Additive manufacturing method of high-temperature-resistant titanium-based composite material with good room-temperature strength and plasticity matching
By combining selective laser melting with annealing heat treatment, the problems of interfacial reaction and insufficient high-temperature mechanical properties of titanium-based composite materials during extremely rapid melting and solidification were solved. High-temperature resistant titanium-based composite materials with excellent room-temperature strength and plasticity were prepared, realizing efficient forming and high-temperature performance improvement of the materials.
Patent Information
- Application Number
- CN202511629172.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-07
- Publication Date
- 2026-01-30
AI Technical Summary
In existing technologies, when selective laser melting is used to prepare titanium-based composite materials, the reinforcing phase and the titanium matrix are prone to adverse interfacial reactions during the extremely rapid melting and solidification process, resulting in brittle phases, which lead to defects such as pores and microcracks inside the material. Furthermore, the high-temperature mechanical properties are poor, making it difficult to achieve both high-temperature resistance and good room-temperature strength and plasticity.
A titanium-based composite material was prepared by selective laser melting combined with annealing heat treatment. TiB2 and Si powders were mixed by low-energy ball milling as reinforcing phases. Annealing heat treatment was then performed in the α+β two-phase region to release residual stress and regulate the microstructure.
A high-temperature resistant titanium-based composite material with good room temperature strength and plasticity matching was prepared. The material has good formability, room temperature tensile strength ≥1190 MPa, elongation ≥10%, and tensile strength ≥410 MPa at 700 ℃, which significantly improves the high temperature strength and plasticity of the material.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of metal matrix composites, in particular to an additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strength-plasticity matching. BACKGROUND
[0002] With the improvement of performance requirements such as flight distance, flight speed and service life of aerospace vehicles, the key components such as the head shell of the vehicle are subjected to severe aerodynamic thermal cycle load during flight, and the temperature they bear is gradually increasing. The traditional titanium alloy components have the problem of being difficult to break through the 600 ℃ use temperature bottleneck, and cannot meet the design requirements. High-temperature alloys cannot meet the weight reduction requirements, although they have high heat resistance. In addition, due to the complex shape and structure of the head shell and other components such as the air rudder, the traditional subtractive manufacturing method has a long processing cycle and low material utilization rate, which is difficult to adapt to the efficient production and manufacturing of complex shell components. Titanium-based composites, by introducing ceramic whisker or particle reinforcement into the titanium alloy matrix, have higher strength, modulus, heat resistance and service temperature while maintaining a density similar to that of titanium alloy, and have broad application prospects in aerospace and transportation fields.
[0003] Selective laser melting is a kind of laser additive manufacturing, whose working principle is: first, lay a very thin layer of metal powder on the forming platform, and then according to the slice data of the three-dimensional model of the part, the high-energy laser beam selectively scans and irradiates, completely melts and solidifies the powder in the specified area to form a part; then the forming platform is lowered, a new layer of powder is laid, and the scanning and melting process is repeated, and it is firmly combined with the previous layer; in this way, the three-dimensional metal parts are finally manufactured from loose powder. Its core advantage is that it can directly manufacture dense metal parts with complex geometry and mechanical properties close to forged parts, thereby achieving unprecedented design freedom and manufacturing efficiency. At the same time, the un-melted powder can be recycled and reused, and the material utilization rate is much higher than that of traditional cutting processing. During the preparation process, no complex mold is needed, which is suitable for rapid manufacturing of small batches and complex parts, greatly shortening the research and production cycle.
