SiC whisker reinforced niobium-based composite material and preparation method thereof
By combining high-energy ball milling of SiC whiskers and niobium alloy powder with laser-directed energy deposition technology, the problems of uneven distribution of SiC whiskers and interfacial reactions in niobium alloys were solved, thereby improving the mechanical properties and manufacturing efficiency of niobium-based composite materials.
Patent Information
- Application Number
- CN202511416903.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-30
- Publication Date
- 2026-01-27
AI Technical Summary
Traditional niobium alloys suffer from insufficient room temperature strength, poor high temperature stability, and weak work hardening ability in the aerospace field. Furthermore, SiC whiskers are difficult to distribute uniformly in the metal matrix and are prone to interfacial reactions, which affect the performance of composite materials.
High-energy ball milling of SiC whiskers and niobium alloy powder combined with laser-directed energy deposition technology was used to achieve grain refinement and optimization of the second phase distribution. By alternating ball milling and laser-directed energy deposition technology, SiC whiskers were ensured to be uniformly distributed in the niobium alloy matrix and form a strong interfacial bond.
It significantly improves the mechanical properties of niobium-based composites, including yield strength, tensile strength, and elongation, making them suitable for the direct manufacture of complex-shaped components, shortening production cycles and reducing costs.
Smart Images
Figure CN121406989A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of metal matrix composite technology, specifically relating to a SiC whisker-reinforced niobium matrix composite material and its preparation method. Background Technology
[0002] Niobium-based alloys, with their low density, high melting point, and excellent high-temperature mechanical properties, have long played a crucial role in the aerospace field (such as rockets, satellites, and hypersonic vehicles). These characteristics also make niobium alloys an ideal choice for next-generation high-temperature structural materials. With the continuous development of the aerospace industry, higher demands are being placed on the mechanical properties of niobium alloys. Traditional niobium alloys generally suffer from insufficient room-temperature strength, poor high-temperature stability, and weak work hardening ability, which seriously restricts their further development and application. Therefore, it is urgent to further improve their mechanical properties.
[0003] In recent years, researchers have attempted to introduce various reinforcing materials to improve the mechanical properties of niobium-based alloys. Among them, silicon carbide (SiC) is widely recognized as one of the most ideal reinforcing materials for ultra-high temperature materials due to its excellent properties such as high melting point, high strength, low density, and good oxidation resistance. Crucially, silicon carbide whiskers (SiC...) w Compared to SiC particles, SiC exhibits more significant mechanical reinforcement advantages. As an important reinforcing material, it has achieved great success in improving the mechanical properties of traditional ceramic matrix composites. However, in metal matrix systems, SiC... w When used in metal-based composite systems, SiC is difficult to distribute uniformly in molten metal due to its density differences and high surface energy; furthermore, SiC... w During high-temperature preparation, SiC readily undergoes interfacial reactions with the metal matrix, generating brittle phases that affect interfacial bonding strength and consequently degrade the composite material's properties. This is especially true for niobium-based alloys, for which there are currently no research reports on the effectiveness of adding SiC. w To enhance. Summary of the Invention
[0004] This invention aims to at least partially solve one of the technical problems in related technologies. Therefore, the main objective of this invention is to provide a SiC whisker-reinforced niobium-based composite material.
[0005] The present invention also provides a method for preparing the SiC whisker-reinforced niobium-based composite material. This method combines the addition of SiC whiskers with laser additive manufacturing to achieve grain refinement and optimization of the second phase distribution, thereby improving the mechanical properties of the material.
[0006] The objective of this invention is achieved through the following technical solution: In a first aspect, a method for preparing a SiC whisker-reinforced niobium-based composite material includes the following steps: 1) The SiC whiskers and niobium alloy powder of the specified amount were subjected to high-energy ball milling to obtain niobium alloy-SiC whisker composite powder; 2) Niobium alloy-SiC whisker composite powder was shaped and printed using laser-directed energy deposition technology to obtain SiC whisker-reinforced niobium-based composite material.
[0007] In some specific embodiments, the SiC whisker-reinforced niobium-based composite material obtained in step 2) is further subjected to heat treatment.
