Preparation method of ZrO2 reinforced TiZrNbTaCu high-entropy alloy
By introducing copper into the TiZrNbTa matrix and preparing a ZrO2 reinforcing phase, the problems of insufficient bioinertness and hardness of traditional titanium alloys were solved, achieving a comprehensive improvement in high strength, antibacterial properties and biocompatibility, and preparing a high-entropy alloy suitable for orthopedic implant materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUANGDONG OCEAN UNIVERSITY
- Filing Date
- 2026-04-09
- Publication Date
- 2026-06-05
AI Technical Summary
Traditional titanium alloys have problems in orthopedic implant materials, such as difficulty in matching mechanical properties, bioinertness, lack of antibacterial ability and insufficient hardness. In addition, TiZrNbTa-based bio-high entropy alloys are prone to compositional segregation and dendrite coarsening during the melting process.
Copper was introduced into the TiZrNbTa matrix, and ZrO2-reinforced TiZrNbTaCu high-entropy alloy was prepared by high-energy ball milling and spark plasma sintering. The antibacterial properties of Cu and the uniformly dispersed reinforcing phase of ZrO2 were utilized to form a highly dense bulk with uniform structure and fine grains.
The prepared ZrO2-reinforced TiZrNbTaCu high-entropy alloy has low modulus, high strength, high wear resistance, strong antibacterial properties and good biocompatibility, making it suitable as a hard tissue repair material.
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Figure CN122147120A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing ZrO2-enhanced TiZrNbTaCu high-entropy alloys, specifically belonging to the field of biomedical materials. Background Technology
[0002] With the accelerating aging of the global population and the frequent occurrence of traffic and sports injuries, the clinical demand for high-performance hard tissue repair and replacement materials (such as artificial joints and bone plates) is experiencing explosive growth. Therefore, the development of novel medical metallic materials with excellent biocompatibility, mechanical adaptability, and functional properties is crucial for improving patients' quality of life and reducing the burden on healthcare. Titanium and its alloys, with their high specific strength and good corrosion resistance, have become the most widely used orthopedic implant materials. However, in long-term clinical service, traditional titanium alloys have gradually revealed a series of problems, such as the "stress barrier" problem caused by difficulty in matching mechanical adaptability, and the bioinertness of traditional titanium alloy surfaces, lacking inherent antibacterial capabilities. In complex physiological environments, bacteria can easily adhere to the implant surface and form biofilms, leading to implant-related infections, making the development of next-generation medical metallic materials imperative. To address the aforementioned challenges, TiZrNbTa-based bio-high-entropy alloys, composed of refractory elements with extremely high biocompatibility, have emerged. These alloys, with their unique high-entropy effect and lattice distortion effect, exhibit significantly higher strength and superior corrosion resistance than traditional titanium alloys. However, they still face three major challenges: First, due to the large differences in melting points among the components, traditional smelting processes easily lead to severe compositional segregation and dendrite coarsening; second, although the material is non-toxic, it lacks active antibacterial and other biological functions, making it difficult to cope with postoperative infection risks; and third, TiZrNbTa-based bio-high-entropy alloys suffer from low hardness and insufficient wear resistance. To overcome these problems, this invention introduces the functional antibacterial element copper into the TiZrNbTa matrix and employs spark plasma sintering combined with high-energy ball milling technology for powder metallurgy preparation of the high-entropy alloy. By taking advantage of the low temperature and rapid sintering of spark plasma sintering, a highly dense bulk with uniform structure and fine grains is obtained. At the same time, by utilizing the antibacterial properties of Cu and the in-situ generation of uniformly dispersed ZrO2 reinforcing phase in the matrix, the alloy is endowed with integrated characteristics of "low modulus, high strength, high wear resistance, strong antibacterial properties, and good biocompatibility". Summary of the Invention
[0003] In view of the above situation, the present invention proposes a method for preparing a ZrO2-enhanced TiZrNbTaCu high-entropy alloy.
