A multi-principal element alloy and a method of making and using the same

Abstract

The application discloses a multi-principal element alloy and a preparation method and application thereof, and comprises the following components calculated in terms of atomic percentage: 28-37% of zirconium, 18-26% of hafnium, 9-14% of tantalum, and the balance of titanium and inevitable impurities. By setting the atomic percentages of titanium (Ti), zirconium (Zr), hafnium (Hf) and tantalum (Ta) within the range of the application, the multi-principal element alloy provided by the application has low elastic modulus and high plasticity. The multi-principal element alloy of the application is composed of non-biologically toxic elements Ti, Zr, Hf and Ta, and has excellent biocompatibility.

Description

Technical Field

[0001] This invention relates to the field of alloy materials technology, and in particular to a multi-principal element alloy, its preparation method, and its application. Background Technology

[0002] Biomedical alloys are widely used in the manufacture of bio-alternatives, such as artificial joints, implants, and dental restorative materials, to replace damaged or missing tissues and organs. These alloys can restore function to affected areas and improve patients' quality of life. However, existing biomedical alloys have an excessively high elastic modulus compared to human bone, which can lead to a "stress shielding" phenomenon between the implant and bone due to the mismatch in elastic modulus. This can cause bone resorption around the implant, resulting in implant loosening or fracture, ultimately leading to implant failure. Furthermore, excellent plasticity is also an important mechanical indicator for the development of biomedical alloys to meet the complex shape requirements of biological implants. Therefore, researching novel biomedical alloys that combine low elastic modulus and high plasticity has become a current research hotspot. However, traditional common biomedical metals include 316L stainless steel (elastic modulus: 210–250 GPa), Co-Cr alloys (elastic modulus: 190–210 GPa), and Ti-6Al-4V alloys (elastic modulus: 110–130 GPa). These alloy phases have an elastic modulus far higher than that of human bone (elastic modulus: 15–30 GPa), thus easily causing a "stress shielding" phenomenon. Furthermore, these alloys contain one or more cytotoxic elements (such as Co, Cr, Ni, V, Al, etc.), which may be released into surrounding tissues due to corrosion in harsh in vivo environments, posing a potential health risk.

[0003] Therefore, it is necessary to develop new non-toxic metallic biomaterials to meet the requirements of elastic modulus, plasticity and biocompatibility of biomedical alloys. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the first aspect of the present invention proposes a multi-principal element alloy, which has low elastic modulus and high plasticity.

[0005] A second aspect of the present invention also provides a method for preparing a multi-principal element alloy.

[0006] A third aspect of the present invention also provides an application of a multi-principal element alloy.

[0007] A multi-principal element alloy according to a first aspect embodiment of the present invention comprises the following components calculated by atomic percentage:

[0008] Zirconium 28%–37%, hafnium 18%–26%, tantalum 9%–14%, balance titanium and unavoidable impurities.

[0009] The multi-principal alloy according to embodiments of the present invention has at least the following beneficial effects:

[0010] By setting the atomic percentages of titanium (Ti), zirconium (Zr), hafnium (Hf), and tantalum (Ta) within the range specified in this invention, the multi-principal element alloy provided by this invention exhibits low elastic modulus and high plasticity. This is because the Ta ratio can significantly alter the β-phase stability of the alloy; the higher the Ta content, the stronger the β-phase stability. The stability of the β-phase can be more precisely controlled by changing the contents of Zr and Hf. This results in a single-phase metastable β-phase matrix in the multi-principal element alloy. During deformation, the metastable β-phase matrix undergoes a β→α' or β→α" martensitic phase transformation, where α' is a close-packed hexagonal martensitic phase and α" is an orthorhombic martensitic phase. The presence of the aforementioned β→α' or β→α" martensitic phase transformation further reduces the elastic modulus of the multi-principal element alloy, making the elastic modulus of the multi-principal element alloy of this invention as low as 29–52 GPa.

[0011] Furthermore, the β→α' or β→α" martensitic transformation in multi-principal alloys introduces transformation-induced plasticity and transformation-induced work hardening, giving multi-principal alloys more than 20% plasticity.

