A high-strength zr-ta alloy material with amorphous and amplitude modulation heterostructure and a preparation method thereof

Abstract

The application discloses a high-strength Zr-Ta alloy material with amorphous and amplitude modulation heterogeneous structures and a preparation method thereof. A zirconium source is repeatedly smelted to obtain a Zr ingot; a Ta source is divided into N parts and then repeatedly smelted to obtain N Ta ingots, and then the Ta ingots are gradually smelted into the Zr ingot for multiple times, and then the obtained Zr-Ta ingot is repeatedly smelted to obtain a Zr-Ta alloy ingot, finally, the Zr-Ta alloy ingot is smelted to obtain a Zr-Ta alloy liquid, and the Zr-Ta alloy liquid is sucked and cast in a mold to obtain the Zr-Ta alloy material. In the Zr-Ta alloy material, the components are as follows in terms of atomic percentage: Zr 40% to 80%, and Ta 20% to 60%. The Zr-Ta alloy provided by the application has both amplitude modulation and amorphous structures, and has excellent mechanical properties and a relatively low elastic modulus.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical zirconium-based alloys, and in particular relates to a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures and a preparation method thereof. Background Art

[0002] The market for advanced medical devices is growing rapidly. Currently, biomedical metal materials primarily include stainless steel, Ti alloys, Co alloys, Mg alloys, shape memory alloys, precious metals, and pure metals (Ta, Nb, Zr). Due to their excellent properties in strength, plasticity, toughness, modulus, hardness, fatigue life, and corrosion resistance, they are widely used in orthopedic treatments such as fixation devices, artificial joints, dentistry, artificial spines, and orthopedic devices. Currently, biomedical titanium alloys are widely used in the field of non-degradable biomaterials. Medical titanium alloys have the following characteristics: ① Low density, effectively reducing the load on the human body; ② Excellent biocompatibility; ③ Low cost, reducing the financial burden on patients. Currently, the most commonly used titanium alloy for treating and replacing hard tissue in the human body is Ti-6Al-4V (TC4). However, TC4 also has significant disadvantages: ① The alloy's high elastic modulus (110 GPa) is much higher than that of human bone, which can cause "stress shielding" effects with long-term use, resulting in insufficient mechanical compatibility; ② The V element in the alloy has certain cytotoxicity, and excessive Al may cause Alzheimer's disease, resulting in insufficient biocompatibility. At the same time, the magnetic susceptibility problem of medical titanium alloy materials cannot be ignored. Materials with higher magnetic susceptibility will cause "artifacts" when patients undergo MRI examinations. The image may be distorted around the metal, causing unnecessary trouble. Although the magnetic susceptibility of biomedical titanium alloys is currently very low, in order to cope with increasingly complex situations in the future, it is necessary to develop a new material with lower magnetic susceptibility. Current research has found that zirconium and titanium are in the same main group and have similar physical and chemical properties. The key is that zirconium has a lower magnetic susceptibility than titanium. Therefore, it is possible to try to develop biomedical zirconium alloys. At the same time, in order to avoid adverse reactions to the human body, it is necessary to select alloying elements with good biocompatibility, good corrosion resistance and low magnetic susceptibility, such as Nb, Ta, Mo, Fe, etc., and alloy them with zirconium to develop a zirconium alloy with good biological properties.

[0003] Tantalum (Ta) is a biophilic metal with superior mechanical properties, corrosion resistance, and biocompatibility compared to titanium and its alloys. Ta promotes osseointegration and bone differentiation earlier than titanium (Ti). Furthermore, the surface structure and chemical properties of the material significantly influence cellular behavior and subsequent osteoinduction. Zirconium (Zr) has similar chemical properties to Ta and can form a eutectoid structure with it. Furthermore, Zr can effectively reduce the elastic modulus of Ta. Compared with Ta, Zr has a lower melting point (1852°C) and a lower elastic modulus (88 GPa), and is also less expensive. Both Zr and Ta exhibit low magnetic susceptibility and cytotoxicity. Furthermore, Zr-Ta binary alloys exhibit a strong tendency to undergo spinodal decomposition. Spinomodal decomposition effectively improves the alloy's strength without significantly increasing the elastic modulus. Therefore, the Zr-Ta binary alloy formed by the combination of Zr and Ta has broad application value, particularly as a dental implant material, and may have broad clinical potential.

