CN116334445A - Rare earth doped Ti-Nb-Dy alloy and preparation and processing methods thereof - Google Patents

Rare earth doped Ti-Nb-Dy alloy and preparation and processing methods thereof Download PDF

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CN116334445A
CN116334445A CN202310250457.7A CN202310250457A CN116334445A CN 116334445 A CN116334445 A CN 116334445A CN 202310250457 A CN202310250457 A CN 202310250457A CN 116334445 A CN116334445 A CN 116334445A
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张建
张鹏
曹瑞城
李威
任镜霖
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/006—Resulting in heat recoverable alloys with a memory effect
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention provides a rare earth doped Ti-Nb-Dy titanium alloy and a preparation and processing method thereof, comprising the steps of weighing Ti, nb and Dy raw materials according to the component proportion of 23-30% of Nb, 0.1-5% of Dy and the balance of Ti, smelting the raw materials into an alloy cast ingot in a vacuum smelting furnace by adopting a non-consumable vacuum arc smelting process, and carrying out solution treatment and processing treatment on the alloy cast ingot to obtain the rare earth element Dy doped Ti-Nb-Dy alloy. By doping rare earth element Dy into Ti-Nb alloy, the alloy contains Ti, nb and Dy elements, the rare earth element Dy has higher affinity to O atoms in melt, interstitial oxygen in an alloy matrix can be extracted, the oxygen content in the alloy matrix is reduced, more defects are introduced into the alloy after the alloy in a solid solution state is processed, the elastic modulus of the titanium alloy is reduced, and meanwhile, the alloy maintains higher yield strength.

Description

Rare earth doped Ti-Nb-Dy alloy and preparation and processing methods thereof
Technical Field
The invention relates to the technical field of titanium alloy, in particular to a rare earth doped Ti-Nb-Dy alloy and a preparation and processing method thereof, and especially relates to a Ti-Nb-Dy alloy with super elasticity, low elastic modulus, chemical stability, high corrosion resistance and good biocompatibility in the biomedical field.
Background
Titanium alloy has been widely used in the fields of aerospace, automobiles and boats, sports equipment, biomedical treatment and the like as a multifunctional material with high strength, low elastic modulus and good thermal stability. Stainless steel and cobalt-based alloys, which have been the main materials for implantation into the human body in the past, have been gradually replaced with titanium alloys due to their excellent comprehensive mechanical properties as well as good corrosion resistance and biocompatibility. It has been found that the human skeletal modulus of elasticity is only about 30GPa, and if the implant elastic modulus is higher than that of the surrounding bone tissue, a stress shielding effect will occur clinically, which can lead to failure fracture of the implant and bone atrophy or even fracture. Therefore, the design and development of low modulus high strength titanium alloys have been a focus of research in the biomedical device field.
The alpha+beta titanium alloy Ti-6Al-4V and Ti-6Al-7Nb are widely applied to clinical medicine, and although the elasticity of the alloy is reduced to about half that of stainless steel and cobalt-based alloy, about 110GPa, the stress shielding effect is reduced to a certain extent, but the alloy of the system can be worn and corroded due to long-term implantation into human bodies so as to release Al and V ions with cytotoxicity and neurotoxicity. TiNi-based shape memory alloy has excellent functional characteristics such as superelasticity and shape memory effect, and comprehensive mechanical properties, but the Ni element can generate anaphylactic reaction and has carcinogenicity to partial population. Thus, researchers have focused on developing biomedical titanium alloy materials that do not contain Ni element since mid nineties.
Currently, alpha+beta and beta type titanium alloys having excellent biocompatibility have been developed successively, including Ti-15Zr-4Nb-4Ta-0.2Pd, ti-15Zr-4Nb-aTa-0.2Pd- (0.20-0.05) N, ti-15Sn-4Nb-2Ta-0.2Pd and Ti-15Sn-4Nb-2Ta-0.2Pd-0.2O, and Ti-12Mo-Zr-2Fe, ti-13Nb-13Zr, ti-15Mo-2.5Nb-0.2Si, ti-16Nb-9.5Hf and Ti-15Mo. The corrosion strength, fatigue strength and corrosion resistance of these alloys are all superior to those of Ti-6Al-4V, with the Ti-Nb series titanium alloys not being present in a minority. Compared with alpha, alpha+beta titanium alloy, metastable beta titanium alloy has lower elastic modulus and thus better human body mechanical compatibility.