[0012] Furthermore, the multi-principal alloy of the present invention is composed of non-biotoxic elements Ti, Zr, Hf and Ta, and naturally possesses excellent biocompatibility.

[0013] According to some embodiments of the present invention, the components include the following components calculated in atomic percentage:

[0014] Zirconium 30%–35%, hafnium 20%–25%, tantalum 10%–12%, with the balance being titanium and unavoidable impurities. As a result, multi-principal-element alloys have lower elastic modulus and higher plasticity.

[0015] According to some embodiments of the present invention, the unavoidable impurities refer to nitrogen and / or oxygen. Specifically, the oxygen content is less than 0.2 wt.% and the nitrogen content is less than 0.05 wt.% based on the total mass of the multi-principal alloy.

[0016] The method for preparing a multi-principal element alloy according to a second aspect embodiment of the present invention includes the following steps:

[0017] S1. Weigh zirconium, hafnium, tantalum and titanium according to the atomic percentage of the elemental composition and melt them into alloy ingots;

[0018] S2. The alloy ingot from step S1 is cold-rolled and deformed into a slab.

[0019] S3. The plate is solution treated and then quenched and cooled to room temperature.

[0020] According to some embodiments of the present invention, in step S3, the solution temperature of the solution treatment is 900℃~1200℃.

[0021] According to some embodiments of the present invention, in step S3, the heat preservation time of the solution treatment is 5 min to 60 min.

[0022] According to some embodiments of the present invention, in step S3, the solution treatment is performed in a vacuum environment.

[0023] According to some embodiments of the present invention, in step S2, the deformation amount of the cold rolling deformation is 50-90%.

[0024] According to some embodiments of the present invention, in step S3, the cooling rate is 550°C / s to 650°C / s.

[0025] According to some embodiments of the present invention, in step S1, the melting temperature is 3000℃~3200℃.

[0026] According to some embodiments of the present invention, in step S1, the smelting is performed several times.

[0027] According to some embodiments of the present invention, in step S1, the smelting apparatus is a non-consumable vacuum electric arc furnace.

[0028] According to some embodiments of the present invention, in step S3, the apparatus used for the solution treatment is a heat treatment furnace or a vacuum quenching furnace.

[0029] According to some embodiments of the present invention, the purity of the zirconium, hafnium, tantalum and titanium elements is ≥99.9 wt%.

[0030] A third aspect of this invention provides the application of the aforementioned multi-principal alloy in the preparation of biomedical materials.

[0031] According to some embodiments of the present invention, the biomedical materials include artificial joints, dental restorative materials, and external fixators for fractures.

[0032] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description

[0033] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0034] Figure 1 This is Embodiment 1 (Ti) of the present invention. 0.35 Zr 0.35 Hf0.2 Ta 0.1 X-ray diffraction pattern of )

[0035] Figure 2 This is Embodiment 1 (Ti) of the present invention. 0.35 Zr 0.35 Hf 0.2 Ta 0.1 SEM images of the tissue characterization;

[0036] Figure 3 This is Embodiment 1 (Ti) of the present invention. 0.35 Zr 0.35 Hf 0.2 Ta 0.1 X-ray diffraction pattern after stretching and deformation;

[0037] Figure 4 This is Embodiment 1 (Ti) of the present invention. 0.35 Zr 0.35 Hf 0.2 Ta 0.1 SEM images of the tissue after stretching deformation. Detailed Implementation

[0038] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0039] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0040] Example 1

[0041] Example 1 provides a multi-principal element alloy, the atomic percentage of which is shown in Table 1, and its preparation method is as follows:

[0042] S1. Weigh zirconium, hafnium, tantalum and titanium according to the atomic percentage of the elemental composition and place them in a magnetically stirred vacuum non-consumable arc furnace for repeated melting five times (3000℃, one minute each time), and vacuum cast them into ingots with uniform composition.

[0043] S2. The alloy ingot from step S1 is cold-rolled and deformed into a plate with a thickness of 1.5 mm and a deformation amount of 90%.