[0008] In some specific embodiments, the SiC whisker-reinforced niobium-based composite material comprises, by mass percentage: 96-99% niobium alloy matrix and 1%-4% SiC whiskers.
[0009] The niobium alloy matrix comprises the following elements by weight percentage: W: 5wt%, Mo: 2wt%, Zr: 1wt%, with the balance being Nb.
[0010] In some specific embodiments, the SiC whiskers have a diameter of 0.1-0.6 μm and a length of 10-50 μm.
[0011] In some specific embodiments, during the high-energy ball milling process described in step 1), the ball mill rotates alternately in clockwise and counterclockwise directions.
[0012] In some specific embodiments, the high-energy ball milling in step 1) is carried out in a ball mill using an agate ball milling jar, with the ball milling speed set to 50-250 rpm and the ball milling time to 0.5-5 h.
[0013] In some specific embodiments, the laser directional energy deposition printing parameters in step 2) are set as follows: laser power 2000-3000W, scanning speed 500-800mm / min, powder feeding rate 10-20g / min, spot diameter 3-8mm, lift 0.1-0.2mm, protective gas is argon, and gas flow rate is 15-25L / min.
[0014] In some specific embodiments, the heat treatment includes solution treatment and aging treatment, wherein the process conditions for solution treatment are: holding at 1300-1500℃ for 2-4 hours, and then water cooling to room temperature; the process conditions for aging treatment are: holding at 700-900℃ for 4-8 hours.
[0015] As part of the same inventive concept, the present invention also provides a SiC whisker-reinforced niobium-based composite material.
[0016] Compared with the prior art, the present invention has at least the following advantages: 1) This invention uses an agate grinding jar to avoid contamination from impurities during the grinding process, and employs a planetary grinding mill for alternating rotation to ensure the SiC... w While ensuring uniform mixing with the niobium alloy matrix powder, the risk of whisker breakage is reduced; combined with the rapid solidification characteristics of laser-directed energy deposition (L-DED), whisker agglomeration and interfacial reactions are effectively suppressed, achieving SiC... w High survival rate and tough interface construction in niobium alloy matrix.
[0017] 2) This invention achieves near-net-shape forming through L-DED, and rapid solidification significantly refines the alloy grains; SiC w It forms a strong interfacial bond with the niobium alloy matrix, which can both hinder dislocation movement and improve strength, and absorb crack energy and toughen through whisker pull-out and bridging effects; SiC w It exhibits a directional distribution trend in the matrix, further optimizing the anisotropy of mechanical properties.
[0018] 3) This invention is applicable to the direct manufacturing of complex-shaped components without the need for large equipment such as traditional forging, which shortens the production cycle and reduces manufacturing costs, especially meeting the needs of high-performance complex components in the aerospace field. Attached Figure Description
[0019] To more clearly illustrate the specific embodiments of the present invention, the accompanying drawings used in the description of the specific embodiments or the prior art will be briefly introduced below.
[0020] Figure 1 This is a SEM image of the SiC whisker-reinforced niobium-based composite material provided in Example 1 of the present invention; Figure 2 This is a process diagram of laser-directed energy deposition in the preparation method provided in Embodiment 1 of the present invention; Figure 3 Microstructure images of SiC whisker-reinforced niobium-based composite materials provided in Example 1(a) and Comparative Example 1(b) of the present invention; Figure 4 The SEM image of the SiC whisker-reinforced niobium-based composite material treated with conventional niobium alloy heat treatment process provided in Comparative Example 5 of this invention. Detailed Implementation
[0021] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. The following embodiments are merely descriptive and not limiting, and should not be construed as limiting the scope of protection of the present invention.
[0022] When a quantity, concentration, or other value or parameter is described as a range, preferred range, or preferred upper and lower limits, it should be understood that it is equivalent to specifically disclosing any range by combining any pair of upper or preferred values with any lower or preferred values, regardless of whether the range is specifically disclosed. Unless otherwise stated, the numerical range values listed herein include the endpoints of the range and all integers and fractions within that range.