[0004] According to the Zr-Ta binary phase diagram, the melting point of Zr is 1852℃, the melting point of Ta is 2996℃, and the density of Zr is 6.49g / cm 3 , and the density of Ta is 16.68g / cm 3 The melting point and density of the two are very different. If Zr-Ta binary alloy is directly smelted, the alloy will inevitably suffer from severe segregation as the tantalum content increases. Summary of the Invention

[0005] To address the shortcomings of the prior art, the first objective of the present invention is to provide a method for preparing a high-strength Zr-Ta alloy material with both an amorphous and spinodal heterostructure. This method utilizes smelting followed by suction casting to produce a high-strength Zr-Ta alloy material with both spinodal and amorphous structures. This method is simple, controllable, and suitable for large-scale production.

[0006] The second object of the present invention is to provide a high-strength Zr-Ta alloy material having both amorphous and spinodal heterostructures prepared by the above-mentioned preparation method. The Zr-Ta alloy provided by the present invention has a spinodal heterostructure and an amorphous structure, and at the same time has excellent mechanical properties and a relatively low elastic modulus.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] The present invention provides a preparation method of a high-strength Zr-Ta alloy material with both amorphous and amplitude-modulated heterostructures. The method comprises the following steps: repeatedly melting a zirconium source to obtain a Zr ingot; dividing a Ta source into N parts and repeatedly melting each of the parts to obtain N Ta ingots; firstly placing one Ta ingot on top of a Zr ingot, melting to obtain a No. 1 Zr-Ta ingot; then taking another Ta ingot and placing it on top of the No. 1 Zr-Ta ingot, melting to obtain a No. 2 Zr-Ta ingot; repeating the above process until the Nth Ta ingot is placed on top of the No. N-1 Zr-Ta ingot, melting to obtain a No. N Zr-Ta ingot; then repeatedly melting the No. N Zr-Ta ingot to obtain a Zr-Ta alloy ingot; finally, melting the Zr-Ta alloy ingot to obtain a Zr-Ta alloy liquid; and sucking and casting the Zr-Ta alloy liquid into a mold to obtain a Zr-Ta alloy material. The Zr-Ta alloy material comprises the following components, calculated by atomic percentage: Zr 40% ~ 80%, Ta: 20% ~ 60%.

[0009] In the present invention, controlling the composition of the Zr-Ta alloy within the aforementioned range allows the resulting alloy to undergo spinodal decomposition, resulting in a spinodal heterostructure. This spinodal strengthening mechanism imparts high strength to the zirconium-tantalum alloy. However, due to the high Ta content, to avoid uneven melting caused by component segregation, the present invention first melts all the low-melting-point Zr particles into an ingot. The Ta chunks obtained from the smelting are then added to the Zr ingot in small amounts multiple times to melt the ingot. This significantly reduces the degree of segregation in the alloy. Finally, the resulting alloy is vacuum-casted in a water-cooled copper mold. This process not only further reduces segregation but also refines the grains, resulting in an amorphous structure and further enhancing material properties. The alloy produced by this method exhibits both high strength and a relatively low elastic modulus.

[0010] Due to the high tantalum content of the alloy in the present invention, even a zirconium source with a low melting point must first be smelted to obtain a Zr ingot, and then Ta blocks obtained by smelting are added to the Zr ingot in small amounts multiple times to obtain a Zr-Ta alloy material that meets the designed composition and is uniform. If the Zr source and Ta source are not smelted separately first, even if Ta blocks are added in small amounts multiple times, macroscopic smelting unevenness is likely to occur.