[0044] S3. The plate is solution treated (950℃ for 30 min), then quenched and cooled to room temperature to obtain a multi-principal element alloy (named: Ti). 0.35 Zr 0.35 Hf 0.2 Ta 0.1 ).

[0045] The multi-principal element alloy of Example 1 of the present invention was subjected to X-ray diffraction and microstructure characterization by SEM before and after deformation. The results are shown in the figure. Figures 1-4 , Figure 1 For Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 The X-ray diffraction pattern of the alloy in the solid solution state shows that only the peak of the β phase was detected, indicating that a single-phase β phase structure was obtained after the above heat treatment. Figure 2 It is Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 The SEM microstructure of the alloy in the solution-treated state shows the formation of single-phase β-phase grains, further proving that the alloy obtained a single-phase β-phase microstructure during the above heat treatment. Figure 3 For Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 In the solid solution state of the alloy, after tensile deformation, the X-ray diffraction pattern shows the appearance of α' phase peaks, proving that a β→α' martensitic phase transformation occurred during the deformation process. Figure 4 For, Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 The microstructure of the alloy under solid solution condition and after tensile deformation by SEM characterization clearly shows α' bands, further proving the β→α' martensitic phase transformation.

[0046] Example 2

[0047] Example 2 provides a multi-principal element alloy, the atomic percentages of each element in which are shown in Table 1, and the preparation method is as follows:

[0048] S1. Weigh zirconium, hafnium, tantalum and titanium according to the atomic percentage of the elemental composition and place them in a magnetically stirred vacuum non-consumable arc furnace for repeated melting five times (3200℃, one minute each time), and vacuum cast them into ingots with uniform composition.

[0049] S2. The alloy ingot from step S1 is cold-rolled and deformed into a plate with a thickness of 1.5 mm and a deformation amount of 80%.

[0050] S3. The plate is solution treated (950℃ for 30 min), then quenched and cooled to room temperature to obtain a multi-principal element alloy (named: Ti). 0.34 Zr 0.34 Hf 0.22 Ta 0.1 ).

[0051] Example 3

[0052] Example 3 provides a multi-principal element alloy, the atomic percentages of each element in which are shown in Table 1, and the preparation method is as follows:

[0053] S1. Weigh zirconium, hafnium, tantalum and titanium according to the atomic percentage of the elemental composition and place them in a magnetically stirred vacuum non-consumable arc furnace for repeated melting five times (3100℃, one minute each time), and vacuum cast them into ingots with uniform composition.

[0054] S2. The alloy ingot from step S1 is cold-rolled and deformed into a plate with a thickness of 1.5 mm and a deformation amount of 70%.

[0055] S3. The plate is solution treated (950℃ for 20 min), then quenched and cooled to room temperature to obtain a multi-principal element alloy (named: Ti). 0.32 Zr 0.32 Hf 0.25 Ta 0.1 ).

[0056] Example 4

[0057] Example 4 provides a multi-principal element alloy, the atomic percentages of each element in which are shown in Table 1, and the preparation method is as follows:

[0058] S1. Weigh zirconium, hafnium, tantalum and titanium according to the atomic percentage of the elemental composition and place them in a magnetically stirred vacuum non-consumable arc furnace for repeated melting five times (3000℃, one minute each time), and vacuum cast them into ingots with uniform composition.

[0059] S2. The alloy ingot from step S1 is cold-rolled and deformed into a plate with a thickness of 1.5 mm and a deformation amount of 90%.

[0060] S3. The plate is solution treated (950℃ for 15 min), then quenched and cooled to room temperature to obtain a multi-principal element alloy (named: Ti). 0.31 Zr 0.31 Hf 0.25 Ta 0.13 ).

[0061] Example 5

[0062] Example 5 provides a multi-principal element alloy, the atomic percentages of each element in which are shown in Table 1, and the preparation method is as follows:

[0063] S1. Weigh zirconium, hafnium, tantalum and titanium according to the atomic percentage of the elemental composition and place them in a magnetically stirred vacuum non-consumable arc furnace for repeated melting five times (3000℃, one minute each time), and vacuum cast them into ingots with uniform composition.

