73 wt.%; C 0.05 wt.%; with the balance being Ni.

[0096] Mixing treatment: Nanoparticle powder and matrix high-temperature alloy powder are added to the acoustic resonance equipment for acoustic resonance mixing treatment; wherein, the powder filling ratio is 90%, and the mixture is first vibrated for 5 minutes under an acceleration of 20g, and then vibrated for 50 minutes under an acceleration of 80g; the entire process is cooled by circulating water to obtain the mixed powder (i.e., acoustic resonance composite powder).

[0097] Treatment to remove free nanoparticles: The mixed powder was placed in alcohol and ultrasonically stirred (for 30 minutes) to allow sedimentation. After the solution was discarded, vacuum drying was performed at a temperature of 200°C for 60 minutes to remove excess nanoparticles and obtain high-temperature alloy powder for additive manufacturing with good adhesion.

[0098] Figure 4 The typical morphology and elemental distribution characteristics of the additive manufacturing high-temperature alloy composite powder prepared in Comparative Example 1 are shown in Figure 1. (a) Figure 1 is a low-magnification SEM image of the additive manufacturing high-temperature alloy powder, (b) Figure 2 is a high-magnification SEM image of the additive manufacturing high-temperature alloy powder, and (c) Figure 3 is an EDS elemental surface scan image of the additive manufacturing high-temperature alloy powder.

[0099] Compared to the etched composite powders prepared in Examples 1 and 2, the powder prepared in Comparative Example 1 exhibits significant disadvantages in terms of microstructure. Specifically, Comparative Example 1, without etching treatment, has a relatively smooth powder surface and lacks effective micro / nano pit structures, resulting in a lower specific surface area. This makes it prone to specular reflection during laser irradiation, hindering effective coupling and absorption of laser energy. Furthermore, the powder in Comparative Example 1 also suffers from deficiencies in its composite structure. Its surface oxide particles are scattered and lack synergistic matching with the surface morphology of the matrix powder, making it difficult to form a stable "pit structure + light-absorbing particles" composite interface. Consequently, the multiple reflection absorption effect of laser on the powder surface is significantly weaker than that of the powders in the examples. In contrast, Examples 1 and 2 introduce uniform etched pits on the powder surface and combine them with nano-oxide particle composite treatment, significantly improving the powder's absorption rate of 1064nm laser light. This results in superior melt pool stability, forming density, and surface quality during subsequent laser additive manufacturing. In summary, Examples 1 and 2 demonstrate significant technical advantages in the control of powder microstructure, and are significantly superior to Comparative Example 1. The embodiments of the present invention can significantly improve the absorption performance and forming quality of powder materials during laser processing.

[0100] Comparative Example 2

[0101] Comparative Example 2 describes the preparation of a high-temperature alloy powder for additive manufacturing, which mainly includes the following steps:

[0102] Raw material preparation: Select raw materials; wherein, by mass fraction, the raw materials include 98 wt.% matrix high-temperature alloy powder and 2 wt.% nanoparticle powder. The matrix high-temperature alloy powder has a particle size of 15-53 μm; the nanoparticle powder is selected from Y2O3 ceramic particles with a particle size of 100 nm.

[0103] The chemical composition of the matrix high-temperature alloy powder is as follows: Cr 28.3 wt.%; Co 33.0 wt.%; Re 1.40 wt.%; W 3.0 wt.%; Al 0.28 wt.%; Ti 0.25 wt.%; Nb 0.73 wt.%; C 0.05 wt.%; with the balance being Ni.

[0104] Mixing treatment: Nanoparticle powder and matrix high-temperature alloy powder are added to the acoustic resonance equipment for acoustic resonance mixing treatment; wherein, the powder filling ratio is 90%, and the mixture is first vibrated for 5 minutes under an acceleration of 20g, and then vibrated for 50 minutes under an acceleration of 80g; the entire process is cooled by circulating water to obtain the mixed powder (i.e., acoustic resonance composite powder).

[0105] Treatment to remove free nanoparticles: The mixed powder was placed in alcohol and ultrasonically stirred (for 30 minutes) and settled. After the solution was discarded, it was vacuum dried at 200°C for 60 minutes to remove excess nanoparticles and obtain high-temperature alloy powder for additive manufacturing with good adhesion.

[0106] Figure 5 The typical morphology and elemental distribution characteristics of the additive manufacturing high-temperature alloy composite powder prepared in Comparative Example 2 are shown in Figure 2. (a) Figure 2 shows a low-magnification SEM image of the additive manufacturing high-temperature alloy powder, (b) Figure 2 shows a high-magnification SEM image of the additive manufacturing high-temperature alloy powder, and (c) Figure 3 shows an EDS elemental surface scan of the additive manufacturing high-temperature alloy powder.

