Improving the corrosion resistance of biocompatible TiZrNbAl refractory high-entropy alloy in simulated body fluids by nanosecond laser shock peening

Abstract

The present invention relates to the technical field of biomedical materials, and in particular to a biocompatible TiZrNbAl refractory high-entropy alloy whose corrosion resistance in simulated body fluids is improved by nanosecond laser shock peening. The method performs surface laser shock peening on the alloy to increase the surface roughness, transform the surface micron-crystals into nanocrystals, and is accompanied by a large number of deformation dislocations. The block microstructure is characterized by a single-phase body-centered cubic structure and a grain size in the range of 10 to 30 μm. The corrosion current density of the LSP-TiZrNbAl refractory high-entropy alloy is only 1 / 3 of that of the untreated state; the resistance R ct 2.29×10 5 Ω·cm 2 , compared with the untreated state (2.79×10 4 Ω·cm 2 ) by an order of magnitude. This invention combines a TiZrNbAl refractory high-entropy alloy with excellent mechanical properties and good biocompatibility with nanosecond LSP surface treatment technology, significantly improving the alloy's corrosion resistance in simulated body fluids. The alloy block preparation process is simple, and the laser surface treatment process is highly efficient, giving it outstanding application value in the field of biomedical materials.

Description

Technical Field

[0001] The present invention relates to the technical field of biomedical materials, and in particular to a biocompatible TiZrNbAl refractory high-entropy alloy whose corrosion resistance in simulated body fluids is improved by nanosecond laser shock peening, including its preparation method, bulk mechanical properties, laser shock peening parameters, surface microstructure characteristics, and corrosion resistance. Background Art

[0002] Metal materials commonly used in biomedical applications, such as stainless steel, CoCrMo alloy, and Ti-6Al-4V alloy, all face challenges related to corrosion resistance and biocompatibility. High-entropy alloys (HEAs), due to their broad compositional design space, can achieve excellent biocompatibility and corrosion resistance by manipulating alloy composition. This is particularly true for biomedical HEAs, such as the Ti-Nb-Ta-Zr-Mo, Ti-Zr-Hf-Nb-Ta-Mo, Ti-Zr-Nb-Ta, Ti-Zr-Ta-Hf-Nb, and Ti-Zr-Hf-Nb-Ta-Sn series of refractory HEAs. Compared to pure Ti, these refractory HEAs with high yield strength exhibit good biocompatibility. However, they exhibit poor plastic deformation, particularly a lack of tensile plasticity, and their density is much higher than that of Ti-6Al-4V alloy, significantly reducing the biomedical value of these refractory HEAs. Therefore, the development of refractory HEAs with high specific strength and tensile plasticity holds significant biomedical potential.

[0003] At the same time, various surface treatment methods, such as chemical / physical vapor deposition or etching, and laser processing, have been widely used to refine the surface microstructure and improve the mechanical properties and corrosion resistance of metal materials. In contrast, laser shock peening (LSP) is a versatile and efficient surface treatment method that achieves functional modification by changing the surface texture, morphology, and chemical properties without changing the overall performance of the metal material.

[0004] Therefore, we try to design a type of refractory high entropy alloy with high specific strength and tensile plasticity. Compared with traditional titanium alloys, this alloy removes the V element and further reduces the Al element to avoid the material releasing V in the human body. 5+ and Al 3+ , achieving greater biocompatibility for refractory high-entropy alloys. Laser pulse surface treatment technology was also used to improve the alloy's surface microstructure and enhance its corrosion resistance in simulated body fluids. The combination of refractory high-entropy alloys and LSP offers a new possibility for the development of biomedical metal materials, greatly enhancing the medical application value of refractory high-entropy alloys and having significant implications for medical devices and social livelihoods. Summary of the Invention

[0005] The primary objective of this invention is to develop a biocompatible TiZrNbAl refractory high-entropy alloy with enhanced corrosion resistance in simulated body fluids through nanosecond laser shock peening (NLSP). The research includes details on its preparation method, bulk mechanical properties, LSP parameters, surface microstructure, and corrosion resistance. The technical problem to be solved is to improve the corrosion resistance of the TiZrNbAl refractory high-entropy alloy in simulated body fluids by preparing the alloy sheet using rapid solidification technology, cold deformation and heat treatment of the sheet, and subsequent surface LSP treatment.