[0011] In a preferred embodiment, the zirconium source is zirconium particles.

[0012] In a preferred embodiment, the process of repeatedly melting the zirconium source to obtain a Zr ingot is as follows: the zirconium source is placed in a vacuum arc melting furnace, first melted at a current of 150-200A to obtain a zirconium liquid, and then the current is increased to 220-270A and repeatedly melted to obtain a Zr ingot. By initially melting the zirconium source at a lower current, the present invention prevents particle scattering caused by direct high-temperature melting.

[0013] More preferably, the repeated smelting is performed 2-3 times.

[0014] In a preferred embodiment, the tantalum source is a tantalum block.

[0015] The inventors have discovered that using zirconium particles and tantalum blocks as raw materials can better ensure the accuracy of the composition.

[0016] In a preferred embodiment, the N is 4 to 5. By controlling the number of Ta sources within the above range, a uniform and segregation-free Zr-Ta alloy can be obtained.

[0017] In a preferred embodiment, the process of repeatedly melting any one Ta source to obtain N Ta ingots is as follows: first, the Ta source is melted with a current of 200-250A to obtain Ta liquid, and then the current is increased to 270-320A and repeatedly melted to obtain Ta ingots.

[0018] More preferably, the repeated smelting is performed 3-4 times.

[0019] In a preferred solution, after any Ta ingot is placed on top of a Zr ingot or any Zr-Ta ingot, the current used for smelting is 300-350A.

[0020] A preferred solution is to repeatedly melt the N-number Zr-Ta ingot using a current of 330A-360A for 10-12 times to obtain a Zr-Ta alloy ingot.

[0021] The present invention adds Ta to Zr in small amounts for multiple times, and according to the above steps, the alloy can be smelted uniformly and segregation can be reduced.

[0022] In a preferred solution, a current of 300-320 A is used to melt the Zr-Ta alloy ingot to obtain a Zr-Ta alloy liquid.

[0023] Preferably, the size of the mold used for the suction casting is ≤10 mm in width, ≤10 mm in thickness, and ≤40 mm in length.

[0024] In the present invention, the mold height for suction casting is not restricted, and other dimensions are within the scope of the present invention. A Zr-Ta alloy material with both a amplitude-modulated heterostructure and an amorphous structure can be obtained. The introduction of the amorphous structure further imparts high strength and toughness, as well as a low elastic modulus. However, the mold size used for suction casting must be controlled within the scope of the present invention. Using a mold within this size range allows for a sufficient cooling rate to obtain an amorphous structure. If the mold size is too large, the cooling rate is too slow, and the amorphous structure cannot be obtained.

[0025] Preferably, the mold is made of copper. Copper has good thermal conductivity, which facilitates rapid cooling of the alloy. It also has good dimensional stability, which helps ensure the mold's dimensional accuracy.

[0026] During the actual operation, the ingot is placed on the edge of the suction casting mold in the vacuum arc melting furnace, the arc is continued to be struck, and the current is increased to 300-320A to melt the ingot. At the same time, the air pressure in the furnace is increased, and the liquid alloy is quickly sucked into the mold through the pressure difference to obtain a block Zr-Ta alloy.

[0027] In a preferred embodiment, the Zr-Ta alloy material has the following composition, calculated by atomic percentage: Zr 60% to 80%, Ta 20% to 40%. Within the above range, the obtained Zr-Ta alloy material has a very obvious amorphous structure.

[0028] Further preferably, the Zr-Ta alloy material has the following composition, calculated in atomic percentage: Zr: 65% to 70%, Ta: 30% to 35%.

[0029] The present invention also provides a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures prepared by the above preparation method.