[0107] Compared to the etched composite powders prepared in Examples 1 and 2, the powder prepared in Comparative Example 2 exhibits significant disadvantages in terms of microstructure. Specifically, Comparative Example 2, without etching treatment, has a relatively smooth powder surface and lacks effective micro / nano pit structures, resulting in a lower specific surface area. This makes it prone to specular reflection during laser irradiation, hindering effective coupling and absorption of laser energy. Furthermore, the powder in Comparative Example 2 also suffers from deficiencies in its composite structure. Its surface oxide particles are scattered and lack synergistic matching with the surface morphology of the matrix powder, making it difficult to form a stable "pit structure + light-absorbing particles" composite interface. Consequently, the multiple reflection absorption effect of laser on the powder surface is significantly weaker than that of the powders in the examples. In contrast, Examples 1 and 2 introduce uniform etched pits on the powder surface and combine them with nano-oxide particle composite treatment, significantly improving the powder's absorption rate of 1064nm laser light. This results in superior melt pool stability, forming density, and surface quality during subsequent laser additive manufacturing. In summary, Examples 1 and 2 demonstrate significant technical advantages in the control of powder microstructure, and are significantly superior to Comparative Example 2. The present invention can significantly improve the absorption performance and forming quality of powder materials during laser processing.

[0108] Comparative Example 3

[0109] Comparative Example 3 describes the preparation of a high-temperature alloy powder for additive manufacturing, which mainly includes the following steps:

[0110] Raw material preparation: Select raw materials; wherein, by mass fraction, the raw materials include 96 wt.% matrix high-temperature alloy powder and 4 wt.% nanoparticle powder. The matrix high-temperature alloy powder has a particle size of 15-53 μm; the nanoparticle powder is selected from Y2O3 ceramic particles with a particle size of 100 nm.

[0111] The chemical composition of the matrix high-temperature alloy powder is as follows: Cr 28.3 wt.%; Co 33.0 wt.%; Re 1.40 wt.%; W 3.0 wt.%; Al 0.28 wt.%; Ti 0.25 wt.%; Nb 0.73 wt.%; C 0.05 wt.%; with the balance being Ni.

[0112] Mixing treatment: Nanoparticle powder and matrix high-temperature alloy powder are added to the acoustic resonance equipment for acoustic resonance mixing treatment; wherein, the powder filling ratio is 90%, and the mixture is first vibrated for 5 minutes under an acceleration of 20g, and then vibrated for 50 minutes under an acceleration of 80g; the entire process is cooled by circulating water to obtain the mixed powder (i.e., acoustic resonance composite powder).

[0113] Treatment to remove free nanoparticles: The mixed powder was placed in alcohol and ultrasonically stirred (for 30 minutes) and settled. After the solution was discarded, vacuum drying was performed at a temperature of 200°C for 1 hour to remove excess nanoparticles and obtain high-temperature alloy powder for additive manufacturing with good adhesion.

[0114] Figure 6 The typical morphology and elemental distribution characteristics of the additive manufacturing high-temperature alloy composite powder prepared in Comparative Example 3 are shown in Figure 3. (a) Figure 3 shows a low-magnification SEM image of the additive manufacturing high-temperature alloy powder, (b) Figure 4 shows a high-magnification SEM image of the additive manufacturing high-temperature alloy powder, and (c) Figure 5 shows an EDS elemental surface scan of the additive manufacturing high-temperature alloy powder.

[0115] Compared to the etched composite powders prepared in Examples 1 and 2, the powder prepared in Comparative Example 3 exhibits significant disadvantages in terms of microstructure. Specifically, Comparative Example 3, without etching treatment, has a relatively smooth powder surface and lacks effective micro / nano pit structures, resulting in a lower specific surface area. This makes it prone to specular reflection during laser irradiation, hindering effective coupling and absorption of laser energy. Furthermore, the comparative example powder also suffers from deficiencies in its composite structure. Its surface oxide particles are scattered and lack synergistic matching with the surface morphology of the matrix powder, making it difficult to form a stable "pit structure + light-absorbing particles" composite interface. Consequently, the multiple reflection absorption effect of laser on the powder surface is significantly weaker than that of the example powders. In contrast, Examples 1 and 2 introduce uniform etched pits on the powder surface and combine them with nano-oxide particle composite treatment, significantly improving the powder's absorption rate of 1064nm laser light. This results in superior melt pool stability, forming density, and surface quality during subsequent laser additive manufacturing. In summary, Examples 1 and 2 demonstrate significant technical advantages in the control of powder microstructure, and are significantly superior to Comparative Example 3. The present invention can significantly improve the absorption performance and forming quality of powder materials during laser processing.