[0006] The purpose of the present invention and the technical problem solved are achieved by adopting the following technical solutions:

[0007] A biocompatible TiZrNbAl refractory high-entropy alloy with improved corrosion resistance in simulated body fluids through nanosecond laser shock strengthening. The bulk microstructure of the alloy is characterized by a single-phase body-centered cubic structure and a grain size in the range of 10 to 30 μm.

[0008] The biocompatible TiZrNbAl refractory high-entropy alloy, which has improved corrosion resistance in simulated body fluids through nanosecond laser shock strengthening, has a room temperature yield strength of 800-900 MPa and a fracture elongation of 20-30% under quasi-static tensile conditions.

[0009] The biocompatible TiZrNbAl refractory high-entropy alloy whose corrosion resistance in simulated body fluids is improved by nanosecond laser shock strengthening has, in atomic percentage, an atomic percentage of Ti of 35-45%, an atomic percentage of Zr of 20-30%, an atomic percentage of Nb of 15-30%, and an atomic percentage of Al of 5-10%.

[0010] The biocompatible TiZrNbAl refractory high-entropy alloy having improved corrosion resistance in simulated body fluids by nanosecond laser shock peening, and the preparation method of such refractory high-entropy alloy plate are as follows:

[0011] (1) Preparation of master alloy ingot: The four element raw materials of Ti / Zr / Nb / Al are placed in a crucible and arc melted, and the melting is repeated until the composition is uniform;

[0012] (2) Preparation of alloy plates: The master alloy ingot is remelted by electric arc and rapidly solidified by copper mold casting to form alloy plates;

[0013] (3) Preparation of deformed alloy plates: The alloy plates are subjected to cold deformation treatment to determine the deformation amount, and then annealed and recrystallized to obtain deformed alloys.

[0014] The biocompatible TiZrNbAl refractory high-entropy alloy whose corrosion resistance in simulated body fluids is improved by nanosecond laser shock peening is subjected to nanosecond laser shock peening surface treatment after annealing and recrystallization treatment. The surface microstructure characteristics of the TiZrNbAl refractory high-entropy alloy obtained are as follows:

[0015] (1) The surface deformation zone of the LSP-TiZrNbAl refractory high-entropy alloy changes from the initial grain size of 10-30 μm to less than 1 μm;

[0016] (2) The surface height difference of LSP-TiZrNbAl refractory high entropy alloy exceeds 15.0 μm, while the surface height difference of the untreated state is less than 8.0 μm;

[0017] (3) The depth of the surface deformation zone of LSP-TiZrNbAl refractory high entropy alloy is 5-15 μm;

[0018] (4) There are a large number of dislocations in the surface deformation zone of the LSP-TiZrNbAl refractory high entropy alloy.

[0019] The biocompatible TiZrNbAl refractory high-entropy alloy with improved corrosion resistance in simulated body fluids through nanosecond laser shock peening has the following process parameters for nanosecond laser shock peening surface treatment: working material Nd:YAG, laser wavelength ~1000nm, pulse energy 3~15J, laser pulse width 10~20ns, spot diameter 2~4mm, operating frequency 0.25~5Hz, and spot overlap rate 30~60%.

[0020] The biocompatible TiZrNbAl refractory high entropy alloy whose corrosion resistance is improved in simulated body fluids by nanosecond laser shock peening has the following corrosion resistance properties in simulated body fluids:

[0021] (1) The electrochemical corrosion current density of LSP-TiZrNbAl refractory high entropy alloy is 1 / 3 to 1 / 5 of that of the untreated state;

[0022] (2) Charge transfer resistance R of LSP-TiZrNbAl refractory high entropy alloy ct An order of magnitude higher than the untreated state.

[0023] The design idea of ​​the present invention is:

[0024] The present invention develops a bulk TiZrNbAl refractory high-entropy alloy with excellent strength-ductility synergy, a low Young's modulus, and a low content of elements harmful to the human body. Nanosecond LSP surface treatment technology is used to reduce grain size, increase surface dislocation density, and improve surface hardness, significantly improving the alloy's corrosion resistance. By combining a TiZrNbAl refractory high-entropy alloy with excellent mechanical properties and good biocompatibility with advanced nanosecond LSP surface treatment technology, the alloy's corrosion resistance in the human body environment is enhanced, thereby giving it greater biomedical value.

