A high-entropy alloy reinforced TC4 titanium alloy composite and a preparation method thereof
By using high-entropy alloys to reinforce TC4 titanium alloy composites, and by employing laser-directed energy deposition technology to prepare fine equiaxed crystals with BCC and HCP structures, the problem of insufficient strength of TC4 titanium alloy in additive manufacturing was solved, and high-performance near-net-shape forming was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- THE AFFILIATED HOSPITAL OF QINGDAO UNIV
- Filing Date
- 2026-04-27
- Publication Date
- 2026-06-16
AI Technical Summary
Traditional TC4 titanium alloys are difficult to control in terms of microstructure and properties in additive manufacturing to meet the service requirements of high-end equipment, especially due to insufficient strength at room temperature and the problem of strength-plasticity mismatch.
A composite material made of TC4 titanium alloy reinforced with high-entropy alloy was prepared by laser-directed energy deposition technology to prepare fine equiaxed grain structures of BCC and HCP. The material properties were then controlled by combining fine grain strengthening and dislocation strengthening mechanisms.
It significantly improves the yield strength and tensile strength of composite materials by 58% and 51% respectively, achieving high-performance near-net-shape forming and avoiding the complexity and high cost of traditional processes.
Smart Images
Figure CN122214710A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of microstructure and property control technology in laser-directed energy deposition additive manufacturing, and in particular to a high-entropy alloy-reinforced TC4 titanium alloy composite material and its preparation method. Background Technology
[0002] TC4 (Ti-6Al-4V) titanium alloy, due to its excellent specific strength, corrosion resistance, good biocompatibility, and wide operating temperature range, has become a core structural material in key fields such as aerospace, marine engineering, weaponry, and biomedicine. Additive manufacturing technologies such as laser-directed energy deposition (LDED) show great promise for the rapid fabrication of complex titanium alloy components due to their high efficiency, flexibility, and near-net-shape forming capabilities. However, with the increasing performance requirements of high-end equipment, the strength of traditional TC4 alloy at room temperature is gradually becoming insufficient to meet service requirements, especially in the field of additive manufacturing, where the control of its microstructure and properties faces more complex challenges. During laser additive manufacturing, the extremely high cooling rate and complex non-equilibrium thermal cycle result in coarse columnar crystals in titanium alloys, leading to anisotropic properties and a strong-plasticity mismatch, which greatly restricts the application of laser additive manufacturing technology in titanium alloy forming. Summary of the Invention
[0003] To overcome the aforementioned problems in the prior art, this invention proposes a high-entropy alloy-reinforced TC4 titanium alloy composite material and its preparation method.
[0004] The technical solution adopted by the present invention to solve its technical problem is: a composite material of high entropy alloy reinforced TC4 titanium alloy, wherein the composite material has a BCC and HCP structure and the grains are fine equiaxed crystals.
[0005] A method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material, used to prepare the composite material as described above, specifically includes the following steps: Step 1, substrate cleaning: Use industrial anhydrous ethanol to clean the substrate surface and remove oil and impurities. Step 2: Prepare the deposited powder, which includes TC4 titanium alloy powder and high-entropy alloy powder. Prepare TC4 composite powder with different contents of high-entropy alloy powder by planetary ball milling and dry at 120°C for two hours. Step 3, laser-directed energy deposition forming: by controlling the configuration of TC4 titanium alloy powder with different contents of high-entropy alloy powder, the TC4 mixed titanium alloy powder containing high-entropy alloy powder is placed in the laser additive powder feeding tank, and laser is used for melting deposition additive manufacturing.
[0006] In the above-mentioned method for preparing a high-entropy alloy reinforced TC4 titanium alloy composite material, the mass fraction of the high-entropy alloy powder in step 2 is 0.1 wt.%~10 wt.%.
[0007] The above-mentioned method for preparing a high-entropy alloy reinforced TC4 titanium alloy composite material, wherein the high-entropy alloy powder in step 2 is specifically a high-entropy alloy that can form a BCC+HCP dual-phase structure with TC4 titanium alloy and can achieve an equiaxed crystal structure through laser directional energy deposition.