[0023] Unless otherwise stated, all percentages, parts, ratios, etc. in this document are by weight.
[0024] The materials, methods, and embodiments described herein are exemplary and should not be construed as limiting unless otherwise stated.
[0025] In the following embodiments, the niobium alloy matrix is described using Nb521 as an example. The niobium alloy matrix (Nb521) includes the following elements by weight percentage: W: 5wt%, Mo: 2wt%, Zr: 1wt%, with the balance being Nb.
[0026] The SiC whiskers have a diameter of 0.1-0.6 μm and a length of 10-50 μm.
[0027] Example 1 This embodiment provides a method for preparing SiC whisker-reinforced niobium-based composite materials, including the following steps: (1) The niobium alloy matrix is Nb521 alloy powder, which contains W 5wt%, Mo 2wt%, Zr 1wt% by weight, with the balance being Nb; the reinforcing material is SiC. w The diameter is 0.1-0.6 μm, the length is 10-50 μm, and the addition amount is 1% of the weight of the niobium alloy matrix; (2) SiC w Nb521 alloy powder was placed in an agate ball mill jar according to the above ratio and subjected to high-energy ball milling using a planetary ball mill. The ball milling speed was set to 150 rpm and the ball milling time was 2 hours. During the ball milling process, the ball mill rotated clockwise and counterclockwise alternately every 10 minutes to obtain Nb521-SiC. w Composite powder; (3) Laser-guided energy deposition equipment was used to deposit Nb521-SiC w Composite powder was used for molding and printing; the printing parameters were set as follows: laser power 2000W, scanning speed 500mm / min, powder feeding rate 10g / min, spot diameter 3mm, lift 0.10mm, protective gas was argon, gas flow rate 20L / min, and SiC whisker-reinforced niobium-based composite material blank was obtained. (4) The printed SiC whisker-reinforced niobium-based composite material blank was subjected to solution treatment at 1400℃ for 3 hours, and then water-cooled to room temperature; finally, it was subjected to aging treatment at 800℃ for 6 hours to obtain the SiC whisker-reinforced niobium-based composite material; the SEM image of the SiC whisker-reinforced niobium-based composite material prepared in this application is shown below. Figure 1 As shown.
[0028] Example 2 This embodiment provides a method for preparing SiC whisker-reinforced niobium-based composite materials, including the following steps: (1) The niobium alloy matrix is Nb521 alloy powder, which contains W 5wt%, Mo 2wt%, Zr 1wt% by weight, with the balance being Nb; the reinforcing material is SiC. w The diameter is 0.1-0.6 μm, the length is 10-50 μm, and the addition amount is 2.5% of the weight of the niobium alloy matrix; (2) SiC w Nb521 alloy powder was placed in an agate ball mill jar according to the above ratio and subjected to high-energy ball milling using a planetary ball mill. The ball milling speed was set to 150 rpm and the ball milling time was 2 hours. During the ball milling process, the ball mill rotated clockwise and counterclockwise alternately every 10 minutes to obtain Nb521-SiC. w Composite powder; (3) Laser-guided energy deposition equipment was used to deposit Nb521-SiC w Composite powder was used for molding and printing; the printing parameters were set as follows: laser power 2500W, scanning speed 600mm / min, powder feed rate 15g / min, spot diameter 5mm, lift 0.15mm, protective gas argon, gas flow rate 20L / min, to obtain SiC whisker-reinforced niobium-based composite material blanks (the schematic diagram of the L-DED process for preparing SiC whisker-reinforced niobium-based composite materials is shown in Figure 1). Figure 2 (as shown) (4) The printed SiC whisker-reinforced niobium-based composite material blank is subjected to solution treatment, kept at 1400℃ for 3 hours, and then water-cooled to room temperature; finally, it is subjected to aging treatment, kept at 800℃ for 6 hours to obtain SiC whisker-reinforced niobium-based composite material.