[0030] Principles and advantages

[0031] The present invention provides a spinodal high-strength Zr-Ta alloy comprising, in atomic percentage, 60% to 80% Zr and 20% to 40% Ta. The inventors have discovered that when the composition of the Zr-Ta alloy is controlled within the aforementioned range, the resulting alloy can undergo spinodal decomposition, resulting in a spinodal heterostructure. The preparation method of the present invention comprises first preparing a Zr source and a Ta source according to a designed composition ratio, then smelting the resulting Zr-Ta alloy ingot. The combination of zirconium and tantalum introduces a spinodal strengthening mechanism, resulting in a high-strength zirconium-tantalum alloy. Furthermore, due to the high Ta content in the designed alloy, to avoid uneven smelting due to component segregation, the present invention first melts all low-melting-point Zr particles into an ingot, then repeatedly adds small amounts of Ta blocks to the Zr ingot to melt it. This significantly reduces the degree of alloy segregation. Finally, the obtained alloy is subjected to water-cooled copper mold suction casting. Suction casting can not only further reduce segregation, but also refine the grains, while obtaining an amorphous structure and further strengthening the material properties. The alloy obtained by the above method not only has high strength, but also has a relatively low elastic modulus. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, without paying any creative work, other drawings obtained based on these drawings still fall within the scope of the present invention.

[0033] Figure 1 This is the Xrd spectrum of the Zr-30Ta alloy in Example 1. From the figure, it can be seen that the diffraction peak is broadened, which has the characteristics of an amorphous composite material.

[0034] Figure 2 This is the TEM bright field image of the Zr-30Ta alloy in Example 1. It can be seen from the figure that the Zr-30Ta alloy has a corrugated spinodal structure, which proves that the Zr-30Ta has undergone spinodal decomposition.

[0035] Figure 3 The TEM high-resolution image and selected area electron diffraction image of the Zr-30Ta alloy in Example 1. Figure 3 Part of the area in the left picture has an amorphous structure, and in the selected area electron diffraction pattern on the right picture, we can see that it has a halo ring unique to the amorphous structure, proving that it has an amorphous structure and is an amorphous composite material.

[0036] Figure 4 This is a strength comparison chart of Example 1 and the mature Ti-6Al-4V alloy.

[0037] Figure 5 This is the loading and unloading curve of the nanoindentation test of Zr-30Ta in Example 1. DETAILED DESCRIPTION

[0038] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention will be described in further detail below with reference to the accompanying drawings.

[0039] Example 1 (Zr-30Ta)

[0040] Zr particles with a purity of 99.95% and tantalum blocks with a thickness of 3-6 mm with a purity of 99.95% are weighed according to the mass ratio of the binary Zr-30% Ta alloy. 30 g are melted at a time. After the sample is prepared, it is cleaned with ultrasonic wave and then blown dry with alcohol. Then it is placed in a clean sample bag. During the melting and setting out process, do not touch the sample with your hands. Close the door of the arc melting furnace and then evacuate the vacuum degree to ≤5×10 -3Pa, then argon protection, repeated vacuuming, and argon flushing twice, finally proceeded to the melting operation. Melting was performed in a vacuum arc furnace. Before melting, low-melting-point zirconium pellets were placed in the vacuum arc melting furnace. A current of 200A was first used to completely melt the zirconium pellets to obtain zircon liquid. The current was then increased to 270A and repeated melting to obtain a Zr ingot. The Ta source was divided into five small portions. A Ta block was first completely melted at 250A to obtain a Ta liquid. The current was then increased to 310A and repeated melting to obtain a Ta ingot. According to the principle of low melting point at the bottom and high melting point at the top, the Ta ingot is placed on top of the Zr ingot, and a current of 350A is used to completely melt it to obtain a Zr-Ta ingot. Ta is added to the Zr in small amounts multiple times. After all the Ta is added to the Zr, it is repeatedly melted 12 times using a current of 360A to obtain a mother ingot with uniform composition. Subsequently, the ingot is placed on the edge of a suction casting mold in a vacuum arc melting furnace, the arc is continued to be struck, and the current is increased to 360A to melt the ingot. At the same time, the air pressure in the furnace is increased, and the liquid alloy is quickly suction-cast into a 10mm*10mm*40mm mold through a pressure difference of 0.05MPa to obtain a block Zr-Ta alloy with a width of 10mm and a thickness of 10mm.