[0004] The method for preparing the ZrO2-reinforced TiZrNbTaCu high-entropy alloy of the present invention involves introducing the antibacterial element copper into the TiZrNbTa matrix, and then obtaining the ZrO2-reinforced TiZrNbTaCu high-entropy alloy through high-energy ball milling and synergistic discharge plasma sintering. The specific process is as follows: Step 1: Mixing powder Titanium powder, zirconium powder, niobium powder, tantalum powder, copper powder, and stearic acid are mixed in a certain proportion to obtain powder raw materials; The atomic ratio of titanium, zirconium, niobium and tantalum is 1~5:1:1:1, the mass ratio of copper powder to titanium zirconium niobium tantalum powder is 3~7:97~93, and the mass ratio of stearic acid to titanium zirconium niobium tantalum copper powder is 0.05~1.5:100. Step 2: High-energy ball milling Place the powdered raw material into a vacuum stainless steel ball mill jar and evacuate the vacuum to below 10°C. -1 Pa, then purged with 99.999% high-purity argon gas to a concentration of 1.1 × 10⁻⁶. 5 After two cycles of vacuuming and filling with high-purity argon, the alloy powder is obtained by high-energy ball milling. Step 3: Loading the furnace The alloy powder is placed into a graphite mold and then placed into a spark plasma sintering furnace. Step 4: Spark Plasma Sintering The vacuum level inside the spark plasma sintering furnace was reduced to below 5 × 10⁻⁶. -1 After Pa, it is subjected to spark plasma sintering, and then cooled to room temperature in the furnace to obtain an in-situ generated ZrO2-enhanced TiZrNbTaCu high-entropy alloy.
[0005] The purity of the titanium powder, niobium powder, tantalum powder and copper powder mentioned are all above 99.99%, and the particle size is 1~100μm.
[0006] The zirconium powder contains 10% to 30% ZrH2 by mass.
[0007] The high-energy ball milling process is as follows: the ball milling speed is 400~600 r / min, the ball milling time is 4~12 h, and the ball-to-material ratio is 5:1.
[0008] The discharge plasma sintering process is as follows: pressure 20~50MPa; sintering temperature 800~1000℃; sintering holding time 5~20min; heating rate: 100℃ / min from room temperature to 600℃, 50℃ / min from 600℃ to the first 50℃ of the sintering temperature, and 10℃ / min from the first 50℃ of the sintering temperature to the sintering temperature.
[0009] The beneficial effects of this invention are as follows: This invention introduces Cu element into TiZrNbTa high-entropy alloys, endowing them with antibacterial properties. The high-entropy alloy is prepared by powder metallurgy using spark plasma sintering combined with high-energy ball milling technology. Taking advantage of the low-temperature and rapid sintering of spark plasma sintering, a highly dense bulk with uniform microstructure and fine grains is obtained. Simultaneously, ZrH2 powder is introduced, forming a uniformly dispersed ZrO2 reinforcing phase in situ during sintering, improving the alloy's hardness and wear resistance. By controlling the Ti content, a titanium-rich region and ZrO2 dual reinforcement are formed on the high-entropy alloy matrix, further enhancing the alloy's hardness and wear resistance. The in-situ generated ZrO2-reinforced TiZrNbTaCu high-entropy alloy prepared by this invention possesses integrated characteristics of low modulus, high strength, high wear resistance, strong antibacterial properties, and good biocompatibility, making it a very promising alternative material for hard tissue repair. Attached Figure Description