In recent years, ti-Nb-based metastable beta-type titanium alloy gradually becomes an important development direction of new generation biomedical titanium alloy. The Ti-Nb binary alloy has lower strength and severely limits the wide application. At present, most researches mainly increase the strength of the steel by adding a large amount of solid solution elements. Metastable beta titanium alloys of Ti 24Nb 4Zr 7.9Sn, ti 29Nb 13Ta 4.6Zr, ti 25Nb 3Mo 3Zr 2Sn, ti 35N 5TaZr, etc. have been developed and have been gradually or clinically used. However, the above alloys have certain disadvantages in large-scale commercial preparation processes. The alloy contains more beta stabilizing elements (Ta, mo and the like) and/or neutral elements (Zr, hf, sn and the like), so that the alloy contains complex alloy composition, impurities are easily introduced in the preparation process, the phenomena of element segregation and the like are caused, and the alloy performance is influenced. In addition, titanium alloy is extremely easy to absorb oxygen and oxidize in the preparation process. Wherein oxygen atoms present as interstitial point defects will greatly increase the elastic modulus of the metastable beta titanium alloy matrix and inhibit the thermoelastic martensitic transformation therein. At present, the preparation and processing of the low-oxygen-content titanium alloy are generally carried out by adopting ultra-high-purity raw material metal and ultra-high vacuum protective atmosphere, and the cost is extremely high.
Disclosure of Invention
The invention aims to provide a rare earth doped Ti-Nb-Dy alloy and a preparation and processing method thereof, so as to solve the problems of complex alloy components, high manufacturing cost and the like of the traditional Ti-Nb-based biomedical alloy, obtain a novel metastable beta-type titanium alloy with low modulus, high strength, super elasticity and good biocompatibility, and can be widely applied to biomedical and aerospace instruments. In order to achieve the above object, the present invention discloses a method for preparing and processing a rare earth doped Ti-Nb-Dy alloy, characterized by comprising the steps of:
(1) Weighing Ti, nb and Dy raw materials according to the component proportion of 23-30 atomic percent of Nb, 0.1-5 atomic percent of Dy and the balance of Ti, and smelting the raw materials into alloy ingots in a vacuum smelting furnace by adopting a non-consumable vacuum arc smelting process;
(2) Carrying out solution treatment on the alloy cast ingot prepared in the step (1) under the protection of argon to obtain a Ti-Nb-Dy super-elastic low-modulus titanium alloy doped with rare earth element Dy;
(3) And (3) processing the Ti-Nb-Dy alloy obtained in the step (2) to obtain a processed alloy.
The titanium alloy is easy to introduce gap O atoms in the smelting and later thermal mechanical treatment processes, so that the O content is higher, and the alloy matrix is in solid solution with O, thereby causing the modulus to rise. By doping rare earth element Dy into Ti-Nb alloy, the alloy contains Ti, nb and Dy elements, the rare earth element Dy has higher affinity to O atoms in melt, dy element can abstract interstitial oxygen in alloy matrix, reduce oxygen content in alloy matrix, and the addition of Dy element can refine titanium alloy crystal grains, reduce elastic modulus of titanium alloy, increase shaping of alloy and simultaneously keep alloy with higher strength. The content of Nb in the titanium alloy is 23-30%, so that the alloy has super elasticity reaching 2%, elastic modulus smaller than 41GPa and high damping performance at room temperature.
In one embodiment of the present invention, the purity of Ti, nb, dy in the raw material is not lower than 99.9%.
In one embodiment of the invention, the percentage of Nb atoms in the alloy is 23 to 26%, preferably 25%.