[0041] The prepared Zr-30Ta alloy was cut into sheets with a thickness of about 0.6 mm by wire cutting, and then cut into tensile samples with a gauge length of 8 mm. During stretching, the wire cutting corrosion liquid on the surface of the tensile part was ground off, and the rate during the stretching process was controlled at 0.336 mm / min.

[0042] Implementation Effect

[0043] 1. The relative mass content of Ta element in the Zr-30Ta alloy prepared in this experiment was measured by energy dispersive spectrometer (EDS) to be 30.8%, and the rest was Zr.

[0044] 2. Figure 1 The XRD spectrum of the Zr-30Ta alloy shows the broadening of the diffraction peaks, which is characteristic of an amorphous composite material.

[0045] 3. Figure 2 This is a TEM bright field image of the Zr-30Ta alloy. It can be seen from the figure that the Zr-30Ta alloy has a corrugated spinodal structure, which proves that the Zr-30Ta alloy has undergone spinodal decomposition.

[0046] 4. Figure 3 TEM high-resolution image and selected area electron diffraction image of Zr-30Ta alloy. Figure 3 Part of the area in the left picture has an amorphous structure, and in the selected area electron diffraction pattern on the right picture, we can see that it has a halo ring unique to the amorphous structure, proving that it has an amorphous structure and is an amorphous composite material.

[0047] 5. Figure 4In comparison with the mature Ti-6Al-4V alloy (yield strength 860MPa, tensile strength 965MPa), Zr-30Ta has a higher yield strength of 1318.2MPa and tensile strength of 1385.8MPa through tensile tests.

[0048] 6. Figure 5 The loading and unloading curves of the nanoindentation test of Zr-30Ta show that its elastic modulus is 94.8 GPa, which is lower than that of Ti-6Al-4V (110 GPa).

[0049] Example 2 (Zr-25Ta)

[0050] 99.95% pure Zr particles and 99.95% pure tantalum blocks with a thickness of 3-6 mm were weighed according to the mass ratio of the binary Zr-40% Ta alloy. 30 g was melted at a time. After the sample was prepared, it was cleaned with ultrasonic wave and then dried with alcohol. Then it was placed in a clean sample bag. During the melting and setting out process, do not touch the sample with your hands. Close the door of the arc melting furnace and then evacuate the sample to a vacuum degree of ≤5×10 -3 Pa, then argon protection, repeated vacuuming, and argon flushing twice, finally proceeded to the melting operation. Melting was performed in a vacuum arc furnace. Before melting, low-melting-point zirconium pellets were placed in the vacuum arc melting furnace. A current of 200A was first used to completely melt the zirconium pellets to obtain zircon liquid. The current was then increased to 270A and repeated melting to obtain a Zr ingot. The Ta source was divided into five small portions. A Ta block was first completely melted at 250A to obtain a Ta liquid. The current was then increased to 310A and repeated melting to obtain a Ta ingot. According to the principle of low melting point at the bottom and high melting point at the top, the Ta ingot is placed on top of the Zr ingot, and a current of 350A is used to completely melt it to obtain a Zr-Ta ingot. Ta is added to the Zr in small amounts multiple times. After all the Ta is added to the Zr, a current of 360A is used to repeatedly melt it 12 times to obtain a mother ingot with uniform composition. Subsequently, the ingot is placed on the edge of a suction casting mold in a vacuum arc melting furnace, the arc is continued to be struck, and the current is increased to 360A to melt the ingot. At the same time, the air pressure in the furnace is increased, and the liquid alloy is quickly suction-cast into the mold through a pressure difference of 0.05MPa to obtain a block Zr-Ta alloy with a width of 10mm and a thickness of 10mm.

