High-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy and method

Abstract

The present invention discloses a high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy and a method. The alloy composition is calculated by atomic percentage as follows: niobium 10% - 14%, titanium 8% - 12%, tantalum 1 - 5%, and the balance is zirconium. The high-strength and high-plasticity zirconium alloy provided by the present invention has a tensile strength of 840 - 870 MPa, an elongation of 8 - 10%, a tensile elastic modulus of 55 - 62 GPa, and a magnetic susceptibility of 1.68 - 1.75×10-6 cm3 g-1. Through the selective laser melting forming technology, a good combination of strength and plasticity is achieved, and at the same time, problems such as time-consuming and laborious traditional casting processing are solved, and the promotion and application prospect is good.

Description

Technical Field

[0001] The present invention relates to the technical field of zirconium alloys, and particularly to a high-strength, high-plasticity, low-magnetic-susceptibility biomedical Zr-Nb-Ti-Ta alloy and a preparation method thereof. Background Art

[0002] Zirconium alloys are widely used in the medical and nuclear fields, and the requirements for their mechanical properties are gradually increasing. Good compatibility, corrosion resistance, low elastic modulus, high strength, high elongation rate, and low magnetic susceptibility are needed. Nuclear magnetic resonance technology has promoted the development of medicine, but due to the influence of metal implants, artifacts will be generated during imaging. Research shows that the size of the artifacts is closely related to the magnetic susceptibility of the implant material, and the artifact volume decreases with the decrease of the magnetic susceptibility. Due to its low magnetic susceptibility performance, zirconium can greatly reduce the magnetization phenomenon of metal implants in the magnetic field during magnetic resonance imaging, reduce the influence of image artifacts, and thus is beneficial for doctors to judge the condition.

[0003] Currently, the commonly used metal implants in the medical field mainly include titanium and its alloys, stainless steel, cobalt-chromium, etc. Among them, titanium and its alloys have good biocompatibility and good mechanical properties and are widely used. However, these materials also have certain effects on the human body. Their elastic modulus is much higher than that of human bones, and the elastic modulus mismatch will lead to the failure of the implant and even cause serious damage to human health. Zirconium and its zirconium alloys have excellent biocompatibility, low magnetic susceptibility and elastic modulus, and good mechanical properties. Based on the above situation, zirconium alloys are considered to have higher potential than titanium alloys in some special applications.

[0004] Metal implants have complex shapes, and at the same time, the shapes vary from person to person without regularity. The traditional preparation methods are all subtractive manufacturing, with low material utilization rate, and it is difficult to prepare a shape that completely fits the implant required by the human body in the casting mold. 3D printing technology can scan the human bone model, then perform modeling, input the model into the device for slicing processing, and directly print and form. The whole process is convenient and fast, can save a lot of manpower and time, and at the same time has high material utilization rate. Complex-shaped parts can be formed by the method of layer-by-layer stacking.

[0005] Currently, there is little research on the additive manufacturing of zirconium alloys. In the article "Effects of process parameters on the mechanical properties of additively manufactured Zr-1Mo alloy builds", a high-strength zirconium alloy was obtained by selective laser melting of Zr-1Mo alloy, but its elongation was low; in the article "Laser powder bed fusion of a Zr-alloy: Tensile properties and biocompatibility", the forming of Zr-702 alloy was studied, and a high-plasticity and low-strength alloy was prepared. To sum up, it is urgent to study a zirconium alloy material to achieve a good combination of high strength and high plasticity. At the same time, with the rise of 3D printing technology, studying 3D printing technology for zirconium alloy forming has good prospects and can reduce the time and energy of medical implant preparers to a certain extent. Summary of the Invention

[0006] The present invention mainly takes a biomedical zirconium alloy as the research object. By adding three elements of niobium, titanium, and tantalum to the zirconium matrix and using selective laser melting technology, a new type of biomedical zirconium alloy with good combination of low magnetic susceptibility, high strength, and high plasticity is prepared, expanding the categories of biomedical materials, and solving problems such as time-consuming and laborious traditional forming of medical models through selective laser melting.

[0007] In order to achieve the above invention purpose, the present invention provides the following technical solutions.

[0008] A high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta series alloy and method, the alloy composition is calculated according to atomic percentage: niobium 8% - 12%, titanium 8% - 12%, tantalum 1 - 5%, and the rest is zirconium.