[0008] The above-mentioned method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material, wherein the high-entropy alloy powder in step 2 is Al 0.5 CoCrFeNi high-entropy alloy powder, wherein Al 0.5 CoCrFeNi high-entropy alloy powder includes Al, Co, Cr, Fe, and Ni, with the following mass percentages: Al: 4.8%-5.9%, Co: 23.0%-25.5%, Cr: 20.5%-22.6%, Fe: 22.3%-24.5%, and Ni: 23.8%-25.0%.
[0009] The above-mentioned method for preparing a high-entropy alloy reinforced TC4 titanium alloy composite material, wherein the TC4 titanium alloy powder in step 2 includes Ti, Al, and V, wherein the mass percentage of Ti, Al, and V is: Ti≥90%, Al: 5.4%-6.2%, V: 3.8%-4.5%.
[0010] The above-mentioned method for preparing a high-entropy alloy reinforced TC4 titanium alloy composite material, wherein the high-entropy alloy powder has a particle size of 45μm-105μm and the TC4 powder has a particle size of 53μm-150μm.
[0011] The above-mentioned method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material includes the following process parameters during laser melting deposition: laser power of 1500W-3000W, scanning speed of 500mm / min-1500mm / min, and powder feeding rate of 5g / min-12g / min.
[0012] The beneficial effect of this invention is that it uses laser-directed energy deposition additive manufacturing technology to prepare TC4-Al 0.5 CoCrFeNi composite materials avoid the limitations of complex and costly traditional processes, can achieve near-net-shape forming, and can meet performance requirements without post-processing, effectively solving the problem of insufficient strength of existing additive manufacturing TC4 alloys.
[0013] This method achieves plastic deformation and recrystallization of the as-cast microstructure through layer-by-layer deposition, eliminating residual stress, and significantly improving the mechanical properties of the material through mechanisms such as grain refinement strengthening, dislocation strengthening, and dislocation reinforcement. At the optimal content, the composite material achieves a yield strength of 1397 MPa and a tensile strength of 1542 MPa, which are 58% and 51% higher than those of pure TC4 alloy, respectively, demonstrating excellent comprehensive mechanical properties.
[0014] With Al 0.5 TC4-Al was prepared using CoCrFeNi high-entropy alloy as the reinforcing phase and laser-directed energy deposition technology. 0.5 CoCrFeNi composite materials utilize the multi-component effect of high-entropy alloys and the rapid solidification characteristics of laser additive manufacturing to achieve the transformation from columnar crystals to equiaxed crystals. Through multiple mechanisms including grain refinement strengthening, dislocation strengthening, and solid solution strengthening, the mechanical properties of the material are significantly improved. This method provides a new approach for the preparation of high-performance titanium-based composite materials and has significant academic value and promising engineering applications. Attached Figure Description
[0015] Figure 1 These are microstructure images of TC4 titanium alloys reinforced with high-entropy alloys of different contents prepared according to embodiments of the present invention, wherein (a) is TC4-xwt.%Al prepared by laser-directed energy deposition. 0.5 Microstructure diagrams of CoCrFeNi (x=0, 3, 5, 7) composite materials; (a1) is the microstructure diagram of the composite material when x=0, (a2) is the microstructure diagram of the composite material when x=3, (a3) is the microstructure diagram of the composite material when x=5, and (a4) is the microstructure diagram of the composite material when x=7; (b1), (c1), and (d1) are magnified views of the upper, middle, and lower regions, respectively; (b2), (c2), and (d2) are magnified views of the upper, middle, and lower regions, respectively; (b3), (c3), and (d3) are magnified views of the upper, middle, and lower regions, respectively; (b3), (c3), and (d3) are magnified views of the upper, middle, and lower regions, respectively. Figure 2 It is TC4 titanium alloy and the 3.0wt% Al content prepared in this invention. 0.5 Tensile properties of CoCrFeNi reinforced TC4 titanium alloy. Detailed Implementation
[0016] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
[0017] This embodiment discloses an Al 0.5 The preparation method of the composite material of CoCrFeNi high-entropy alloy reinforced TC4 alloy includes the following steps: Step 1: Substrate cleaning treatment. Use industrial anhydrous ethanol to clean the surface of the substrate to remove oil and impurities, so as to avoid adverse effects on the forming process and alloy properties.