[0051] Implementation Effect

[0052] Energy dispersive spectroscopy (EDS) analysis revealed a relative mass content of 25.4% Ta in the Zr-25Ta alloy prepared in this experiment, with the remainder being Zr. Scanning electron microscopy (SEM) images of the as-cast Zr-25Ta alloy revealed a distinct wavy spinodal decomposition structure. This demonstrates spinodal decomposition, and TEM analysis revealed an amorphous structure.

[0053] Example 3 (Zr-35Ta)

[0054] 99.95% pure Zr particles and 99.95% pure tantalum blocks with a thickness of 3-6 mm were weighed according to the mass ratio of binary Zr-35% Ta alloy. 30 g was melted at a time. After the sample was prepared, it was cleaned with ultrasonic wave and then dried with alcohol. Then it was placed in a clean sample bag. During the melting and setting out process, do not touch the sample with your hands. Close the door of the arc melting furnace and then evacuate the sample to a vacuum degree of ≤5×10 -3 Pa, then argon protection, repeated vacuuming, and argon flushing twice, finally proceeded to the melting operation. Melting was performed in a vacuum arc furnace. Before melting, low-melting-point zirconium pellets were placed in the vacuum arc melting furnace. A current of 200A was first used to completely melt the zirconium pellets to obtain zircon liquid. The current was then increased to 270A and repeated melting to obtain a Zr ingot. The Ta source was divided into five small portions. A Ta block was first completely melted at 250A to obtain a Ta liquid. The current was then increased to 310A and repeated melting to obtain a Ta ingot. According to the principle of low melting point at the bottom and high melting point at the top, the Ta ingot is placed on top of the Zr ingot, and a current of 350A is used to completely melt it to obtain a Zr-Ta ingot. Ta is added to the Zr in small amounts multiple times. After all the Ta is added to the Zr, a current of 360A is used to repeatedly melt it 12 times to obtain a mother ingot with uniform composition. Subsequently, the ingot is placed on the edge of a suction casting mold in a vacuum arc melting furnace, the arc is continued to be struck, and the current is increased to 360A to melt the ingot. At the same time, the air pressure in the furnace is increased, and the liquid alloy is quickly suction-cast into the mold through a pressure difference of 0.05MPa to obtain a block Zr-Ta alloy with a width of 10mm and a thickness of 10mm.

[0055] Specific data

[0056] Energy dispersive spectroscopy (EDS) analysis revealed a relative mass content of 35.4% Ta in the Zr-35Ta alloy prepared in this experiment, with the remainder being Zr. Scanning electron microscopy (SEM) observations of the as-cast Zr-35Ta alloy revealed a distinct wavy spinodal decomposition structure, demonstrating spinodal decomposition. TEM analysis revealed an amorphous structure.

[0057] Comparative Example 1 (no suction casting after smelting)

[0058] Zr particles with a purity of 99.95% and tantalum blocks with a thickness of 3-6 mm with a purity of 99.95% are weighed according to the mass ratio of the binary Zr-30% Ta alloy. 30 g are melted at a time. After the sample is prepared, it is cleaned with ultrasonic wave and then blown dry with alcohol. Then it is placed in a clean sample bag. During the melting and setting out process, do not touch the sample with your hands. Close the door of the arc melting furnace and then evacuate the vacuum degree to ≤5×10 -3Pa, then argon protection is adopted, vacuum is repeatedly drawn, argon is flushed in 2 times, and finally smelting operation is carried out. Smelting is carried out in a vacuum arc furnace. Before smelting, zirconium particles with low melting point are first placed in a vacuum arc melting furnace, and the zirconium particles are first completely melted with a current of 200A to obtain zirconium liquid, and then the current is increased to 270A and repeatedly smelted to obtain Zr ingot. The Ta source is divided into several 5 small portions, and the Ta block is first completely melted with a current of 250A to obtain Ta liquid, and then the current is increased to 310A and repeatedly smelted to obtain Ta ingot. According to the principle of low melting point at the bottom and high melting point at the top, the Ta ingot is placed above the Zr ingot, and it is completely melted with a current of 350A to obtain a Zr-Ta ingot. Ta is added to Zr in small amounts many times, and after all Ta is added to Zr, a master ingot with uniform composition is obtained after repeated smelting for more than 10 times. The master alloy ingot is obtained and observed by SEM, which does not have an amorphous structure.