[0009] The raw materials used in the present invention are sponge zirconium, sponge titanium, niobium blocks, and tantalum wires with a purity exceeding 99.0 wt%.

[0010] A high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta series alloy prepared by the present invention, the tensile strength of the alloy is 830 - 870 MPa, the elongation is 8% - 10%, the tensile elastic modulus is 55 - 62 GPa, and the magnetic susceptibility is 1.68 - 1.75×10 -6 cm 3 g -1 .

[0011] The present invention provides a preparation method of a high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta series alloy, including the following steps.

[0012] (1) Raw material weighing: According to the nominal composition of the alloy, sponge zirconium, sponge titanium, niobium blocks, and tantalum wires with industrial purity exceeding 99.0 wt% are selected as raw materials, and weighed and proportioned according to atomic percentages.

[0013] (2) Raw material mixing: The weighed zirconium, niobium, titanium, and tantalum are mixed evenly by means of stirring and mixing.

[0014] (3) Alloy melting: The alloy is melted using a water-cooled copper crucible non-consumable vacuum arc furnace. In order to ensure that the high-melting-point niobium and tantalum elements can be melted smoothly during the melting process, the high-melting-point materials should be placed in the inner wall area of the crucible during the first melting. After the raw materials are put into the crucible, vacuum pumping is carried out. When the vacuum degree in the furnace reaches a state of 2×10 -2 ~4×10 -2 Pa, argon is introduced for protection, and the air pressure is controlled at one standard atmospheric pressure; the current during melting is 300~380A, and the entire melting time is maintained at 600~840s. After melting, cooling is carried out by circulating cooling water through the bottom of the crucible. To ensure uniform mixing of the components, the ingot needs to be flipped and remelted 5 times to obtain the Zr-Nb-Ti-Ta alloy system.

[0015] (4) Atomization powder making: The ingot is atomized using a rotating electrode induction gas atomization device. During atomization, the melted ingot must be fixed in the fixture of the gas atomization device, and then vacuum pumping is carried out, and argon is introduced for protection. During the atomization process, the pressure of the atomization nozzle is set to 4.5~5.5MPa, the rotation speed of the rod is 13cm / min, and the melting current of the induction coil during the atomization process is 88~96A. The zirconium alloy rod is heated until the bottom of the zirconium alloy rod melts to form droplets, and the droplets are broken by high-pressure argon. The droplets are quickly cooled and solidified. When the atomization gas pressure is lower than 4.5MPa, atomization is stopped, and finally spherical Zr-Nb-Ti-Ta alloy powder with good sphericity is obtained.

[0016] (5) 3D printing: The powder is melted and formed using a selective laser melting device. Before forming, argon needs to be introduced into the chamber for purging. The forming process parameters are as follows: laser power: 180 - 250W, scanning speed: 600 - 1100mm / s, scanning spacing 0.07 - 0.11mm, scanning layer thickness 0.3mm, and the oxygen content during the forming process is controlled at 400 - 600ppm. During the forming process, the zirconium alloy powder quickly melts and solidifies under high-energy laser, and is stacked layer by layer to obtain the Zr-Nb-Ti-Ta alloy system.

[0017] The high-strength and high-ductility biomedical Zr-Nb-Ti-Ta alloy system prepared by the present invention selects four elements of zirconium, niobium, titanium, and tantalum with good biocompatibility and is formed by selective laser melting technology, which can solve the problem of personalized manufacturing in biomedical applications. The formed sample has a low magnetic susceptibility (1.68~1.75×10 -6cm 3 g -1 ), which can effectively reduce the influence of metal artifacts during nuclear magnetic resonance, and at the same time achieve a good combination of high strength and high plasticity. The high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy prepared by the present invention can be widely used in the fields of biomedical implant materials and the like.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy of the present invention has good biocompatibility. By adding three elements of niobium, titanium, and tantalum, alloying is achieved, and it has no toxic or side effects on the human body.

[0020] 2. The tensile strength of the high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy of the present invention can reach up to 867 MPa at most, the elongation rate is 9.6%, and at the same time, the tensile Young's modulus remains between 55 and 62 GPa, which can meet the performance requirements of the vast majority of biomedical materials. The Young's modulus is close to that of human bone and far lower than that of titanium and its alloys, which can effectively alleviate the "stress shielding" problem caused by the mismatch of elastic modulus between the implant and human bone.