In one embodiment of the present invention, the percentage content of Dy atoms in the alloy is 0.3 to 4%, preferably 0.5 to 4%.
In one embodiment of the present invention, the sum of the atomic percentage contents of Nb and Dy in the alloy is not higher than 35%. The total content of Nb and Dy is not higher than 35%, so that the oxygen content is controlled on the basis of ensuring the alloy performance, and a better strengthening effect is obtained.
In one embodiment of the invention, the heat treatment process is solution treatment for 1-40 hours at 800-1200 ℃ under argon environment, and quenching.
In one embodiment of the present invention, the cooling means comprises water quenching or ice salt water quenching.
In one embodiment of the invention, the working process is cold working comprising at least one of cold rolling, cold wire drawing, cold swaging or cold heading.
In one embodiment of the invention, the deformation ratio upon cold working is greater than 80%.
In one embodiment of the present invention, the total deformation rate after the processing is 80 to 99% and the single deformation is 0.1 to 4%.
The invention also discloses a Ti-Nb-Dy alloy obtained by the preparation and processing method.
The invention aims to provide the application of the Ti-Nb-Dy alloy in biomedical devices, aerospace devices and sports equipment.
In one embodiment of the invention, the use includes use of a Ti-Nb-based titanium alloy in biomedical human implants including artificial knee joints, femoral stems, luminal bones, medullary bones, screws, and tooth roots.
The invention has the beneficial effects that:
1. by doping rare earth element Dy into Ti-Nb alloy, the alloy contains Ti, nb and Dy elements, the rare earth element Dy has higher affinity to O atoms in melt, dy element can abstract interstitial oxygen in alloy matrix, reduce oxygen content in alloy matrix, not only refine titanium alloy crystal grains, but also reduce elastic modulus of titanium alloy, and simultaneously maintain higher strength of alloy.
2. The Ti-Nb-Dy alloy is manufactured by adopting a non-consumable vacuum arc melting process, and is subjected to heat treatment and cold processing to obtain an alloy plate, and after the alloy in a solid solution state is subjected to cold processing, more defects are introduced into the alloy, so that the elastic modulus of the alloy is greatly reduced, the yield strength is increased, the elastic modulus of the Ti-Nb-Dy alloy is as low as 35.9GPa, and the yield strength is as high as 680MPa.
3. The alloy obtained by the method has the advantages of low modulus, high strength, super elasticity, shape memory, damping characteristic, corrosion resistance and high biocompatibility. The modulus of the titanium alloy obtained by the invention is similar to that of human bone, and the titanium alloy can be used as a bone implant or a medical instrument.
Drawings
FIG. 1 is a back-scattering contrast-scanning electron microscope photograph of a Ti-25Nb-0.5Dy alloy solid solution state sample of the present invention;
FIG. 2 is a back-scattering contrast-scanning electron microscope photograph of a solid solution sample of the Ti-25Nb-2Dy alloy of the present invention;
FIG. 3 is a back-scattering contrast-scanning electron microscope photograph of a solid solution sample of the Ti-25Nb-4Dy alloy of the present invention;
FIG. 4 is a drawing curve of a Ti-25Nb-0.5Dy alloy of the present invention after cold rolling;
FIG. 5 is a graph showing the superelastic elongation of the Ti-25Nb-0.5Dy alloy of the present invention after cold rolling;
FIG. 6 is a drawing curve of a Ti-25Nb-2Dy alloy of the present invention after cold rolling;
FIG. 7 is a graph showing the superelastic elongation of the Ti-25Nb-2Dy alloy of the present invention after cold rolling;
FIG. 8 is a drawing curve of a Ti-25Nb-4Dy alloy of the present invention after cold rolling.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings, which are given by way of illustration only and are not to be construed as limiting the invention.