[0059] The resulting Zr-30Ta alloy was cut into sheets approximately 0.6 mm thick using wire cutting. Tensile specimens were then cut from these sheets with a gauge length of 8 mm. During stretching, the wire cutting etchant on the surface of the tensile specimens was removed by grinding. The stretching rate was controlled at 0.336 mm / min. Direct melting without suction casting revealed severe segregation and coarse dendrites in the alloy, resulting in brittle fracture and poor mechanical properties during tensile testing.

[0060] Comparative Example 2 (Suction casting after melting, different suction casting sizes)

[0061] Zr particles with a purity of 99.95% and tantalum blocks with a thickness of 3-6 mm with a purity of 99.95% are weighed according to the mass ratio of the binary Zr-30% Ta alloy. 30 g are melted at a time. After the sample is prepared, it is cleaned with ultrasonic wave and then blown dry with alcohol. Then it is placed in a clean sample bag. During the melting and setting out process, do not touch the sample with your hands. Close the door of the arc melting furnace and then evacuate the vacuum degree to ≤5×10 -3 Pa, then argon protection is adopted, vacuum is repeatedly drawn, argon is flushed in 2 times, and finally the melting operation is carried out. Melting is carried out in a vacuum arc furnace. Before smelting, low-melting-point zirconium particles are first placed in a vacuum arc melting furnace, and the zirconium particles are first completely melted with a current of 200A to obtain zirconium liquid, and then the current is increased to 270A and repeatedly melted to obtain Zr ingots. The Ta source is divided into 5 small portions, and the Ta block is first completely melted with a current of 250A to obtain Ta liquid, and then the current is increased to 310A and repeatedly melted to obtain Ta ingots. According to the principle of low melting point at the bottom and high melting point at the top, the Ta ingot is placed above the Zr ingot, and it is completely melted with a current of 350A to obtain a Zr-Ta ingot. Ta is added to Zr in small amounts many times. After all Ta is added to Zr, it is repeatedly melted for more than 10 times to obtain a mother ingot with uniform composition.

[0062] The ingot was then placed on the edge of a suction casting mold in a vacuum arc melting furnace. The arc was continued, and the current was increased to 360A to melt the ingot. At the same time, the pressure in the furnace was increased. Through a pressure difference of 0.05MPa, the liquid alloy was quickly suction-cast into molds of different sizes. Suction-cast samples with sizes of 12mm*12mm*30mm, 15mm*15mm*25mm, and 6*25*45mm were produced. A comparison found that the Zr-30Ta alloys produced at these sizes did not have an amorphous structure and had insufficient mechanical properties.

[0063] Comparative Example 3 (Zr and Ta are directly smelted together)