[0025] By means of the above technical solution, the advantages and beneficial effects of the present invention are:

[0026] 1. TiZrNbAl refractory high entropy alloy has better specific strength and tensile plasticity than existing biomedical refractory high entropy alloys. Compared with traditional titanium alloys, it removes the V element and further reduces the Al element to avoid the material releasing V in the human body. 5+ and Al 3+ , achieving better biocompatibility of the alloy. At the same time, the LSP surface treatment technology is used to improve the surface microstructure of the alloy and enhance the corrosion resistance of the refractory high entropy alloy in simulated body fluids. In simulated body fluids, the electrochemical corrosion current density of the LSP-TiZrNbAl refractory high entropy alloy is 1 / 3 to 1 / 5 of that of the untreated state; the charge transfer resistance R ct The combination of refractory high-entropy alloys and LSP technology provides a new possibility for the development of biomedical metal materials, greatly improving the medical application value of refractory high-entropy alloys and having important significance for medical devices and social livelihood.

[0027] 2. This invention proposes for the first time to combine the TiZrNbAl refractory high-entropy alloy with excellent mechanical properties and good biocompatibility with advanced nanosecond LSP surface treatment technology, significantly improving the corrosion resistance of the TiZrNbAl refractory high-entropy alloy in simulated body fluids. The alloy block preparation process is simple and the laser surface treatment process is efficient, giving it outstanding application value in the field of biomedical materials.

[0028] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Ti 1.5 Al 0.3XRD pattern of ZrNb refractory high entropy alloy plate after cold rolling and heat treatment.

[0030] Figure 2 Ti 1.5 Al 0.3 Tensile stress-strain diagram of ZrNb refractory high entropy alloy plate after cold rolling and heat treatment.

[0031] Figure 3 Ti 1.5 Al 0.3 Surface TEM image of the ZrNb refractory high entropy alloy plate after cold rolling and heat treatment and LSP treatment.

[0032] Figure 4 Ti after LSP treatment 1.5 Al 0.3 Potentiodynamic polarization curve of ZrNb refractory high entropy alloy in simulated body fluid.

[0033] Figure 5(a)-Figure 5(b) Ti after LSP treatment 1.5 Al 0.3 Electrochemical impedance spectroscopy of ZrNb refractory high entropy alloy in simulated body fluid. Figure 5(a) is the Nyquist plot, the inset is the enlarged view of the dotted line area, and the horizontal axis Z Re is the real part of the impedance (kΩ·cm 2 ), vertical coordinate -Z Im is the imaginary part of the impedance (kΩ·cm 2 ); Figure 5(b) is a Bode plot, where the horizontal axis logf is the logarithm of the impedance frequency (Hz), and the vertical axis log|Z| is the logarithm of the absolute value of the impedance (Ω·cm 2 ). DETAILED DESCRIPTION

[0034] In a specific implementation process, the present invention improves the corrosion resistance of a biocompatible TiZrNbAl refractory high-entropy alloy in simulated body fluids by nanosecond laser shock peening, including its preparation method, bulk mechanical properties, laser shock peening parameters, surface microstructure characteristics, and corrosion resistance as follows:

[0035] 1. A biocompatible TiZrNbAl refractory high-entropy alloy with improved corrosion resistance in simulated body fluids by nanosecond laser shock peening. The preparation method is described as follows:

[0036] First, determine the atomic ratio of each element in the TiZrNbAl refractory high-entropy alloy, convert it into a weight ratio, and then smelt it according to the ratio to prepare an alloy ingot; then melt the master alloy ingot by arc melting, and repeatedly smelt it 4 to 6 times until the composition is uniform, thus obtaining the TiZrNbAl refractory high-entropy alloy. The specific process is as follows:

[0037] (1) Preparation of master alloy ingot: Ti / Zr / Nb / Al four elements are weighed according to the preset composition ratio and placed in a crucible. When arc melting is used, the vacuum chamber is pre-evacuated to 10 -4 ~10 -3 Pa, and then fill with high-purity argon (volume purity 99.999%) until the vacuum gauge shows 4×10 4 ~8×10 4 The alloy smelting current is 300-500A, and each smelting takes 1-2 minutes. After each smelting, the alloy is turned over and smelted again. The smelting is repeated until the composition is uniform to obtain a master alloy ingot.

[0038] (2) Preparation of alloy plates: Place the master alloy ingot into a water-cooled copper crucible and evacuate the vacuum chamber to 10 -4 ~10 -3 Pa, and then fill with high-purity argon (volume purity 99.999%) until the vacuum gauge shows 4×10 4 ~8×10 4 The master alloy ingot is arc remelted and the alloy melt is quickly poured into a copper mold of corresponding size using a copper mold casting method to obtain alloy plates with dimensions of 50 mm × 20 mm × 4 mm. The obtained alloy plates are cold rolled using a double-track rolling mill at room temperature in a fixed direction with each pass being 0.1 to 0.3 mm thick, with a rolling allowance of 60% to 80%.