[0018] Step 2: Prepare the deposition powder, which includes TC4 titanium alloy powder and Al. 0.5 CoCrFeNi high-entropy alloy powder was prepared using a planetary ball mill to produce Al content powders of varying amounts. 0.5 The CoCrFeNi TC4 composite powder was dried at 120°C for two hours.
[0019] Al 0.5 The mass fraction (wt.%) of CoCrFeNi high-entropy alloy powder is 0.1%~10%, and the balance is TC4 titanium alloy powder.
[0020] Al 0.5 The particle size of CoCrFeNi high-entropy alloy powder is 45-105μm, and the particle size of TC4 powder is 53-150μm.
[0021] TC4 titanium alloy powder contains Ti, Al, and V, with the following mass percentages: Ti ≥ 90%, Al: 5.4%-6.2%, and V: 3.8%-4.5%. 0.5 The CoCrFeNi high-entropy alloy powder contains Al, Co, Cr, Fe, and Ni, with the following mass percentages: Al: 4.8%-5.9%, Co: 23.0%-25.5%, Cr: 20.5%-22.6%, Fe: 22.3%-24.5%, and Ni: 23.8%-25.0%.
[0022] Step 3: Laser-directed energy deposition to prepare TC4-Al 0.5 CoCrFeNi composite components were prepared. High-entropy alloy composite powders with different contents were prepared and formed layer-by-layer using laser-directed energy deposition (EDD). A 3-second interval was maintained between each deposition pass before proceeding to the next pass, with 25 cycles completed to achieve a forming height of 12 mm. The same experimental parameters were used to form components with different Al contents. 0.5 A CoCrFeNi-reinforced TC4 component was constructed using the following parameters: laser power of 2100W, scanning speed of 1000mm / min, and powder feed rate of 8g / min. The experimental substrate was a pure Ti plate with Al... 0.5 The particle size of CoCrFeNi high-entropy alloy powder is 45μm-105μm, and the particle size of TC4 powder is 53μm-150μm.
[0023] The microstructure and properties of laser-added TC4 titanium alloy were designed and controlled using Al, Co, Cr, Fe, and N elemental composition. Al is a stabilizing element for the α phase, while V, Cr, and Fe are stabilizing elements for the β phase. The relative contents of the α and β phases can be controlled to improve the strength and plasticity of the TC4 titanium alloy, and the grain morphology can be controlled to achieve the transformation from columnar to equiaxed grains. Plastic deformation and recrystallization of the as-cast microstructure are achieved through layer-by-layer deposition, residual stress is eliminated, and the mechanical properties of the TC4 alloy are significantly improved through mechanisms such as grain refinement strengthening and dislocation strengthening.
[0024] This embodiment also provides a method for controlling the microstructure and properties of TC4 titanium alloy by composition design. This method uses laser melting deposition additive manufacturing technology to improve the microstructure and properties of TC4 titanium alloy.
[0025] The specific technical solution is as follows: TC4-Al fabrication using laser melting deposition additive manufacturing 0.5 CoCrFeNi alloy was processed layer by layer, with a 3-second interval between each deposition pass before proceeding to the next, repeated 25 times to achieve a forming height of 12 mm. This method enables laser melting deposition additive manufacturing of TC4-Al. 0.5 Microstructure and property control of CoCrFeNi alloy. Specific steps are as follows: S1. Exploring suitable laser melting deposition of TC4-Al 0.5 Forming parameters for CoCrFeNi alloy, and forming TC4-Al using laser melting deposition technology. 0.5 CoCrFeNi alloy.