[0064] Zr particles with a purity of 99.95% and tantalum blocks with a thickness of 3-6 mm with a purity of 99.95% are weighed according to the mass ratio of the binary Zr-30% Ta alloy. 30 g are melted at a time. After the sample is prepared, it is cleaned with ultrasonic wave and then blown dry with alcohol. Then it is placed in a clean sample bag. During the melting and setting out process, do not touch the sample with your hands. Close the door of the arc melting furnace and then evacuate the vacuum degree to ≤5×10 -3 Pa, then argon protection is used, vacuum is repeatedly drawn, argon is injected twice, and finally the melting operation is carried out. The melting is carried out in a vacuum arc furnace. Before melting, the low-melting-point zirconium particles are placed at the bottom and the tantalum block is placed at the top, and then the arc is directly struck for melting. The inventor found that directly melting large pieces of Zr-Ta alloy, because the melting point of Zr is 1852 ° C, the melting point of Ta is 2996 ° C, and the density of Zr is 6.49 g / cm 3 , and the density of Ta is 16.68g / cm 3 The significant difference in melting point and density between the two, coupled with the excessively effective water cooling in the melting furnace, resulted in Ta depositing visible large particles within the mother ingot during the melting of large alloy blocks. This resulted in uneven melting. This was due to the fact that the upper layer of alloy near the arc melted, while the alloy near the bottom of the copper crucible remained unmelted. Even after repeated remelting, small portions of Ta remained unmelted. Therefore, we could not directly melt Zr and Ta together in a large alloy block; otherwise, the experiment would be impossible.

Claims

1. A method for preparing a high-strength Zr-Ta alloy material with both amorphous and amplitude-modulated heterostructures, characterized by: The zirconium source is repeatedly smelted 2-3 times to obtain a Zr ingot; the Ta source is divided into N parts and then repeatedly smelted 3-4 times to obtain N Ta ingots, where N is 4 or 5; then one Ta ingot is placed on top of the Zr ingot, smelted to obtain Zr-Ta ingot No. 1, then another Ta ingot is taken and placed on top of the Zr-Ta ingot No. 1, smelted to obtain Zr-Ta ingot No. 2, and the above process is repeated until the Nth Ta ingot is placed on top of the N-1 Zr-Ta ingot, smelted to obtain Zr-Ta ingot No. N, and then the N Zr-Ta ingot is repeatedly smelted 10-12 times to obtain a Zr-Ta alloy ingot, and finally the Zr-Ta alloy ingot is melted to obtain a Zr-Ta alloy liquid, and the Zr-Ta alloy liquid is suction-casted into a mold to obtain a Zr-Ta alloy material; the Zr-Ta alloy material is composed of the following components in terms of atomic percentage: Zr 40%~80%, Ta:20%~60%.

2. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: The zirconium source is zirconium particles; The process of repeatedly melting the zirconium source to obtain the Zr ingot is as follows: placing the zirconium source in a vacuum arc melting furnace, first melting the zirconium source with a current of 150-200A to obtain zirconium liquid, and then increasing the current to 220-270A to repeatedly melt to obtain the Zr ingot.

3. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: The tantalum source is a tantalum block; The process of repeatedly melting any Ta source to obtain N Ta ingots is as follows: first, melt the Ta source with a current of 200-250A to obtain Ta liquid, and then increase the current to 270-320A to repeatedly melt to obtain Ta ingots.

4. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: When any Ta ingot is placed on top of a Zr ingot or any No. 1 Zr-Ta ingot, the current used for smelting is 300-350A.

5. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: The Zr-Ta alloy ingot was obtained by repeatedly melting the N-number Zr-Ta ingot 10-12 times with a current of 330A-360A.

6. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: The Zr-Ta alloy ingot is melted with a current of 300-320A to obtain a Zr-Ta alloy liquid.

7. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: The inner cavity of the mold used in the suction casting has a width of ≤10 mm, a thickness of ≤10 mm, and a length of ≤40 mm.

8. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: The material of the mold is copper mold.

9. The method for preparing a high-strength Zr-Ta alloy material having both amorphous and amplitude-modulated heterostructures according to claim 1, characterized in that: The Zr-Ta alloy material has the following composition, calculated by atomic percentage: Zr 60%-80%, Ta 20%-40%.

10. A high-strength Zr-Ta alloy material having both amorphous and spinodal heterostructures prepared by the preparation method according to any one of claims 1 to 9.

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