[0029] Example 3 This embodiment provides a method for preparing SiC whisker-reinforced niobium-based composite materials, including the following steps: (1) The niobium alloy matrix is Nb521 alloy powder, which contains W 5wt%, Mo 2wt%, Zr 1wt% by weight, with the balance being Nb; the reinforcing material is SiC. wThe diameter is 0.1-0.6 μm, the length is 10-50 μm, and the addition amount is 4% of the weight of the niobium alloy matrix; (2) SiC w Nb521 alloy powder was placed in an agate ball mill jar according to the above ratio and subjected to high-energy ball milling using a planetary ball mill. The ball milling speed was set to 150 rpm and the ball milling time was 2 hours. During the ball milling process, the ball mill rotated clockwise and counterclockwise alternately every 10 minutes to obtain Nb521-SiC. w Composite powder; (3) Laser-guided energy deposition equipment was used to deposit Nb521-SiC w Composite powder was used for molding and printing; the printing parameters were set as follows: laser power 3000W, scanning speed 800mm / min, powder feeding rate 20g / min, spot diameter 5mm, lift 0.15mm, protective gas was argon, gas flow rate 25L / min, and SiC whisker-reinforced niobium-based composite material blank was obtained. (4) The printed SiC whisker-reinforced niobium-based composite material blank is subjected to solution treatment, kept at 1500℃ for 2 hours, and then water-cooled to room temperature; finally, it is subjected to aging treatment, kept at 900℃ for 4 hours to obtain SiC whisker-reinforced niobium-based composite material.
[0030] Comparative Example 1 Comparative Example 1 provides a method for preparing a niobium alloy matrix, which is basically the same as that in Example 1, except that SiCw is not added. Specifically: The niobium alloy matrix is Nb521 alloy powder, which contains W 5wt%, Mo 2wt%, Zr 1wt% by weight, with the balance being Nb; 2) Place the Nb521 alloy powder into an agate ball mill jar according to the above proportion, and perform high-energy ball milling using a planetary ball mill; set the ball milling speed to 150 rpm and the ball milling time to 2 hours; during the ball milling process, the ball mill rotates clockwise and counterclockwise alternately, once every 10 minutes, to obtain Nb521 alloy powder. 3) Nb521 alloy powder was shaped and printed using a laser directional energy deposition equipment. The printing parameters were set as follows: laser power 2000W, scanning speed 500mm / min, powder feeding rate 10g / min, spot diameter 3mm, lift 0.10mm, protective gas argon, gas flow rate 20L / min, to obtain niobium alloy matrix material blanks. (4) The printed niobium alloy matrix material blank is subjected to solution treatment, held at 1400℃ for 3 hours, and then water-cooled to room temperature; finally, it is subjected to aging treatment, held at 800℃ for 6 hours to obtain pure Nb521 alloy.
[0031] Comparative Example 2 Comparative Example 1 provides a method for preparing a niobium alloy matrix, which is basically the same as that in Example 1, except that step 2) uses only a single ball milling process, specifically: (1) The niobium alloy matrix is Nb521 alloy powder, which contains W 5wt%, Mo 2wt%, Zr 1wt% by weight, with the balance being Nb; the reinforcing material is SiC. w The diameter is 0.1-0.6 μm, the length is 10-50 μm, and the addition amount is 1% of the weight of the niobium alloy matrix; (2) SiC w Nb521 alloy powder was placed in an agate ball mill jar according to the above ratio and subjected to high-energy ball milling using a planetary ball mill. The ball milling speed was set to 150 rpm and the ball milling time was 2 hours. During the ball milling process, the ball mill rotated clockwise to obtain Nb521-SiC. w Composite powder; (3) Laser-guided energy deposition equipment was used to deposit Nb521-SiC w Composite powder was used for molding and printing; the printing parameters were set as follows: laser power 2000W, scanning speed 500mm / min, powder feeding rate 10g / min, spot diameter 3mm, lift 0.10mm, protective gas was argon, gas flow rate 20L / min, and SiC whisker-reinforced niobium-based composite material blank was obtained. (4) The printed SiC whisker-reinforced niobium-based composite material blank is subjected to solution treatment, kept at 1400℃ for 3 hours, and then water-cooled to room temperature; finally, it is subjected to aging treatment, kept at 800℃ for 6 hours to obtain SiC whisker-reinforced niobium-based composite material.