[0010] Figure 1 XRD pattern of the TiZrNbTa-5Cu alloy prepared in Example 1 of this invention; Figure 2 SEM-BSE image of the TiZrNbTa-5Cu alloy prepared in Example 1 of this invention; Figure 3 XRD pattern of the Ti4ZrNbTa-5Cu alloy prepared in Example 2 of this invention; Figure 4 SEM-BSE image of the Ti4ZrNbTa-5Cu alloy prepared in Example 2 of this invention; Figure 5 The micro Vickers hardness of the TiZrNbTa-5Cu and Ti4ZrNbTa-5Cu alloys prepared in Examples 1 and 2 of this invention; Figure 6 Typical compressive stress-strain curves of TiZrNbTa-5Cu and Ti4ZrNbTa-5Cu alloys prepared in Examples 1 and 2 of this invention; Figure 7 Friction coefficient curves of TiZrNbTa-5Cu and Ti4ZrNbTa-5Cu alloys prepared in Examples 1 and 2 of this invention, after being milled against Si4N3 ceramic balls for 30 minutes; Figure 8 Linear wear track diagrams of TiZrNbTa-5Cu and Ti4ZrNbTa-5Cu alloys prepared in Examples 1 and 2 of this invention after being ground against Si4N3 ceramic balls for 30 minutes; Figure 9 : Bacterial colony diagram of commercial medical pure titanium co-cultured with Escherichia coli for 24 hours; Figure 10: Bacterial colony diagram of the Ti4ZrNbTa-5Cu alloy prepared in Example 2 of this invention after co-culturing with Escherichia coli for 24 hours. Detailed Implementation
[0011] Example 1 The preparation process of ZrO2-enhanced TiZrNbTaCu high-entropy alloy is as follows: Step 1: Mixing powder Titanium powder, zirconium powder, niobium powder, tantalum powder, copper powder, and stearic acid are mixed in a certain proportion to obtain powder raw materials; The amounts of titanium powder, zirconium powder, niobium powder, tantalum powder, copper powder, and stearic acid are 11.01, 20.98, 21.37, 41.64, 5.00, and 1.00 grams, respectively. The zirconium powder contains 20% ZrH2 powder by mass.
[0012] The purity of titanium powder, niobium powder, tantalum powder, and copper powder is all 99.99%. The particle sizes of titanium powder, zirconium powder, niobium powder, tantalum powder and copper powder are ~45μm, ~48μm, ~48μm, ~48μm and ~10μm, respectively.
[0013] Step 2: High-energy ball milling Place the powdered raw material into a vacuum stainless steel ball mill jar and evacuate the vacuum to below 10°C. -1 Pa, then purged with 99.999% high-purity argon gas to a concentration of 1.1 × 10⁻⁶. 5 After two cycles of vacuuming and filling with high-purity argon, the alloy powder is obtained by high-energy ball milling. The ball milling speed was 500 r / min, the ball milling time was 6 h, and the ball-to-material ratio was 5:1.
[0014] Step 3: Loading the furnace The alloy powder is placed into a graphite mold and then placed into a spark plasma sintering furnace. Step 4: Spark Plasma Sintering The vacuum level inside the spark plasma sintering furnace was reduced to below 5 × 10⁻⁶. -1 After Pa, spark plasma sintering is performed, followed by furnace cooling to room temperature to obtain an in-situ generated ZrO2-enhanced TiZrNbTaCu high-entropy alloy (labeled as TiZrNbTa-5Cu).
[0015] The pressure was 40 MPa, the sintering temperature was 900℃, and the sintering holding time was 10 min.
[0016] The heating rates are as follows: 100℃ / min for room temperature to 600℃, 50℃ / min for 600℃ to 850℃, and 10℃ / min for 850℃ to 900℃.
[0017] Example 2 The preparation process of ZrO2-enhanced TiZrNbTaCu high-entropy alloy is as follows: Step 1: Mixing powder Titanium powder, zirconium powder, niobium powder, tantalum powder, copper powder, and stearic acid are mixed in a certain proportion to obtain powder raw materials; The amounts of titanium powder, zirconium powder, niobium powder, tantalum powder, copper powder, and stearic acid are 32.67, 15.57, 15.86, 30.89, 5.00, and 1.00 grams, respectively. The zirconium powder contains 20% ZrH2 by mass.