[0004] Titanium-based composites achieve significant performance improvements by introducing high-strength reinforcing phases into a titanium alloy matrix. Their core advantages lie in their superior specific strength, excellent high-temperature performance, and outstanding wear resistance. While their density is similar to that of traditional titanium alloys, their strength and hardness are significantly higher. They also maintain strength and creep resistance at higher temperatures, while greatly improving wear resistance, making them an ideal choice for cutting-edge equipment in aerospace, biomedical, and other fields. Currently, the processes for preparing titanium-based composites using traditional methods such as hot pressing and casting are relatively mature. However, selective laser melting (SLM) for preparing titanium-based composites still faces unresolved issues. During extremely rapid solidification, the reinforcing phase and the titanium matrix are prone to adverse interfacial reactions, generating brittle phases. Furthermore, the poor wettability of the reinforcing phase makes uniform distribution difficult, leading to defects such as porosity and microcracks within the material and inducing significant residual thermal stress. Ultimately, although the strength and hardness of the composite material are improved, its plasticity and toughness often deteriorate severely, and macroscopic cracking may even occur. Meanwhile, compared with traditional preparation methods, titanium-based composite materials prepared by selective laser melting have poor high-temperature mechanical properties, indicating room for improvement. Summary of the Invention
[0005] This invention addresses the problem that current additive manufacturing methods for titanium-based composite materials, especially those using titanium alloy TA15 and TiB2 / Si powder as reinforcing phases, cannot simultaneously achieve high-temperature resistance and near-net-shape forming. Instead, it provides an additive manufacturing method for high-temperature resistant titanium-based composite materials with excellent room-temperature strength-plasticity matching. By combining selective laser melting and annealing heat treatment, a high-temperature resistant titanium-based composite material with excellent room-temperature strength-plasticity matching was successfully prepared.
[0006] The present invention discloses an additive manufacturing method for a high-temperature resistant titanium-based composite material with good room-temperature strength-plasticity matching, wherein the method is carried out in the following manner:
[0007] Step 1: Using TA15 titanium alloy powder as the matrix and TiB2 and Si powder as the reinforcing phases, the composite material powder is obtained by low-energy ball milling under an argon atmosphere.
[0008] Step 2: Place the composite material powder in a vacuum drying oven for drying;
[0009] Step 3: On a preheated substrate, titanium-based composite material is prepared by selective laser melting technology. The laser power is 160~220 W, the scanning speed is 800~1200 mm / s, the powder layer thickness is 0.02~0.05 mm, the scanning spacing is 0.08~0.10 mm, the substrate preheating temperature is 150~200 ℃, and the preparation process is carried out under argon atmosphere.
[0010] Step 4: The titanium-based composite material prepared by selective laser melting is subjected to annealing heat treatment in the α+β two-phase region. The heat treatment process is carried out under argon atmosphere with an atmosphere pressure of 0~0.05 MPa, a temperature range of 850~950 ℃, a heating rate of 5~10 ℃ / min, a holding time of 2~4 h, and a furnace cooling method. This completes the additive manufacturing method. The high-temperature resistant titanium-based composite material prepared can withstand 700℃.
[0011] Furthermore, the TiB2 accounts for 0.2~1.0 wt.% of the TA15 alloy by mass, and the Si accounts for 0.1~1.0 wt.% of the TA15 alloy by mass.
[0012] Furthermore, the average particle size of the TA15 titanium alloy powder is 15~53 μm, the average particle size of the TiB2 powder is 0.3~0.7 μm, and the average particle size of the Si powder is 1~5 μm.
[0013] Furthermore, the low-energy ball milling conditions described in step one are as follows: under an argon atmosphere, with a ball-to-material ratio of 1:1 to 2:1, a ball milling speed of 200 to 230 rpm / min, and a ball milling time of 4 to 5 h.
[0014] Furthermore, the drying conditions described in step two are: vacuum degree of -0.1 to -0.05 MPa, drying temperature of 80 to 150 ℃, and drying time of 3 to 6 h.
[0015] Furthermore, in step three, the laser power is 170~210W, the scanning speed is 900~1100 mm / s, the powder layer thickness is 0.03~0.04 mm, the scanning spacing is 0.09~0.10 mm, and the substrate preheating temperature is 160~180 ℃.
[0016] Furthermore, in step three, the laser power is 180~200W, the scanning speed is 1000~1100 mm / s, the powder layer thickness is 0.03~0.04 mm, the scanning spacing is 0.09~0.10 mm, and the substrate preheating temperature is 170~180 ℃.