[0021] 3. The magnetic susceptibility of the high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy of the present invention is 1.75×10 -6 cm 3 g -1 , far lower than that of titanium and its alloys, which can effectively alleviate the influence of metal artifacts during nuclear magnetic resonance.

[0022] 4. The high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy of the present invention expands the types of biomedical materials and provides a new type of material for biomedical implants.

[0023] 5. The high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy of the present invention realizes a good combination of strength and plasticity through the selective laser melting forming technology, can meet the requirements of the market, and at the same time solves the problems such as time-consuming and laborious traditional casting processing, and greatly reduces the energy input of medical parts. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is the powder morphology of a high-strength and high-plasticity biomedical Zr-Nb-Ti-Ta alloy prepared by the present invention;

[0025] Figure 2 is the tensile stress-strain curve of Example 2 of the present invention;

[0026] Figure 3 is the M-H curve of Example 2 of the present invention;

[0027] Figure 4 Comparison image of the magnetic susceptibilities of the biomedical zirconium alloy prepared according to the present invention and other alloys. Detailed implementation manners

[0028] The present invention will be further described below in conjunction with specific technical solutions and test steps, but this does not limit the protection scope of the present invention.

[0029] Example 1:

[0030] Component ratio: Industrial materials with a purity of more than 99.0% are selected as raw materials. The atomic percentages of the components of the alloy are: zirconium 83%, niobium 8%, titanium 8%, and tantalum 1%.

[0031] Preparation method:

[0032] (1) Raw material weighing: Weigh and proportion the raw materials according to the atomic percentages of the components.

[0033] (2) Raw material mixing: Mix the weighed zirconium, niobium, titanium, and tantalum evenly by means of stirring and mixing.

[0034] (3) Alloy melting: The alloy is melted using a water-cooled copper crucible non-consumable vacuum arc furnace. In order to ensure the smooth melting of high-melting-point niobium and tantalum elements during the melting process, the high-melting-point materials should be placed in the inner wall area of the crucible during the first melting. After the raw materials are put into the crucible, vacuum treatment is carried out. When the vacuum degree in the furnace reaches 3×10 -2 Pa, argon is introduced for protection, and the air pressure is controlled at one standard atmospheric pressure; the current during melting is 360A. During the melting process, pay attention to observing the situation in the furnace, and the materials need to be completely melted. After the melting is completed, cooling is carried out by circulating cooling water through the bottom of the crucible. To ensure uniform mixing of the components, the ingot needs to be flipped and remelted 5 times to obtain a Zr-Nb-Ti-Ta alloy system.

[0035] (4) Atomization powder making: The ingot is atomized using a rotating electrode induction gas atomization device. During atomization, the melted ingot must be fixed in the fixture in the gas atomization device, and then vacuum treatment is carried out, and argon is introduced for protection. During the atomization process, the pressure of the atomization nozzle is set to 4.5 MPa, the rotation speed of the rod is 13 cm / min, the melting current of the induction coil during the atomization process is 90 A, the zirconium alloy rod is heated until the bottom of the zirconium alloy rod melts to form droplets, and the droplets are broken by high-pressure argon. The droplets are quickly cooled and solidified. When the atomization gas pressure is lower than 4.5 MPa, stop atomization. Finally, spherical Zr-Nb-Ti-Ta alloy powder with good sphericity is obtained. The powder morphology of this high-strength and high-ductility biomedical Zr-Nb-Ti-Ta alloy system is as Figure 1 shown.

[0036] (5) 3D printing: The powder is melted and formed using a selective laser melting equipment. Before forming, argon gas is introduced into the chamber for purging. The laser power is 190 W, the scanning speed is 900 mm / s, the scanning spacing is 0.075 mm, the scanning layer thickness is 0.03 mm, and the energy density is 93.8 J / mm 3 . During the forming process, the oxygen content is controlled within 400 - 600 ppm. During the forming process, the zirconium alloy powder rapidly melts and solidifies under high-energy laser, and is stacked layer by layer to obtain a Zr-Nb-Ti-Ta series alloy with uniform structure.

[0037] Alloy testing: The high-strength and high-ductility biomedical Zr-Nb-Ti-Ta series alloy formed by selective laser melting is subjected to tensile mechanical property testing on an electronic universal testing machine (Instron8890). The tensile elastic modulus of the alloy sample is measured to be 56 GPa, the tensile strength is 842 MPa, and the elongation is 7.5%. The magnetic susceptibility of the zirconium-based alloy is analyzed using a vibrating sample magnetometer to obtain the M-H curve, and the magnetic susceptibility of the alloy sample is 1.69×10 -6 cm -3 g -1 .