[0026] This embodiment includes the following features: The Al selected in step S1 0.5 CoCrFeNi powder and TC4 titanium alloy powder were used to prepare Al content powders of different amounts using a planetary ball mill. 0.5 CoCrFeNi TC4 composite powder was prepared and dried at 120℃ for two hours. The TC4 titanium alloy powder contains Ti, Al, and V, with the following mass percentages: Ti ≥ 90%, Al: 5.4%-6.2%, V: 3.8%-4.5%. 0.5 The CoCrFeNi high-entropy alloy powder contains Al, Co, Cr, Fe, and Ni, with the following mass percentages: Al: 4.8%-5.9%, Co: 23.0%-25.5%, Cr: 20.5%-22.6%, Fe: 22.3%-24.5%, and Ni: 23.8%-25.0%.
[0027] The laser melting deposition additive manufacturing process parameters in step S1 include: laser power, scanning speed, powder feeding speed, etc.
[0028] Al 0.5 The particle size of CoCrFeNi high-entropy alloy powder is 45-105μm, and the particle size of TC4 powder is 53-150μm.
[0029] The laser power control range of the laser melting deposition additive manufacturing system is 1500W-3000W.
[0030] The scanning speed control range of the laser melting deposition additive manufacturing system is 500 mm / min to 1500 mm / min.
[0031] The powder feeding speed control range of the laser melting deposition additive manufacturing system is 5g / min-12g / min.
[0032] This invention prepares TC4-Al using laser melting deposition additive manufacturing technology. 0.5 CoCrFeNi alloys can be prepared using a method that avoids the limitations of traditional processes, such as complexity and high cost, while also achieving a good balance between microstructure and properties. This method can be used as a preparation method for TC4-Al alloys. 0.5 Common methods for processing CoCrFeNi alloys.
[0033] Composite materials were prepared based on the above method. Figure 1 Demonstrates the preparation of TC4-Al by laser-directed energy deposition 0.5 The microstructure of the CoCrFeNi composite material and magnified observation of the upper, middle, and lower regions show that the TC4 alloy exhibits a coarse columnar crystal structure. However, the composite material after high-entropy alloying shows a transformation from coarse columnar crystals to fine equiaxed crystals.
[0034] Figure 2 The tensile properties of TC4 and a 3.0 wt% high-entropy alloy composite were compared. Experimental results showed that the TC4 alloy had a yield strength of 886 MPa and a tensile strength of 1021 MPa. The 3.0 wt% Al composite... 0.5 After CoCrFeNi reinforcement, the yield strength and tensile strength of the composite material increased to 1397 MPa and 1542 MPa, respectively, representing increases of 58% and 51%, significantly enhancing the mechanical properties of the material.
[0035] In summary, this invention discloses a TC4-Al 0.5 CoCrFeNi composite materials and their preparation methods: preparation of materials with different Al contents using a planetary ball mill. 0.5 A titanium-based composite material with high strength and good properties was successfully prepared by combining TC4 composite powder of CoCrFeNi high-entropy alloy with laser-directed energy deposition additive manufacturing technology. This method is simple and cost-effective, providing an effective approach for the preparation and promotion of high-performance TC4 alloys.
[0036] It should be noted that the present invention uses Al 0.5 This invention uses a CoCrFeNi high-entropy alloy as an example, but the technical concept is not limited to high-entropy alloys with this specific composition. From a theoretical perspective, high-entropy alloys possess four core effects: a high mixing entropy effect in thermodynamics, a hysteresis diffusion effect in kinetics, a lattice distortion effect, and a "cocktail" effect in performance. These effects enable high-entropy alloys of different systems (such as the CoCrFeNi system, refractory high-entropy alloy systems, and other component variants in the AlCoCrFeNi system) to improve the mechanical properties and anisotropy resistance of materials during laser-directed energy deposition. Specifically, the various alloying elements added to the high-entropy alloy (such as Al, Co, Cr, Fe, Ni, Ti, V, Mo, W, Zr, etc.) can induce compositional supercooling in the TC4 titanium alloy molten pool, promoting heterogeneous nucleation; simultaneously, the high mixing entropy characteristic of the high-entropy alloy lowers the nucleation barrier of the melt, which is beneficial for the transformation of columnar crystals to equiaxed crystals. Furthermore, the introduction of high-entropy alloys can significantly improve the yield strength and tensile strength of materials through various mechanisms such as solid solution strengthening, grain refinement strengthening, and dislocation strengthening, thereby significantly improving their service performance under extreme conditions. The high-entropy alloy Al used in this patent... 0.5 CoCrFeNi is just one of many high-entropy alloy systems, and its composition design and performance optimization provide a good foundation for subsequent research.