[0017] Furthermore, in step three, the laser power is 180W, the scanning speed is 1000 mm / s, the powder layer thickness is 0.03 mm, the scanning spacing is 0.09 mm, and the substrate preheating temperature is 180 ℃.
[0018] Furthermore, the heat treatment process in step four is carried out under argon atmosphere, with an atmosphere pressure of 0~0.04MPa, a temperature range of 880~930 ℃, a heating rate of 8~10 ℃ / min, and a holding time of 2~4 h.
[0019] Furthermore, the heat treatment process in step four is carried out under argon atmosphere, with an atmosphere pressure of 0.01~0.03MPa, a temperature range of 900~920 ℃, a heating rate of 8~10 ℃ / min, and a holding time of 2~4 h.
[0020] This invention selects TA15, a near-α type titanium alloy with excellent thermal strength and good comprehensive mechanical properties below 500 °C, as the matrix, and TiB ceramic and Si as reinforcements. The titanium-based composite material is prepared through low-energy ball milling, selective laser melting, and annealing heat treatment. During selective laser melting, TiB2 reacts with the TA15 matrix in situ to form TiB. The cooling rate of the material during selective laser melting reaches as high as 10⁻⁶. 7 At ℃ / s, the β phase of the TA15 matrix does not have enough time to transform into the α phase, and therefore transforms into α' martensite in the form of martensitic transformation, resulting in high strength and low plasticity at room temperature. The presence of TiB refines the grain size of the TA15 matrix. During tension, the external load is effectively transferred to TiB through the matrix-TiB interface, and TiB bears most of the load, thus improving the strength of the composite material. Si exists in the solid solution form in the printed composite material. After annealing heat treatment, silicides precipitate. The dispersed fine silicides hinder dislocation slip, pin grain boundaries, and prevent grain boundary sliding, thereby improving the high-temperature mechanical properties of the composite material. Due to residual stress and the presence of acicular α' martensite, the printed composite material has high strength but low plasticity at room temperature. After annealing heat treatment, the residual stress is released, and the α' martensite decomposes into the α+β phase, significantly improving plasticity. However, due to the coarsening of the α and β lamellars, the grain refinement strengthening effect is weakened, and the room temperature strength is slightly reduced. In summary, this invention introduces a reinforcing agent and optimizes its composition, prepares a composite material using selective laser melting, releases residual stress and improves and regulates the microstructure through annealing heat treatment, and achieves a room temperature strength-plasticity match for the selective laser melting titanium-based composite material. At the same time, due to the load transfer strengthening of TiB and the silicide's obstruction of dislocation and grain boundary movement, the heat resistance temperature of the composite material reaches 700℃ at high temperatures.
[0021] The present invention has the following beneficial effects:
[0022] This invention selects TA15, a near-α type titanium alloy with excellent thermal strength and good comprehensive mechanical properties below 500 °C, as the matrix, and TiB ceramic and Si as reinforcements. A titanium-based composite material with excellent room-temperature strength-ductility matching and high-temperature resistance was successfully prepared by combining selective laser melting and annealing heat treatment. The material exhibits good formability and no macroscopic cracking. Compared with the composite material prepared by selective laser melting, the annealed material shows α' martensite decomposition, lamellar coarsening, and silicide precipitation. At room temperature, the tensile strength is ≥1190 MPa, and the elongation is ≥10%; at 700 °C, the tensile strength is ≥410 MPa.