[0039] (3) The cold rolled sheet is annealed and the vacuum degree is 10 -3 ~10 -2 Pa, annealing temperature 800℃, heating rate 8~15℃ / min, heating time is heating time + holding time, holding time is 1~2h;

[0040] 2. A biocompatible TiZrNbAl refractory high-entropy alloy with enhanced corrosion resistance in simulated body fluids through nanosecond laser shock peening. Its composition and microstructural characteristics are as follows:

[0041] (1) In terms of atomic percentage, the atomic percentage of Ti is 35-45%, the atomic percentage of Zr is 20-30%, the atomic percentage of Nb is 15-30%, and the atomic percentage of Al is 5-10%. The microstructure is a single-phase body-centered cubic structure with a grain size in the range of 10-30 μm;

[0042] 3. A biocompatible TiZrNbAl refractory high-entropy alloy with improved corrosion resistance in simulated body fluids through nanosecond laser shock strengthening. Under quasi-static tensile conditions, the room temperature yield strength is 800-900 MPa and the elongation at break is 20-30%.

[0043] 4. A biocompatible TiZrNbAl refractory high-entropy alloy with enhanced corrosion resistance in simulated body fluids by nanosecond laser shock peening. The surface microstructure characteristics of the LSP-TiZrNbAl refractory high-entropy alloy are as follows:

[0044] (1) The surface deformation zone of the LSP-TiZrNbAl refractory high-entropy alloy changes from the initial grain size of 10-30 μm to less than 1 μm;

[0045] (2) The surface height difference of LSP-TiZrNbAl refractory high entropy alloy exceeds 15.0 μm, while the surface height difference of the untreated state is less than 8.0 μm;

[0046] (3) The depth of the surface deformation zone of LSP-TiZrNbAl refractory high entropy alloy is 5-15 μm;

[0047] (4) There are a large number of dislocations in the surface deformation zone of the LSP-TiZrNbAl refractory high entropy alloy.

[0048] 5. A biocompatible TiZrNbAl refractory high-entropy alloy with improved corrosion resistance in simulated body fluids through nanosecond laser shock peening. The process parameters of nanosecond LSP are: working material Nd:YAG, laser wavelength ~1000nm, pulse energy 3~15J, laser pulse width 10~20ns, spot diameter 2~4mm, operating frequency 0.25~5Hz, and spot overlap rate 30~60%.

[0049] 6. A biocompatible TiZrNbAl refractory high-entropy alloy with enhanced corrosion resistance in simulated body fluids by nanosecond laser shock peening. The corrosion resistance of the alloy in simulated body fluids is:

[0050] (1) The electrochemical corrosion current density of LSP-TiZrNbAl refractory high entropy alloy is 1 / 3 to 1 / 5 of that of the untreated state;

[0051] (2) Charge transfer resistance R of LSP-TiZrNbAl refractory high entropy alloy ct An order of magnitude higher than that of the untreated state;

[0052] The present invention first uses rapid solidification technology to prepare alloy sheets, which are then cold-deformed and heat-treated. Laser shock peening (LSP) is then applied to the surface to increase surface roughness and simultaneously transform surface micron-sized crystals into nanocrystalline ones, accompanied by a large number of deformation dislocations. This laser pulse treatment significantly enhances the corrosion resistance of the TiZrNbAl refractory high-entropy alloy in simulated body fluids.

[0053] Below, in conjunction with the accompanying drawings and specific embodiments, the preparation method, bulk mechanical properties, laser shock strengthening parameters, surface microstructure characteristics, and corrosion resistance of the biocompatible TiZrNbAl refractory high-entropy alloy of the present invention, which is improved in corrosion resistance in simulated body fluids by nanosecond laser shock strengthening, are described in detail.