[0038] Example 2:

[0039] Composition ratio: Industrial materials with a purity of over 99.0% are selected as raw materials. The atomic percentages of each component of the alloy are: zirconium 77.5%, niobium 10%, titanium 10%, and tantalum 2.5%.

[0040] Preparation method:

[0041] (1) Raw material weighing: Weigh and mix the raw materials according to the atomic percentages of each component raw material.

[0042] (2) Raw material mixing: The weighed zirconium, niobium, titanium, and tantalum are mixed evenly by means of stirring and mixing.

[0043] (3) Alloy melting: The alloy is melted using a water-cooled copper crucible non-consumable vacuum arc furnace. In order to ensure that the high-melting-point niobium and tantalum elements can be melted smoothly during the melting process, the high-melting-point materials should be placed in the inner wall area of the crucible during the first melting. After the raw materials are put into the crucible, vacuum treatment is carried out. When the vacuum degree in the furnace reaches 2×10 -2 Pa, argon gas is introduced for protection, and the air pressure is controlled at one standard atmosphere; the current during melting is 380 A. During the melting process, pay attention to observing the situation in the furnace, and the materials need to be completely melted. After melting, cooling is carried out by circulating cooling water through the bottom of the crucible. In order to ensure uniform mixing of components, the ingot needs to be flipped and remelted 5 times to obtain a Zr-Nb-Ti-Ta series alloy.

[0044] (4) Atomization powder production: The ingot is atomized using a rotating electrode induction gas atomization device. During atomization, the smelted ingot must be fixed in the fixture of the gas atomization device, and then vacuum treatment is carried out, followed by the introduction of argon for protection. During the atomization process, the atomization nozzle pressure is set to 5 MPa, the rotation speed of the rod is 13 cm / min, and the melting current of the induction coil during atomization is 96 A. The zirconium alloy rod is heated until the bottom of the zirconium alloy rod melts to form droplets, and high-pressure argon is used to break up the droplets. The droplets are rapidly cooled and solidified. When the atomization gas pressure is lower than 5 MPa, atomization is stopped, and finally, Zr-Nb-Ti-Ta alloy powder with good sphericity is obtained.

[0045] (5) 3D printing: The powder is melted and formed using a selective laser melting device. Before forming, argon is introduced into the chamber for purging. The laser power is 180 W, the scanning speed is 1050 mm / s, the scanning spacing is 0.11 mm, the scanning layer thickness is 0.03 mm, and the energy density is 51.9 J / mm 3 . During the forming process, the oxygen content is controlled within 400 - 600 ppm. During the forming process, the zirconium alloy powder rapidly melts and solidifies under high-energy laser, and is stacked layer by layer to obtain a Zr-Nb-Ti-Ta alloy with uniform structure.

[0046] Alloy testing: The high-strength and high-ductility biomedical Zr-Nb-Ti-Ta alloy after selective laser melting forming is subjected to tensile mechanical property testing on an electronic universal testing machine (Instron8890). The tensile stress-strain curve is as Figure 2 shown. The measured tensile elastic modulus of the alloy sample is 60 GPa, the tensile strength is 867 MPa, and the elongation is 9.6%. The magnetic susceptibility of the zirconium-based alloy is analyzed using a vibrating sample magnetometer to obtain the M-H curve, as Figure 3 shown. The magnetic susceptibility of the alloy sample is obtained as 1.72×10 -6 cm -3 g -1 . The comparison image of the magnetic susceptibility between the biomedical zirconium alloy prepared in this invention and other alloys is as Figure 4 shown. The comparison of the mechanical properties related to the additive manufacturing of zirconium alloy in this example is shown in Table 1. Compared with the current additive manufacturing of zirconium alloy, Example 2 achieves a good combination of plasticity and strength.