[0064] S2. The alloy ingot from step S1 is cold-rolled and deformed into a plate with a thickness of 1.5 mm and a deformation amount of 90%.

[0065] S3. The plate is solution treated (950℃ for 60 min), then quenched and cooled to room temperature to obtain a multi-principal element alloy (named: Ti). 0.29 Zr 0.29 Hf 0.25 Ta 0.14 ).

[0066] Comparative Examples 1-2

[0067] Comparative Examples 1 and 2 provide a multi-principal element alloy, the atomic percentages of each element in which are shown in Table 1, and the preparation method is the same as that in Example 1.

[0068] Table 1. Atomic percentage content of Examples 1-5 and Comparative Examples 1-2

[0069] titanium zirconium hafnium Tantalum Example 1 35％ 35％ 20％ 10％ Example 2 34％ 34％ 22％ 10％ Example 3 32％ 32％ 25％ 10％ Example 4 31％ 31％ 25％ 13％ Example 5 29％ 29％ 25％ 14％ Comparative Example 1 25％ 25％ 25％ 25％ Comparative Example 2 20％ 25％ 25％ 30％

[0070] Performance testing

[0071] The elastic modulus and elongation of the multi-principal element alloys prepared in Examples 1-5 and Comparative Examples 1-2 were tested.

[0072] The testing method is as follows: Multiple tensile dog bone samples, with gauge dimensions of 12*4*1.5mm, were prepared from the original samples via wire EDM. Tensile tests (MTS E45.504) were performed at room temperature with a strain rate of 10. -3 s -1 The digital image correlation (DIC) instrument and its onboard video extensometer are synchronized with the tensile testing machine to directly capture stress-strain data at a frame rate of 1Hz during the tensile process, obtaining stress-strain curves. The elastic modulus is obtained by fitting the slope of the elastic segment of the curve, and the elongation is obtained from the stress-strain curve. The results are shown in Table 2.

[0073] Table 2 Examples 1-5 and Comparative Examples 1-2

[0074]

[0075]

[0076] As can be seen from the data in Table 2, the multi-principal element alloy provided by the present invention has a low elastic modulus and high plasticity (the greater the elongation, the higher the plasticity). Although the elemental composition of Comparative Examples 1 and 2 is consistent with that of the present invention, their atomic percentages are outside the range of the present invention, resulting in high elastic modulus and low plasticity, which does not meet the requirements.

[0077] The present invention has been described in detail above with reference to the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A multi-principal element alloy, characterized in that, Includes the following components, calculated as atomic percentages: Zirconium 28%~37%, Hafnium 18%~26%, Tantalum 9%~14%, balance titanium and unavoidable impurities; The multi-principal element alloy is prepared by the following method: S1. Weigh zirconium, hafnium, tantalum and titanium according to the atomic percentage of the elemental composition and melt them into alloy ingots; S2. The alloy ingot from step S1 is cold-rolled and deformed into a slab. S3. The plate is solution treated, and then quenched and cooled to room temperature; The solution temperature of the solution treatment is 900℃~1200℃; the deformation amount of the cold rolling deformation is 50~90%; and the cooling rate is 550℃ / s~650℃ / s.

2. The multi-principal element alloy according to claim 1, characterized in that, Includes the following components, calculated as atomic percentages: Zirconium 30%~35%, hafnium 20%~25%, tantalum 10%~12%, balance titanium and unavoidable impurities.

3. The multi-principal element alloy according to claim 1, characterized in that, In step S3, the heat treatment time for the solution treatment is 5 min to 60 min.

4. The multi-principal element alloy according to claim 1, characterized in that, In step S1, the melting temperature is 3000℃~3200℃.

5. The multi-principal element alloy according to claim 1, characterized in that, In step S1, the smelting apparatus is a non-consumable vacuum arc furnace.

6. The application of the multi-principal alloy according to any one of claims 1 to 5 in the preparation of biomedical materials.

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