[0018] The purity of titanium powder, niobium powder, tantalum powder and copper powder is 99.99%, and the particle sizes are ~45μm, ~48μm, ~48μm, ~48μm and ~10μm, respectively.
[0019] Step 2: High-energy ball milling Place the powdered raw material into a vacuum stainless steel ball mill jar and evacuate the vacuum to below 10°C. -1 Pa, then purged with 99.999% high-purity argon gas to a concentration of 1.1 × 10⁻⁶. 5 After two cycles of vacuuming and filling with high-purity argon, the alloy powder is obtained by high-energy ball milling. The ball milling speed was 500 r / min, the ball milling time was 6 h, and the ball-to-material ratio was 5:1.
[0020] Step 3: Loading the furnace The alloy powder is placed into a graphite mold and then placed into a spark plasma sintering furnace. Step 4: Spark Plasma Sintering The vacuum level inside the spark plasma sintering furnace was reduced to below 5 × 10⁻⁶. -1 After Pa, spark plasma sintering is performed, followed by furnace cooling to room temperature to obtain an in-situ generated ZrO2-enhanced TiZrNbTaCu high-entropy alloy (labeled as Ti4ZrNbTa-5Cu).
[0021] The pressure was 40 MPa, the sintering temperature was 900℃, and the sintering holding time was 10 min.
[0022] The heating rates are as follows: 100℃ / min for room temperature to 600℃, 50℃ / min for 600℃ to 850℃, and 10℃ / min for 850℃ to 900℃.
[0023] Example 3 The preparation process of ZrO2-enhanced TiZrNbTaCu high-entropy alloy is as follows: Steps 1 through 3 are the same as in Example 2. Step 4: Process parameters for spark plasma sintering: pressure 40MPa, sintering temperature 950℃, sintering holding time 10min.
[0024] The heating rate is as follows: 100℃ / min for the temperature range from room temperature to 600℃, 50℃ / min for the temperature range from 600℃ to 900℃, and 10℃ / min for the temperature range from 900℃ to 950℃. Attached Figure Analysis
[0025] from Figure 1 As can be seen, after ball milling, the alloy powder mainly consists of the BCC phase and the ZrH2 phase, indicating that during the ball milling process, Ti, Zr, Nb, Ta, and Cu powders all undergo mutual solid solution to form the BCC phase, while the ZrH2 in the powder still exists independently. After spark plasma sintering, the TiZrNbTa-5Cu alloy mainly consists of the BCC phase and the ZrO2 phase, indicating that ZrH2 is oxidized in situ during the sintering process to form the ZrO2 phase.
[0026] from Figure 2 As can be seen, the morphology of the TiZrNbTa-5Cu alloy is mainly composed of black particles with an average particle size of 0.78 micrometers that are uniformly and diffusely distributed in the matrix. Analysis shows that the black particles are ZrO2 phase, while the matrix is a TiZrNbTaCu high-entropy alloy.
[0027] from Figure 3 As can be seen, with the increase of Ti powder content, α-Ti appeared in the alloy powder in addition to the BCC phase and ZrH2 phase, indicating that the Ti powder content has exceeded the solid solubility of Ti in the BCC phase, and some Ti can only exist in the form of elemental Ti. After spark plasma sintering, the Ti4ZrNbTa-5Cu alloy is mainly composed of BCC, ZrO2 and Cu2O phases, indicating that during the sintering process, the excess Ti in the powder is still dissolved in the BCC phase, while Cu precipitates from the BCC phase to form the Cu2O phase.
[0028] from Figure 4 As can be seen, the morphology of the Ti4ZrNbTa-5Cu alloy mainly consists of black particles with an average particle size of 1.29 micrometers and gray regions that are uniformly dispersed in the matrix. Analysis shows that the black particles are ZrO2 phase, the gray regions are Ti enrichment areas, and the matrix is a TiZrNbTaCu high-entropy alloy.