[0023] This invention significantly improves the problems of poor room temperature plasticity and insufficient heat resistance of titanium-based composite materials prepared by selective laser melting. By annealing heat treatment, the microstructure of the material is improved and residual stress is released. By introducing Si elements to precipitate silicides, the high temperature strength of the material is enhanced, resulting in a significant improvement in room temperature plasticity and heat resistance temperature. Attached Figure Description
[0024] Figure 1 Macroscopic photograph of TiB / (TA15-Si) composite material;
[0025] Figure 2 Microscopic images of TiB / (TA15-Si) composite material obtained by selective laser melting;
[0026] Figure 3 Microstructure of TiB / (TA15-Si) composite material in selected area laser melting + heat treatment state;
[0027] Figure 4 Room temperature tensile curves of TiB / (TA15-Si) composite material in the selected area laser melting + heat treatment state;
[0028] Figure 5 Tensile curve of TiB / (TA15-Si) composite material under selective laser melting and heat treatment at 700 °C;
[0029] Figure 6 Tensile curve of TA15 alloy in selective laser melting and heat treatment state at 700 ℃;
[0030] Figure 7 Tensile curve of TiB / (TA15-Si) composite material at 700 °C after selective laser melting;
[0031] Figure 8 Macroscopic cracking photographs of TiB / TC11 composite material obtained by selective laser melting. Detailed Implementation
[0032] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the spirit of the contents disclosed in the present invention will be described in detail below. After understanding the embodiments of the present invention, any person skilled in the art can make changes and modifications based on the technology taught in the present invention without departing from the spirit and scope of the present invention.
[0033] The illustrative embodiments and descriptions of the present invention are used to explain the present invention, but are not intended to limit the present invention.
[0034] Example 1
[0035] This embodiment describes a high-temperature resistant titanium-based composite material with good room-temperature strength-plasticity matching and its additive manufacturing method, which is carried out according to the following steps:
[0036] (1) Near-α phase titanium alloy TA15 (nominal composition Ti-6.5Al-2.5Zr-1Mo-1V) powder was selected as the matrix, and titanium diboride (chemical formula TiB2) powder and silicon (chemical formula Si) powder were selected as the reinforcing phases, wherein the mass fraction of TiB2 was 0.5% and the mass fraction of Si was 0.3%. The composite material powder was obtained by low-energy ball milling at a ball-to-powder ratio of 3:2, a ball milling speed of 220 rpm / min, and a ball milling time of 5 h under an argon atmosphere.
[0037] (2) Place the composite material powder in a vacuum drying oven with a vacuum degree of -0.1 MPa, a drying temperature of 130 ℃, and a drying time of 5 h to remove any residual moisture or ethanol in the powder and improve the powder's flowability.
[0038] (3) Using the powder obtained in (2) as raw material, titanium-based composite material was prepared by selective laser melting. The process parameters were: laser power 180 W, scanning speed 1000 mm / s, powder layer thickness 0.03 mm, scanning spacing 0.09 mm, substrate preheating temperature 180 ℃, and the preparation process was carried out in an argon atmosphere to obtain a blocky titanium-based composite material.
[0039] (4) The titanium-based composite material obtained in (3) is subjected to annealing heat treatment with argon as the protective atmosphere. The process parameters are: atmosphere pressure is 0.02 MPa, holding temperature is 900℃, heating rate is 10℃ / min, holding time is 4 h, and then cooled to room temperature with the furnace.
[0040] In this embodiment, the microstructure of the annealed titanium-based composite material is as follows: Figure 3 As shown, the microstructure of the titanium-based composite material after selective laser melting without annealing heat treatment is as follows: Figure 2 As shown, it can be seen that after annealing heat treatment, the matrix structure is significantly coarsened, TiB whiskers grow, and silicides precipitate in the form of particles.
[0041] The mechanical properties of the annealed titanium-based composite material were tested and found to be: room temperature tensile strength of 1198 MPa and elongation of 10.8%. Figure 4 As shown, the test conditions were: tensile rate 0.5 mm / min, gauge length of 15 mm. Tensile strength at 700℃ was 420 MPa. Figure 5 As shown, the test conditions were: tensile rate 1 mm / min, gauge length of the specimen 15 mm.
[0042] The results show that the present invention prepares TiB / (TA15-Si) titanium-based composite material by mixing TiB2 powder, Si powder and TA15 titanium alloy through low-energy ball milling and selective laser melting technology, followed by annealing heat treatment. The material exhibits good room temperature strength and plasticity matching, and significantly improved high temperature tensile strength, effectively increasing the heat resistance temperature of the material to 700 ℃.