[0037] In fact, the composition of high-entropy alloys can be adjusted according to the performance requirements of the target material. For example, by introducing different proportions of transition metal elements (such as Ni, Fe, Co, Cr, etc.) or adding specific alloying elements (such as Al, Ti, V, etc.), the microstructure and properties of the material can be further optimized. This flexibility makes high-entropy alloys have broad application potential in different application scenarios, especially in fields with extremely high material performance requirements such as aerospace, marine engineering, and biomedicine.
[0038] Therefore, those skilled in the art should understand that any high-entropy alloy system (including but not limited to AlCoCrFeNi, CoCrFeMnNi, FeCoNiCrMn, TiZrHfNbTa, etc.) that can form a BCC+HCP dual-phase structure with TC4 titanium alloy and achieve an equiaxed crystal structure through laser-directed energy deposition falls within the scope of protection of this invention. Titanium alloy composite materials obtained by rationally selecting other high-entropy alloy systems based on the preparation method and microstructure control mechanism disclosed in this invention also fall within the substantive protection scope of this invention.
[0039] The above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art can make various modifications or equivalent substitutions to the present invention within its scope and spirit, and such modifications or equivalent substitutions should also be considered to fall within the scope of protection of the present invention.
Claims
1. A composite material of TC4 titanium alloy reinforced with a high-entropy alloy, characterized in that, The composite material has a BCC and HCP structure, and the grains are fine equiaxed crystals.
2. A method for preparing a composite material of high-entropy alloy-reinforced TC4 titanium alloy, characterized in that, The method for preparing the composite material as described in claim 1 specifically includes the following steps: Step 1, substrate cleaning: Use industrial anhydrous ethanol to clean the substrate surface and remove oil and impurities. Step 2: Prepare the deposited powder, which includes TC4 titanium alloy powder and high-entropy alloy powder. Prepare TC4 composite powder with different contents of high-entropy alloy powder by planetary ball milling and dry at 120°C for two hours. Step 3, laser-directed energy deposition forming: by controlling the configuration of TC4 titanium alloy powder with different contents of high-entropy alloy powder, the TC4 mixed titanium alloy powder containing high-entropy alloy powder is placed in the laser additive powder feeding tank, and laser is used for melting deposition additive manufacturing.
3. The method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material according to claim 2, characterized in that, In step 2, the high-entropy alloy powder is specifically a high-entropy alloy that can form a BCC+HCP dual-phase structure with TC4 titanium alloy and can achieve an equiaxed crystal structure through laser-directed energy deposition.
4. The method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material according to claim 2, characterized in that, In step 2, the high-entropy alloy powder is Al. 0.5 CoCrFeNi high-entropy alloy powder, wherein Al 0.5 CoCrFeNi high-entropy alloy powder includes Al, Co, Cr, Fe, and Ni, with the following mass percentages: Al: 4.8%-5.9%, Co: 23.0%-25.5%, Cr: 20.5%-22.6%, Fe: 22.3%-24.5%, and Ni: 23.8%-25.0%.
5. The method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material according to claim 2, characterized in that, In step 2, the mass fraction of the high-entropy alloy powder is 0.1 wt.% to 10 wt.%.
6. The method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material according to claim 2, characterized in that, In step 2, the TC4 titanium alloy powder contains Ti, Al, and V, with the following mass percentages: Ti ≥ 90%, Al: 5.4%-6.2%, and V: 3.8%-4.5%.
7. The method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material according to claim 2, characterized in that, The high-entropy alloy powder has a particle size of 45μm-105μm, and the TC4 powder has a particle size of 53μm-150μm.
8. The method for preparing a high-entropy alloy-reinforced TC4 titanium alloy composite material according to claim 2, characterized in that, The process parameters for the laser melting deposition process are as follows: laser power of 1500W-3000W, scanning speed of 500mm / min-1500mm / min, and powder feeding rate of 5g / min-12g / min.