[0116] In summary, compared with Comparative Examples 1-3, Embodiments 1-2 of the present invention have at least the following beneficial effects:

[0117] 1) The powder prepared in the embodiments of the present invention has uniformly distributed nanoscale pits (approximately 50-200 nm in diameter) on its surface, which significantly improves the surface area.

[0118] 2) In this embodiment of the invention, the nano-oxide particles are embedded in the pits to form a "pit-particle-matrix" composite interface structure. Compared with the particles that are simply physically adsorbed in the comparative example, the bonding strength of the powder in this embodiment of the invention is significantly improved.

[0119] 3) For the powder prepared in the embodiments of the present invention, the EDS surface scan shows that the distribution of Y element is more continuous and uniform, and the particle agglomeration phenomenon is significantly reduced;

[0120] 4) For the powder prepared in the embodiments of the present invention, cross-sectional TEM observation showed that some nanoparticles were locally coated on the surface of the matrix, achieving a dual physical-chemical combination.

[0121] The aforementioned structural features make it easier for the composite powder to form a stable molten pool under laser irradiation, resulting in high absorption rate and uniform energy distribution.

[0122] Therefore, the powder prepared in this embodiment of the invention has a 10-25% higher absorption rate at a 1064nm laser wavelength, which effectively improves the energy utilization rate and forming stability of the laser molten pool.

[0123] Laser absorptivity tests were performed on the base high-temperature alloy powder, the high-temperature alloy powders for additive manufacturing prepared in Examples 1 and 2, and Comparative Examples 1-3. The test results are shown below. Figure 7 As shown.

[0124] like Figure 7 As shown, compared with the high-temperature alloy powder used in the matrix, and compared with the high-temperature alloy powder used in additive manufacturing prepared in Comparative Examples 1-3, the high-temperature alloy powder used in additive manufacturing prepared in this embodiment of the invention has a significantly improved laser absorption rate. From a theoretical perspective, the reason why the corrosion composite powder prepared in this embodiment of the invention is significantly superior to Comparative Examples 1-3 in terms of laser absorption rate is mainly due to the synergistic optimization of its powder surface structure and energy coupling mechanism. First, the powder in the embodiment undergoes controlled corrosion treatment, forming a uniformly distributed nanoscale pit structure on its surface, effectively increasing the specific surface area and surface roughness of the powder, thereby enhancing the multiple scattering effect and light trapping effect during laser irradiation, and significantly reducing specular reflection and energy loss of the laser. Second, high-absorbency nano-oxide particles (such as Y2O3) are further composited on the powder surface. These particles have high dielectric constants and optical absorption coefficients, enabling them to preferentially absorb energy under laser irradiation and conduct it to the metal matrix, forming local hot spots, which helps to improve laser melting efficiency and molten pool uniformity. More importantly, the synergistic "microstructure-functional material" system formed between the pit structure and the light-absorbing particles enhances the residence time and optical path complexity of the laser in the powder layer, further improving energy coupling efficiency. In contrast, the powders in Comparative Examples 1-3, without corrosion and composite treatment, have smooth surfaces and no significant structural features. Laser light on these surfaces is prone to specular reflection, resulting in low energy absorption efficiency and unstable molten pools during the forming process. Therefore, considering multiple mechanisms such as optical absorption, thermal conduction, and powder surface structure control, the embodiments of this invention possess superior laser energy absorption capabilities, significantly outperforming the comparative powders, and are suitable for high-energy beam additive manufacturing processes such as laser powder bed melting.

[0125] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A method for the production of a high-temperature alloy powder for additive manufacturing, characterized in that It includes the following steps: Raw material preparation: Select raw materials; wherein, the raw materials include matrix high-temperature alloy powder and nanoparticle powder; Corrosion treatment: The base high-temperature alloy powder is subjected to corrosion treatment to form a nano-pit structure on the surface of the base high-temperature alloy powder; then it is cleaned and dried to obtain the corrosion-treated base high-temperature alloy powder. Mixing treatment: The nanoparticle powder and the corrosion-treated matrix high-temperature alloy powder are mixed to load the nanoparticles onto the corrosion-treated matrix high-temperature alloy powder, resulting in a mixed powder. Treatment to remove free nanoparticles: The powder after the mixed treatment is subjected to treatment to remove free nanoparticles to obtain high-temperature alloy powder for additive manufacturing.

2. The method of producing a high-temperature alloy powder for additive manufacturing according to claim 1, characterized by, In the step of preparing raw materials: The raw materials comprise, by mass fraction, 96-99 wt.% matrix high-temperature alloy powder and 1-4 wt.% nanoparticle powder.