[0043] Comparative Example 1
[0044] (1) Near-α phase titanium alloy TA15 (nominal composition Ti-6.5Al-2.5Zr-1Mo-1V) powder was selected as the matrix with a particle size of 15~53μm. It was placed in a vacuum drying oven with a vacuum degree of -0.1 MPa, a drying temperature of 130 ℃, and a drying time of 5 h to remove any residual moisture or ethanol in the powder and improve the flowability of the powder.
[0045] (2) Using the powder obtained in (1) as raw material, TA15 titanium alloy was prepared by selective laser melting. The process parameters were: laser power 180 W, scanning speed 1000 mm / s, powder layer thickness 0.03 mm, scanning spacing 0.09 mm, substrate preheating temperature 180 ℃, and the preparation process was carried out in an argon atmosphere to obtain blocky TA15 titanium alloy.
[0046] (3) The TA15 titanium alloy obtained in (2) was subjected to annealing heat treatment with argon as the protective atmosphere. The process parameters were: atmosphere pressure of 0.02 MPa, holding temperature of 900℃, heating rate of 10℃ / min, holding time of 4 h, and furnace cooling to room temperature.
[0047] In this embodiment, the annealed TA15 titanium alloy was tested and its high-temperature mechanical properties were obtained: tensile strength at 700℃ was 350 MPa, as shown in the figure. Figure 6 As shown.
[0048] Comparative Example 2
[0049] (1) Near-α phase titanium alloy TA15 (nominal composition Ti-6.5Al-2.5Zr-1Mo-1V) powder was selected as the matrix, and titanium diboride (chemical formula TiB2) powder and silicon (chemical formula Si) powder were selected as the reinforcing phases, wherein the mass fraction of TiB2 was 0.5% and the mass fraction of Si was 0.3%. The composite material powder was obtained by low-energy ball milling at a ball-to-powder ratio of 3:2, a ball milling speed of 220 rpm / min, and a ball milling time of 5 h under an argon atmosphere.
[0050] (2) Place the composite material powder in a vacuum drying oven with a vacuum degree of -0.1 MPa, a drying temperature of 130 ℃, and a drying time of 5 h to remove any residual moisture or ethanol in the powder and improve the powder's flowability.
[0051] (3) Using the powder obtained in (2) as raw material, titanium-based composite material was prepared by selective laser melting. The process parameters were: laser power 180 W, scanning speed 1000 mm / s, powder layer thickness 0.03 mm, scanning spacing 0.09 mm, substrate preheating temperature 180 ℃, and the preparation process was carried out in an argon atmosphere to obtain a blocky titanium-based composite material.
[0052] The titanium-based composite material in this embodiment was tested and its high-temperature mechanical properties were found to be: tensile strength of 370 MPa at 700 ℃. Figure 7 As shown.
[0053] Comparative Example 3
[0054] (1) α+β type titanium alloy TC11 (nominal composition Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) powder was selected as the matrix, and titanium diboride (chemical formula TiB2) powder was selected as the reinforcing phase, wherein the mass fraction of TiB2 was 0.5%. The composite material powder was obtained by low-energy ball milling at a ball-to-powder ratio of 3:2, a ball milling speed of 220 rpm / min, and a ball milling time of 5 h under an argon atmosphere.
[0055] (2) Place the composite material powder in a vacuum drying oven with a vacuum degree of -0.1 MPa, a drying temperature of 130 ℃, and a drying time of 5 h to remove any residual moisture or ethanol in the powder and improve the powder's flowability.
[0056] (3) Using the powder obtained in (2) as raw material, titanium-based composite material was prepared by selective laser melting. The process parameters were: laser power 180 W, scanning speed 1000 mm / s, powder layer thickness 0.03 mm, scanning spacing 0.09 mm, substrate preheating temperature 180 ℃, and the preparation process was carried out in an argon atmosphere to obtain titanium-based composite material.