[0029] from Figure 5 As can be seen, the Ti4ZrNbTa-5Cu alloy has a hardness of 956.1 HV. 100g Compared to the TiZrNbTa-5Cu alloy's 689.7 HV 100gThe microhardness of TiZrNbTa-5Cu and Ti4ZrNbTa-5Cu alloys is 38.6% higher than that of conventional TC4 alloys (~330 HV). 100g This indicates that the in-situ formed ZrO2-enhanced TiNbZrTaCu high-entropy alloy prepared by this invention has excellent microhardness and is expected to improve the wear resistance of the alloy.
[0030] from Figure 6 As can be seen, the compressive strength of the Ti4ZrNbTa-5Cu alloy is 2034.78±60.59 MPa, which is nearly 15% higher than that of TiZrNbTa-5Cu (1780.14±29.67 MPa). The compressibility also increased from 8.02±1.47% for TiZrNbTa-5Cu to 13.62±2.18%. This coordinated improvement in strength and plasticity is mainly due to the increase in Ti, which forms a large number of uniformly distributed Ti-rich regions in the high-entropy alloy matrix. Furthermore, the compressive elastic modulus of TiZrNbTa-5Cu is 31.43±1.90 GPa, while that of the Ti4ZrNbTa-5Cu alloy is 29.48±2.14 GPa. Both alloys have elastic moduli very close to the modulus of human cortical bone (<30 GPa), effectively reducing the "stress shielding" effect of the alloy.
[0031] from Figure 7 As can be seen, the friction coefficient of the TiZrNbTa-5Cu alloy is relatively stable, at ~0.5, while the friction coefficient of the Ti4ZrNbTa-5Cu alloy fluctuates more, averaging 0.8. The significant difference in friction coefficients between the two alloys is mainly due to the lower hardness of the TiZrNbTa-5Cu alloy, where the primary wear mechanism is abrasive wear, resulting in a more stable friction coefficient. In contrast, the higher hardness of the Ti4ZrNbTa-5Cu alloy leads to mass transfer from the Si4N3 ceramic balls to the alloy surface, resulting in primarily adhesive and oxidative wear, and thus a more volatile friction coefficient.
[0032] from Figure 8 As can be seen, the wear tracks on the TiZrNbTa-5Cu alloy surface are wide and deep, while those on the Ti4ZrNbTa-5Cu alloy surface are narrow and shallow. Although the Ti4ZrNbTa-5Cu alloy has a higher coefficient of friction, a Si-based oxide glaze layer forms on its surface, resulting in less wear. In contrast, the lower-hardness TiZrNbTa-5Cu alloy experiences abrasive wear, leading to greater wear. Figure 8 The wear rate of the TiZrNbTa-5Cu alloy is calculated to be 7.11 × 10⁻⁶. -4 mm 3 ·N -1 ·min -1The wear rate of Ti4ZrNbTa-5Cu alloy is only 0.09×10⁻⁶. -4 mm 3 ·N -1 ·min -1 The hardness decreased by two orders of magnitude. This demonstrates that adjusting the Ti powder content can effectively improve the alloy's hardness and wear resistance.