3. The method for preparing high-temperature alloy powder for additive manufacturing according to claim 1 or 2, characterized in that, In the step of preparing raw materials: The nanoparticle powder comprises one or more of ceramic particles, graphene particles, and rare earth particles; preferably, the ceramic particles are one or more of Y₂O₃ particles, ZrO₂ particles, and Al₂O₃ particles; the rare earth elements are one or more of La, Sc, and Ce particles; and / or The primary particle size range of the nanoparticle powder is 50-200 nm.

4. The method for preparing high-temperature alloy powder for additive manufacturing according to any one of claims 1-3, characterized in that, In the step of preparing raw materials: In the matrix high-temperature alloy powder: the mass percentage of Cr is 27.0-31.0 wt.%; the mass percentage of Co is 30.0-33.0 wt.%; the mass percentage of Re is 1.0-3.0 wt.%; the mass percentage of W is 1.0-4.0 wt.%; the mass percentage of Al is 0.1-1.0 wt.%; the mass percentage of Ti is 0.1-1.0 wt.%; the mass percentage of Nb is 0.1-1.0 wt.%; the mass percentage of C is 0.01-0.2 wt.%, with the balance being Ni; and / or The particle size of the matrix high-temperature alloy powder is 15-53 μm.

5. The method for preparing high-temperature alloy powder for additive manufacturing according to any one of claims 1-4, characterized in that, In the corrosion treatment step: The high-temperature alloy base powder was placed in aqua regia and chemically etched for 10-60 seconds to create nano-pits on the surface of the high-temperature alloy base powder. Preferably, after chemical etching, the powder after chemical etching is ultrasonically cleaned with a volatile cleaning solvent, then after sedimentation, the cleaning solution is removed and vacuum drying is performed to obtain the etched high-temperature alloy matrix powder; preferably, the volatile cleaning solvent is alcohol. More preferably, during the ultrasonic cleaning process: the ultrasonic vibration frequency is 15-35 kHz, the vibration mode is continuous vibration mode or pulse vibration mode, the ultrasonic cleaning time is 30-60 min, and the mechanical stirring speed is 50-150 r / min.

6. The method for preparing high-temperature alloy powder for additive manufacturing according to any one of claims 1-5, characterized in that, In the mixing process step: The corroded matrix high-temperature alloy powder and nanoparticle powder are placed in an acoustic resonance device for acoustic resonance mixing treatment, so as to load the nanoparticles on the corroded matrix high-temperature alloy powder to obtain the mixed powder. Preferably, the parameters of the acoustic resonance mixing process are as follows: the filling ratio is 80%-90%; first, vibrate for 5-10 minutes under an acceleration of 10-30g, and then vibrate for 50-70 minutes under an acceleration of 70-90g; Preferably, a cooling process is required during the acoustic resonance mixing process; preferably, the cooling process is a circulating water cooling process.

7. The method for preparing high-temperature alloy powder for additive manufacturing according to any one of claims 1-6, characterized in that, In the step of removing free-state nanoparticles: The mixed powder was placed in a volatile solvent, ultrasonically stirred, and then settled. After the solution was discarded, the powder was dried to obtain the composite powder. Preferably, the volatile solvent is alcohol; Preferably, the drying process is vacuum drying; wherein the temperature of the vacuum drying process is 200-300℃ and the time of the vacuum drying process is 1-4 hours.

8. The method for preparing high-temperature alloy powder for additive manufacturing according to any one of claims 1-7, characterized in that, The method for preparing the high-temperature alloy powder for additive manufacturing further includes: Sieving process: The high-temperature alloy powder for additive manufacturing is sieved to obtain high-temperature alloy powder for additive manufacturing with the required particle size; Preferably, the required particle size is 15-53 μm.

9. A high-temperature alloy powder for additive manufacturing, characterized in that, The high-temperature alloy powder for additive manufacturing is prepared by the method for preparing high-temperature alloy powder for additive manufacturing according to any one of claims 1-8.

10. The high-temperature alloy powder for additive manufacturing according to claim 9, characterized in that, The additive manufacturing high-temperature alloy powder comprises: a matrix high-temperature alloy powder with a nano-sized pit structure on its surface and nanoparticles; wherein the nanoparticles are loaded on the surface of the pit structure and the matrix high-temperature alloy powder. Preferably, the diameter of the pit structure is 50-200 nm and the depth is 20-100 nm; Preferably, the size of the nanoparticles is 50-150 nm; Preferably, the high-temperature alloy powder for additive manufacturing has an absorption rate of 75-85% at a 1064nm laser wavelength.

Images