[0054] Example

[0055] An embodiment of the present invention proposes Ti 1.5 Al 0.3 A method for preparing a ZrNb refractory high entropy alloy comprises the following steps:

[0056] (1) Preparation of master alloy ingot: weighing according to the preset composition ratio, weighing industrial grade purity Ti: 27.2g, Zr: 34.5g, Nb: 35.2g, Al: 3.1g, wherein all raw materials are industrial grade purity; placing the four elements in a crucible, using arc melting, first pre-evacuate the vacuum chamber to 10 -3 Pa, and then fill with high-purity argon (volume purity 99.999%) until the vacuum gauge shows 4×10 4 The alloy was melted at a current of 350A for 2 minutes each time. After each melting, the alloy was turned over and melted again. This process was repeated at least 5 times to obtain a master alloy ingot.

[0057] (2) Preparation of alloy plates: Place the master alloy ingot into a water-cooled copper crucible and evacuate the vacuum chamber to 3×10 -4 Pa, and then fill with high-purity argon gas (volume purity 99.999%) until the vacuum gauge shows 6×10 4 The master alloy ingot is arc remelted and the alloy melt is quickly poured into a copper mold of corresponding size using a copper mold casting method to obtain alloy plates with dimensions of 50mm×20mm×4mm. The obtained alloy plates are then cold rolled using a dual-track rolling mill at room temperature in a fixed direction with small steps and multiple passes. Each pass is rolled with a rolling depth of 0.2mm and a rolling allowance of 60%. That is, the plate thickness is reduced from the original 4mm to 1.6mm.

[0058] (3) The cold-rolled plate is annealed and sealed in a vacuum quartz tube with a vacuum degree of 5×10 -3 Pa, annealing temperature 800℃, heating rate 10℃ / min, holding time 1h, Ti 1.5 Al 0.3 ZrNb refractory high entropy alloy;

[0059] like Figure 1 As shown, the Ti prepared by the above preparation method 1.5 Al 0.3The ZrNb refractory high-entropy alloy has a single-phase body-centered cubic structure. Using wire cutting, tensile specimens with a gauge length of 14 mm, a cross-sectional size of 2.5 mm × 1.5 mm, and a total length of 36 mm were cut from the rolled annealed plate. The room-temperature tensile test was conducted using an Instron 5582 universal testing machine at a tensile rate of 1 × 10 -3 s -1 , the tensile curve of the alloy is shown in Figure 2 , Ti 1.5 Al 0.3 The ZrNb alloy has a yield strength of 821 MPa and exhibits a stable deformation phase after yield, with a total deformation of 25%. The alloy plate was then subjected to LSP treatment, using the following parameters: Nd:YAG laser, 1064 nm laser wavelength, 5 J pulse energy, 20 ns pulse width, 2 mm spot diameter, 5 Hz operating frequency, and 50% spot overlap.

[0060] like Figure 3 As shown, LSP-Ti 1.5 Al 0.3 The dark field TEM image of the ZrNb surface shows that there is a high density of dislocations in the surface area, and many dislocation tangles are generated by the interaction of dislocations. In addition, the selected area electron diffraction (SAED) pattern in the upper right corner shows that the LSP-Ti 1.5 Al 0.3 Nanocrystals have formed on the ZrNb surface, indicating grain refinement. The lower left corner, away from the surface, is less affected by LSP, but a high density of dislocation debris still forms in this area. The SAED pattern in the lower left corner shows that nanocrystals are no longer present in this area.

[0061] like Figure 4 As shown, LSP-Ti 1.5 Al 0.3 The potentiodynamic polarization curve of ZrNb alloy shifts to the left in the entire range, indicating that the corrosion current density decreases. 1.5 Al 0.3 The current density of ZrNb alloy is only 1.5 Al 0.3 ~1 / 3 of ZrNb alloy. Figure 5(a)-Figure 5(b) As shown in Figure 5, electrochemical impedance spectroscopy (EIS) also confirmed the effectiveness of laser treatment. 1.5 Al 0.3 ZrNb alloy and LSP-Ti 1.5 Al 0.3 EIS results of ZrNb alloy. LSP-Ti 1.5 Al0.3 Resistance R of ZrNb alloy ct 2.29×10 5 Ω·cm 2 , than the untreated state Ti 1.5 Al 0.3 Resistance R of ZrNb alloy ct (2.79×10 4 Ω·cm 2 ) is one order of magnitude higher. 1.5 Al 0.3 Resistance R of ZrNb alloy f 635.5Ω·cm 2 , only the unprocessed state Ti 1.5 Al 0.3 ZrNb alloy (2847Ω·cm 2 ) is 1 / 4, indicating that the passivation film is 1.5 Al 0.3 The above results show that LSP significantly improves the Ti 1.5 Al 0.3 Corrosion resistance of ZrNb alloys in simulated body fluids.