[0032] Comparative Example 3 Comparative Example 1 provides a method for preparing a niobium alloy matrix, which is basically the same as that in Example 1, except that SiC particles are used instead of SiC. w Specifically: (1) The niobium alloy matrix is Nb521 alloy powder, which contains W 5wt%, Mo 2wt%, Zr 1wt% by weight, with the balance being Nb; the reinforcing material is SiC with a particle size of 0.5μm, and the amount added is 1% of the weight of the niobium alloy matrix; (2) SiC and Nb521 alloy powders were placed in an agate ball mill jar according to the above ratio and subjected to high-energy ball milling using a planetary ball mill. The ball milling speed was set to 150 rpm and the ball milling time was 2 h. During the ball milling process, the ball mill was rotated clockwise and counterclockwise alternately every 10 minutes to obtain Nb521-SiC composite powder. (3) The Nb521-SiC composite powder was shaped and printed using a laser directional energy deposition equipment. The printing parameters were set as follows: laser power 2000W, scanning speed 500mm / min, powder feeding rate 10g / min, spot diameter 3mm, lift 0.10mm, protective gas argon, gas flow rate 20L / min, and SiC reinforced niobium-based composite material blank was obtained. (4) The printed SiC reinforced niobium-based composite material blank is subjected to solution treatment, kept at 1400℃ for 3 hours, and then water-cooled to room temperature; finally, it is subjected to aging treatment, kept at 800℃ for 6 hours to obtain SiC reinforced niobium-based composite material.
[0033] Comparative Example 4 Comparative Example 1 provides a method for preparing a niobium alloy matrix, which is basically the same as that in Example 1, except that aluminum alloy powder is used instead of niobium alloy powder. As a result, the Al element in the aluminum alloy (model 7075) is prone to react with SiC to form a brittle phase Al4C3, which in turn affects the interfacial bonding and final properties.
[0034] Comparative Example 5 Comparative Example 5 provides a method for preparing a niobium alloy matrix, which is basically the same as that of Example 1, except that the heat treatment process is different. Specifically, steps (1), (2), and (3) are the same as those in Example 1. Step (4) is to perform solid solution treatment on the printed SiC whisker-reinforced niobium-based composite material blank, keep it at 1300°C for 2 hours, and then furnace cool it to room temperature to obtain the SiC whisker-reinforced niobium-based composite material.
[0035] The resulting SiC whisker-reinforced niobium-based composite material has coarse grains (e.g., ...). Figure 4 As shown in the figure, this leads to a decrease in mechanical properties.
[0036] This application conducted room temperature tensile mechanical tests on the materials prepared in Examples 1, 3, and Comparative Examples 1-3. The test results are shown in Table 1. Table 1. Mechanical properties of materials prepared in each embodiment and comparative example. As can be seen from the data in Table 1, compared to Comparative Example 1 without SiC addition... w The Nb521 alloy prepared by the method shown in Example 1 exhibited significantly improved SiC whisker-reinforced niobium-based composite material. This is because SiC... w As heterogeneous nucleation sites, they promote heterogeneous nucleation of the melt during the rapid solidification process of laser-directed energy deposition, achieving grain refinement (fine grain strengthening). The crystal phase diagrams of the composite materials prepared in Example 1 and Comparative Example 1 are respectively derived from... Figure 3(as shown in 3(a) and 3(b)), simultaneously improving strength and toughness. Furthermore, SiC w SiC forms a strong interfacial bond with the niobium matrix, transferring external stress from the matrix to the high-strength whiskers through a load transfer effect, significantly improving the material's load-bearing capacity; simultaneously, during material fracture under stress, SiC... w The pull-out and bridging effects consume a large amount of energy, effectively inhibiting crack propagation, thereby significantly improving fracture toughness and elongation.