[0033] from Figure 9 and Figure 10 As can be seen, commercially available medical-grade pure titanium has no antibacterial properties, and *E. coli* grows and multiplies extensively on its surface, while no *E. coli* was observed on the Ti4ZrNbTa-5Cu alloy. This indicates that the Ti4ZrNbTa-5Cu alloy exhibits an antibacterial rate of >99.9% against *E. coli*, demonstrating excellent antibacterial performance. Similarly, co-culturing the Ti4ZrNbTa-5Cu alloy with *Staphylococcus aureus* for 24 hours also showed an antibacterial rate of >99.9%. Furthermore, co-culturing the TiZrNbTa-5Cu alloy with both *E. coli* and *Staphylococcus aureus* for 24 hours also resulted in antibacterial rates of >99.9%. This is mainly due to the addition of Cu to the alloy, which endows it with superior antibacterial properties. To further verify the antibacterial properties of the alloys, the co-culture time with *Escherichia coli* and *Staphylococcus aureus* was reduced to 12 hours. The antibacterial rates of the TiZrNbTa-5Cu alloy were 97.47% and 95.15%, respectively, while the antibacterial rates of the Ti4ZrNbTa-5Cu alloy were both >99.9%. This indicates that the Ti4ZrNbTa-5Cu alloy has stronger antibacterial properties than the TiZrNbTa-5Cu alloy. This is mainly because the Cu in Ti4ZrNbTa-5Cu exists in the form of Cu2O, which has superior antibacterial properties. Furthermore, when the TiZrNbTa-5Cu and Ti4ZrNbTa-5Cu alloys were co-cultured with MC3T3-E1 osteoblasts for 1–5 days, the cell viability was >90% and the cytotoxicity was grade 1, indicating that both the TiZrNbTa-5Cu and Ti4ZrNbTa-5Cu alloys have good cell compatibility.
Claims
1. A method for preparing ZrO2-reinforced TiZrNbTaCu high-entropy alloy, characterized in that: The preparation method described above introduces the antibacterial element copper into a TiZrNbTa matrix, and then prepares a ZrO2-reinforced TiZrNbTaCu high-entropy alloy by high-energy ball milling combined with spark plasma sintering. The specific process is as follows: Step 1: Mixing powder Titanium powder, zirconium powder, niobium powder, tantalum powder, copper powder, and stearic acid are mixed in a certain proportion to obtain powder raw materials; The atomic ratio of titanium, zirconium, niobium and tantalum is 1~5:1:1:1, the mass ratio of copper powder to titanium zirconium niobium tantalum powder is 3~7:97~93, and the mass ratio of stearic acid to titanium zirconium niobium tantalum copper powder is 0.05~1.5:
100. Step 2: High-energy ball milling Place the powdered raw material into a vacuum stainless steel ball mill jar and evacuate the vacuum to below 10°C. -1 Pa, then purged with 99.999% high-purity argon gas to a concentration of 1.1 × 10⁻⁶. 5 After two cycles of vacuuming and filling with high-purity argon, the alloy powder is obtained by high-energy ball milling. Step 3: Loading the furnace The alloy powder is placed into a graphite mold and then placed into a spark plasma sintering furnace. Step 4: Spark Plasma Sintering The vacuum level inside the spark plasma sintering furnace was reduced to below 5 × 10⁻⁶. -1 After Pa, spark plasma sintering is performed, followed by furnace cooling to room temperature to obtain an in-situ ZrO2-enhanced TiZrNbTaCu high-entropy alloy.
2. The preparation method of ZrO2-reinforced TiZrNbTaCu high-entropy alloy according to claim 1, characterized in that: The purity of the titanium powder, niobium powder, tantalum powder and copper powder mentioned are all above 99.99%, and the particle size is 1~100μm.
3. The preparation method of ZrO2-reinforced TiZrNbTaCu high-entropy alloy according to claim 1, characterized in that: The zirconium powder contains 10% to 30% ZrH2 by mass.
4. The preparation method of ZrO2-reinforced TiZrNbTaCu high-entropy alloy according to claim 1, characterized in that: The high-energy ball milling process is as follows: the ball milling speed is 400~600 r / min, the ball milling time is 4~12 h, and the ball-to-material ratio is 5:
1.
5. The method for preparing ZrO2-reinforced TiZrNbTaCu high-entropy alloy according to claim 1, characterized in that: The discharge plasma sintering process is as follows: pressure 20~50MPa; sintering temperature 800~1000℃; sintering holding time 5~20min; heating rate: 100℃ / min from room temperature to 600℃, 50℃ / min from 600℃ to the first 50℃ of the sintering temperature, and 10℃ / min from the first 50℃ of the sintering temperature to the sintering temperature.