[0062] In this work, LSP-Ti 1.5 Al 0.3 The improved corrosion resistance of ZrNb alloys can be attributed to multiple factors, including the compressive residual stresses induced by LSP and the unique surface morphology, including grain refinement (nanocrystalline), a high density of dislocations and their fragments. LSP also promotes the formation of a denser passive film, which also accounts for the significant improvement in corrosion resistance.

[0063] The results of the examples demonstrate that the biocompatible TiZrNbAl refractory high-entropy alloy described in this invention, enhanced in corrosion resistance in simulated body fluids through nanosecond laser shock peening, can overcome existing corrosion limitations and achieve substantial improvements in corrosion performance. Furthermore, the alloy's simple preparation process and highly efficient surface treatment enable the low-cost, efficient preparation of metal materials with excellent biomedical potential, demonstrating significant application value in the field of biomedical materials.

[0064] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiment based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A biocompatible TiZrNbAl refractory high entropy alloy with improved corrosion resistance in simulated body fluids by nanosecond laser shock peening, characterized in that: TiZrNbAl refractory high-entropy alloy sheets were cold rolled using a dual-track rolling mill at room temperature along a fixed direction with each pass of 0.1-0.3 mm and a rolling thickness of 60%-80%. After annealing and recrystallization, the surface was treated with nanosecond laser shock peening. The blocky microstructure is characterized by a single-phase body-centered cubic structure and a grain size ranging from 10 to 30 μm. Under quasi-static tensile conditions, the room temperature yield strength is 800~900MPa and the elongation at break is 20~30%; In terms of atomic percentage, the atomic percentage of Ti is 35-45%, the atomic percentage of Zr is 20-30%, the atomic percentage of Nb is 15-30%, and the atomic percentage of Al element is 5-10%.

2. The biocompatible TiZrNbAl refractory high entropy alloy with improved corrosion resistance in simulated body fluids by nanosecond laser shock processing according to claim 1, characterized in that: The preparation method of refractory high entropy alloy is: (1) Preparation of master alloy ingot: Place the four element raw materials Ti / Zr / Nb / Al into a crucible and perform arc melting, repeatedly melting until the composition is uniform; (2) Preparation of alloy plates: The master alloy ingot is remelted by electric arc and rapidly solidified by copper mold casting to form alloy plates; (3) Preparation of deformed alloy plates: The alloy plates are subjected to cold deformation treatment to determine the deformation amount, and then annealed and recrystallized to obtain deformed alloys.

3. The biocompatible TiZrNbAl refractory high entropy alloy with improved corrosion resistance in simulated body fluids by nanosecond laser shock peening according to claim 2, characterized in that: After annealing and recrystallization treatment, nanosecond laser shock peening surface treatment is performed to obtain the surface microstructure characteristics of the TiZrNbAl refractory high entropy alloy: (1) The surface deformation zone of the LSP-TiZrNbAl refractory high entropy alloy changes from the initial grain size of 10-30 μm to less than 1 μm; (2) The surface height difference of LSP-TiZrNbAl refractory high entropy alloy exceeds 15.0 μm, while the surface height difference of the untreated state is less than 8.0 μm; (3) The depth of the surface deformation zone of LSP-TiZrNbAl refractory high entropy alloy is 5~15μm; (4) There are a large number of dislocations in the surface deformation zone of the LSP-TiZrNbAl refractory high entropy alloy.

4. The biocompatible TiZrNbAl refractory high entropy alloy with improved corrosion resistance in simulated body fluids by nanosecond laser shock peening according to claim 3, characterized in that: The process parameters of nanosecond laser shock peening surface treatment are: working material Nd:YAG, laser wavelength ~1000nm, pulse energy 3~15J, laser pulse width 10~20ns, spot diameter 2~4mm, working frequency 0.25~5Hz, and spot overlap rate 30~60%.

5. The biocompatible TiZrNbAl refractory high entropy alloy with improved corrosion resistance in simulated body fluids by nanosecond laser shock peening according to claim 3 or 4, characterized in that: The corrosion resistance of TiZrNbAl refractory high entropy alloy in simulated body fluid is: (1) The electrochemical corrosion current density of LSP-TiZrNbAl refractory high entropy alloy is 1 / 3~1 / 5 of that of the untreated state; (2) Charge transfer resistance of LSP-TiZrNbAl refractory high entropy alloy R ct An order of magnitude higher than the untreated state.

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