[0037] Compared to the unidirectional ball milling process used in Comparative Example 2, the SiC whisker-reinforced niobium-based composite material prepared by the alternating ball milling method in Example 1 exhibits superior performance. This is because the alternating clockwise and counterclockwise ball milling (alternating every 10 minutes) avoids the SiC... w Under uniaxial shear force, directional agglomeration and excessive fracture occur, resulting in a more uniform distribution of whiskers in the Nb521 matrix and the retention of more intact whiskers; uniformly distributed SiC w It can more effectively hinder dislocation movement and play a more significant pull-out toughening role during fracture; while the local agglomeration of whiskers caused by unidirectional ball milling is prone to forming stress concentration points, which reduces the mechanical properties of the material.
[0038] In Comparative Example 3, the SiC particle-reinforced niobium-based composite material prepared with SiC particles showed a significant increase in strength, but also increased brittleness. In contrast, the SiC whisker-reinforced niobium-based composite material in Example 1 exhibited more pronounced advantages. This is because SiC... w The high aspect ratio (10-50 μm / 0.1-0.6 μm) of whiskers makes them far superior to equal-volume-fraction SiC particles in terms of load transfer, crack bridging, and pull-out toughening. The linear distribution of whiskers can form a continuous strengthening network, while particles can only achieve local strengthening through point contact. In addition, whiskers have a more significant disturbance to melt flow, promoting more uniform grain refinement, while particles have lower heterogeneous nucleation efficiency and are prone to forming micropores at the interface, resulting in a decrease in elongation.
[0039] Example 1 uses a lower addition amount (1 wt%) and a lower laser power, while Example 3 uses an upper addition amount (4 wt%) and a higher energy input. The two examples serve as a comparison to demonstrate the different SiC addition amounts. w The effect of SiC content on microstructure evolution and mechanical properties. Table 1 shows that SiC... w With increasing SiC whisker content, the yield strength, tensile strength, and elongation of niobium-based composites all increase. w The increased number of particles provides more heterogeneous nucleation sites, which contributes more to grain refinement and crack arrest, thus achieving the enhancement and toughening of SiC particle-reinforced niobium-based composites.
[0040] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be covered within the scope of the claims and specification of the present invention.
Claims
1. A method for preparing SiC whisker-reinforced niobium-based composite materials, characterized in that, Includes the following steps: 1) The SiC whiskers and niobium alloy powder of the specified amount were subjected to high-energy ball milling to obtain niobium alloy-SiC whisker composite powder; 2) Niobium alloy-SiC whisker composite powder was shaped and printed using laser-directed energy deposition technology to obtain SiC whisker-reinforced niobium-based composite material.
2. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 1, characterized in that, It also includes heat treatment of the SiC whisker-reinforced niobium-based composite material obtained in step 2).
3. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 1 or 2, characterized in that, The SiC whisker-reinforced niobium-based composite material comprises, by mass percentage: 96-99% niobium alloy matrix and 1%-4% SiC whiskers.
4. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 3, characterized in that, The SiC whiskers have a diameter of 0.1-0.6 μm and a length of 10-50 μm.
5. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 1, characterized in that, During the high-energy ball milling process described in step 1), the ball mill rotates alternately in clockwise and counterclockwise directions.
6. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 5, characterized in that, Step 1) The high-energy ball milling is carried out in a ball mill using an agate ball mill jar, with the ball milling speed set to 50-250 rpm and the ball milling time to 0.5-5 h.
7. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 1, characterized in that, The printing parameters for the laser directional energy deposition technology described in step 2) are set as follows: laser power 2000-3000W, scanning speed 500-800mm / min, powder feeding rate 10-20g / min, spot diameter 3-8mm, lift 0.1-0.2mm, protective gas is argon, and gas flow rate is 15-25L / min.
8. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 2, characterized in that, The heat treatment includes solution treatment and aging treatment. The process conditions for solution treatment are: holding at 1300-1500℃ for 2-4 hours, and then water cooling to room temperature. The process conditions for aging treatment are: holding at 700-900℃ for 4-8 hours.
9. The method for preparing SiC whisker-reinforced niobium-based composite material according to claim 2, characterized in that, The preparation method is also applicable to other alloys that do not react with SiC whiskers, including but not limited to nickel-based alloys and titanium alloys.
10. A SiC whisker-reinforced niobium-based composite material prepared by the preparation method according to any one of claims 1-9.