[0057] The titanium-based composite material in this embodiment exhibits significant macroscopic cracking, such as... Figure 8 As shown, due to macroscopic cracking, the sample failed to form and could not be tested for mechanical properties, thus rendering subsequent annealing heat treatment meaningless.
Claims
1. A method of additive manufacturing of a high-temperature-resistant titanium-based composite material with a good match of room-temperature ductility and strength, characterized in that, The method is carried out in the following manner: Step one, taking TA15 titanium alloy powder as the matrix, TiB2 and Si powder as the reinforcing phase, low-energy ball milling is carried out in an argon atmosphere to obtain composite material powder; Step two, the composite material powder is placed in a vacuum drying box for drying; Step three, a titanium-based composite material is prepared on a preheated substrate by selective laser melting technology, the laser power is 160-220 W, the scanning speed is 800-1200 mm / s, the powder layer thickness is 0.02-0.05 mm, the scanning interval is 0.08-0.10 mm, the substrate preheating temperature is 150-200 ℃, and the preparation process is carried out in an argon atmosphere; Step four, the titanium-based composite material prepared by selective laser melting is annealed in the α+β two-phase region, the heat treatment process is carried out in an argon atmosphere, the atmosphere pressure is 0-0.05 MPa, the temperature is in the range of 850-950 ℃, the heating rate is 5-10 ℃ / min, the holding time is 2-4 h, and the cooling method is furnace cooling, thereby completing the additive manufacturing method, and the prepared high-temperature-resistant titanium-based composite material is resistant to 700 ℃.
2. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1, characterized in that, The mass fraction of TiB2 in TA15 alloy is 0.2-1.0 wt.%, and the mass fraction of Si in TA15 alloy is 0.1-1.0 wt.%.
3. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1, characterized in that, The average particle size of the TA15 titanium alloy powder is 15-53 μm, the average particle size of the TiB2 powder is 0.3-0.7 μm, and the average particle size of the Si powder is 1-5 μm.
4. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1, characterized in that, The low-energy ball milling conditions in step one are as follows: a ball-to-material ratio of 1:1-2:1, a ball milling speed of 200-230 rpm / min, and a ball milling time of 4-5 h in an argon atmosphere.
5. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1, characterized in that, The drying conditions in step two are as follows: a vacuum degree of -0.1 to -0.05 MPa, a drying temperature of 80-150 ℃, and a drying time of 3-6 h.
6. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1, characterized in that, The laser power in step three is 170-210 W, the scanning speed is 900-1100 mm / s, the powder layer thickness is 0.03-0.04 mm, the scanning interval is 0.09-0.10 mm, and the substrate preheating temperature is 160-180 ℃.
7. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1 or 6, characterized in that, The laser power in step three is 180-200 W, the scanning speed is 1000-1100 mm / s, the powder layer thickness is 0.03-0.04 mm, the scanning interval is 0.09-0.10 mm, and the substrate preheating temperature is 170-180 ℃.
8. A method of additive manufacturing of a high-temperature-resistant titanium-based composite material with good room-temperature-ductility-matching according to claim 7, characterized in that The laser power in step three is 180 W, the scanning speed is 1000 mm / s, the powder layer thickness is 0.03 mm, the scanning interval is 0.09 mm, and the substrate preheating temperature is 180 ℃.
9. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1, characterized in that, The heat treatment process in step four is carried out in an argon atmosphere, the atmosphere pressure is 0-0.04 MPa, the temperature is in the range of 880-930 ℃, the heating rate is 8-10 ℃ / min, and the holding time is 2-4 h.
10. The additive manufacturing method of a high-temperature-resistant titanium-based composite material with good room-temperature strong plasticity matching according to claim 1 or 9, characterized in that, The heat treatment process in step four is carried out under argon atmosphere, the pressure of the atmosphere is 0.01-0.03 MPa, the temperature is in the range of 900-920 ℃, the heating rate is 8-10 ℃ / min, and the holding time is 2-4 h.