[0047] Table 1 Comparison of mechanical properties of zirconium alloy additive manufacturing

[0048] Alloy material Preparation method Tensile strength / MPa Elongation rate (%) Zr-10Nb-10Ti-2.5Ta Selective laser melting 867 9.6 Zr-1Mo Selective laser melting 1176 6.2 Zr-702 Selective laser melting 606 29

[0049] Comparative Example 1

[0050] The Zr-Nb-Ti-Ta series alloy powder prepared in Example 2 was melted by 3D printing using a selective laser melting equipment. Before forming, argon gas was introduced into the chamber for purging. In this comparative example, high energy density forming parameters were used to form a contrast with Example 2. The specific process parameters were: laser power 220W, scanning speed 650mm / s, scanning spacing 0.1mm, scanning layer thickness 0.03mm, and energy density 112.8J / mm 3 , and the oxygen content during the forming process was controlled within 400 - 600 ppm. During the forming process, the zirconium alloy powder was rapidly melted and solidified under high energy laser, and stacked layer by layer to obtain a Zr-Nb-Ti-Ta series alloy with uniform structure.

[0051] Alloy testing: The high-strength and high-ductility biomedical Zr-Nb-Ti-Ta series alloy after selective laser melting forming was subjected to tensile mechanical property testing on an electronic universal testing machine (Instron8890). The tensile elastic modulus of the alloy sample was measured to be 53.4 GPa, the tensile strength was 733 MPa, and the elongation was 1.44%. The magnetic susceptibility of the zirconium-based alloy was analyzed using a vibrating sample magnetometer to obtain the M-H curve, and the magnetic susceptibility of the alloy sample was 1.76×10 -6 cm -3 g -1 . It can be seen from Comparative Example 1 that the designed alloy can achieve a good combination of high strength and high plasticity at low energy density.

[0052] Example 3:

[0053] Composition ratio: Industrial materials with a purity of over 99.0% were selected as raw materials. The atomic percentages of each component of the alloy were: zirconium 71%, niobium 12%, titanium 12%, and tantalum 5%.

[0054] Preparation method:

[0055] (1) Raw material weighing: Weigh and mix the raw materials according to the atomic percentages of each component.

[0056] (2) Raw material mixing: Mix the weighed zirconium, niobium, titanium, and tantalum evenly by stirring.

[0057] (3) Alloy melting: The alloy was melted using a water-cooled copper crucible non-consumable vacuum arc furnace. To ensure the smooth melting of high melting point niobium and tantalum elements during the melting process, the high melting point materials should be placed in the inner wall area of the crucible during the first melting. After the raw materials were put into the crucible, vacuum treatment was carried out, and the vacuum degree in the furnace was 3×10 -2After the state of Pa, argon is introduced for protection, and the air pressure is controlled at one standard atmosphere; during melting, the current is 346 A. During the melting process, it is necessary to observe the situation inside the furnace, and the material needs to be completely melted. After melting, cooling is carried out by circulating cooling water through the bottom of the crucible. To ensure uniform mixing of components, the ingot needs to be turned over and remelted 5 times to obtain the Zr-Nb-Ti-Ta alloy system.

[0058] (4) Atomization and powder making: The ingot is atomized using a rotating electrode induction gas atomization device. During atomization, the melted ingot must be fixed in the fixture of the gas atomization device, and then vacuum pumping is carried out, followed by introducing argon for protection. During the atomization process, the pressure of the atomization nozzle is set to 5.5 MPa, the rotation speed of the rod is 13 cm / min, and the melting current of the induction coil during atomization is 98 A. The zirconium alloy rod is heated until the bottom of the zirconium alloy rod melts to form droplets, and high-pressure argon is used to break up the droplets. The droplets are rapidly cooled and solidified. When the atomization gas pressure is lower than 5.5 MPa, atomization stops, and finally, Zr-Nb-Ti-Ta alloy powder with good sphericity is obtained.

[0059] (5) 3D printing: The powder is melted and formed using a selective laser melting device. Before forming, argon is introduced into the chamber for purging. The laser power is 250 W, the scanning speed is 1100 mm / s, the scanning spacing is 0.09 mm, the scanning layer thickness is 0.03 mm, and the energy density is 84.1 J / mm 3 , and the oxygen content during the forming process is controlled at 400 - 600 ppm. During the forming process, the zirconium alloy powder rapidly melts and solidifies under high-energy laser, and is stacked layer by layer to obtain a Zr-Nb-Ti-Ta alloy with uniform structure.

[0060] Alloy detection: The high-strength and high-ductility biomedical Zr-Nb-Ti-Ta alloy after selective laser melting forming is subjected to tensile mechanical property testing on an electronic universal testing machine (Instron8890). The tensile elastic modulus of the alloy sample is measured to be 62 GPa, the tensile strength is 853 MPa, and the elongation is 8.3%. The magnetic susceptibility of the zirconium-based alloy is analyzed using a vibrating sample magnetometer to obtain the M-H curve, and the magnetic susceptibility of the alloy sample is obtained as 1.75×10 -6 cm -3 g -1 .

[0061] The above embodiments are the preferred embodiments of the present invention. All processes similar to the present invention and equivalent changes made shall fall within the protection scope of the present invention.

Claims

1. A high-strength and high-ductility biomedical Zr-Nb-Ti-Ta alloy system, characterized in that, Add three highly biocompatible elements of niobium, titanium, and tantalum. The composition of the zirconium-based alloy is calculated by atomic percentage: niobium 10% - 12%, titanium 8% - 12%, tantalum 1 - 5%, and the balance is Zr; the tensile strength of the zirconium-based alloy is 830 - 870 MPa, the elongation is 8% - 10%, the tensile elastic modulus is 55 - 62 GPa, and the magnetic susceptibility is 1.68×10 -6 ~1.75×10 -6 cm 3 g -1 ; It is applied to the preparation of biomedical products through selective laser melting technology, and the biomedical products include artificial joints, dentures, and prosthetics.

2. A method for preparing the high-strength and high-ductility biomedical Zr-Nb-Ti-Ta alloy system according to claim 1, characterized in that, comprises the following steps: (1) Raw material weighing: According to the nominal composition of the alloy, select zirconium sponge, titanium sponge, niobium block, and tantalum wire as raw materials, and weigh and mix them according to the atomic percentage; (2) Raw material mixing: Mix the weighed zirconium, niobium, titanium, and tantalum evenly by means of stirring and mixing; (3) Alloy melting: Use a water-cooled copper crucible non-consumable vacuum arc furnace to melt the alloy. In order to ensure that the high-melting-point niobium and tantalum elements can be melted smoothly during the melting process, place the high-melting-point materials in the inner wall area of the crucible during the first melting. After the raw materials are put into the crucible, evacuate and introduce argon for protection. After the melting is completed, cool it by circulating cooling water through the bottom of the crucible to obtain the Zr-Nb-Ti-Ta alloy system; (4) Atomization powder making: Use a rotating electrode induction gas atomization device to atomize the ingot. During atomization, fix the melted ingot in the fixture in the gas atomization device, then evacuate and introduce argon for protection. During the atomization process, heat the zirconium alloy rod until the bottom of the zirconium alloy rod melts to form droplets, and use high-pressure argon to break up the droplets. The droplets are rapidly cooled and solidified to form Zr-Nb-Ti-Ta alloy powder; (5) 3D printing: Use a selective laser melting device to melt and form the powder. Before forming, introduce argon into the chamber for purging. During the forming process, the zirconium alloy powder rapidly melts and solidifies under high-energy laser, and is stacked layer by layer to obtain a Zr-Nb-Ti-Ta alloy system with uniform structure.

3. The preparation method according to claim 2, characterized in that, In step (3), the vacuum degree in the furnace is 2×10 -2 ~4×10 -2 Pa; the air pressure of the introduced argon is controlled at one standard atmosphere; the current during melting is 320 - 380 A, and the entire melting time is maintained at 600 - 840 s. To ensure uniform mixing of components, the ingot is turned over and remelted 5 times to obtain a Zr-Nb-Ti-Ta alloy with uniform composition.

4. The preparation method according to claim 2, characterized in that, In step (4), the atomization nozzle pressure is 4.5 - 5.5 MPa, the rotational speed of the rod is 13 cm / min, the melting current of the induction coil during atomization is 88 - 98 A. When the atomization gas pressure is lower than 4.5 MPa, stop atomization, and finally obtain Zr-Nb-Ti-Ta alloy powder with good sphericity.

5. The preparation method according to claim 2, characterized in that, In step (5), use the Zr-Nb-Ti-Ta alloy powder for 3D printing and forming. The forming process parameters are: laser power: 180 - 250 W, scanning speed: 600 - 1100 mm / s, scanning spacing 0.07 - 0.11 mm, scanning layer thickness 0.3 mm, and the oxygen content during the forming process is controlled at 400 - 600 ppm. Finally, obtain the Zr-Nb-Ti-Ta alloy system.

6. The preparation method according to claim 2, characterized in that: The purity of the zirconium sponge, titanium sponge, niobium block, and tantalum wire described in step (1) all exceeds 99.0 wt%.

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