Example 1
Three pure metal raw materials of Ti, nb and Dy with purity not lower than 99.9 percent and content proportion of 74.5 percent, 25 percent and 0.5 percent respectively are put into a non-consumable vacuum arc furnace for smelting, and the alloy ingot is prepared by repeatedly smelting for ten times to ensure the uniform alloy components and overturning the ingot. And (3) carrying out solid solution treatment on the sample after sand paper grinding and polishing treatment under the protection of argon, wherein the heat treatment temperature is 1000 ℃, the treatment time is 24 hours, and the cooling mode is ice-salt water quenching. Cold rolling the alloy ingot casting sample after solid solution, wherein the cold rolling deformation amount is 0.5% each time before the total deformation amount is lower than 80%; when the total deformation amount is higher than 80%, the deformation amount of each cold rolling is 0.25%, the sample after cold rolling treatment is in a sheet shape, and the total deformation amount is about 95%.
The microstructure of the solid solution Ti-25Nb-0.5Dy alloy sample is shown in FIG. 1, and the average grain size is 60 μm. Grain refinement is evident compared to grain sizes (2 mm) of solid solution Ti-25Nb samples obtained under the same preparation and heat treatment conditions. Dy element Dy 2 O 3 Oxide grain forms exist in both grain boundaries and within grains, wherein the grain boundaries are Dy 2 O 3 Larger size (1 μm), and intra-crystalline Dy 2 O 3 The size is finer, and the nanometer scale is mainly (-100 nm).
Example 2
Three pure metal raw materials of Ti, nb and Dy with purity not lower than 99.9 percent and content proportion of 73 percent, 25 percent and 2 percent respectively are put into a non-consumable vacuum arc furnace to be smelted, and the ingot is turned over and repeatedly smelted for ten times to prepare the alloy ingot for ensuring the uniform alloy components. And (3) carrying out solid solution treatment on the sample after sand paper grinding and polishing treatment under the protection of argon, wherein the heat treatment temperature is 1000 ℃, the treatment time is 24 hours, and the cooling mode is ice-salt water quenching. Cold rolling the alloy ingot casting sample after solid solution, wherein the cold rolling deformation amount is 0.5% each time before the total deformation amount is lower than 80%; when the total deformation amount is higher than 80%, the deformation amount per cold rolling is 0.25%. The sample after cold rolling treatment is in the shape of a sheet, and the total deformation is about 95%.
The microstructure of the solid solution Ti-25Nb-2Dy alloy sample is shown in FIG. 2, and the average grain size is 35 μm. Compared with Dy in the sample of example 1 2 O 3 The grain size, the density and the volume fraction are all obviously increased, wherein the grain boundary Dy 2 O 3 The dimensional change is not large (about 2 μm), and Dy in the crystal 2 O 3 The size increase is significant, predominantly on the sub-micron scale (-0.5 μm).
Example 3
Three pure metal raw materials of Ti, nb and Dy with purity not lower than 99.9 percent and content proportion of 71 percent, 25 percent and 4 percent respectively are put into a non-consumable vacuum arc furnace to be smelted, and the ingot is turned over and repeatedly smelted for ten times to prepare the alloy ingot for ensuring the uniform alloy components. And (3) carrying out solid solution treatment on the sample after sand paper grinding and polishing treatment under the protection of argon, wherein the heat treatment temperature is 1000 ℃, the treatment time is 24 hours, and the cooling mode is ice-salt water quenching. Cold rolling the alloy ingot casting sample after solid solution, wherein the cold rolling deformation amount is 0.5% each time before the total deformation amount is lower than 80%; when the total deformation amount is higher than 80%, the deformation amount per cold rolling is 0.25%. The sample after cold rolling treatment is in the shape of a sheet, and the total deformation is about 95%.
The microstructure of the solid solution Ti-25Nb-4Dy alloy sample is shown in FIG. 3, and the average grain size is 30 μm. Compared with Dy in the sample of example 2 2 O 3 The grain size, the density and the volume fraction are all obviously increased, wherein the grain boundary Dy 2 O 3 Are connected in a line shape, and Dy in the crystal 2 O 3 The size increase is significant, mainly on the micrometer scale (-2 μm).
Testing of tensile Properties
The titanium alloy sheets prepared in examples 1, 2 and 3 were wire cut into 20X 4X 1mm specimens at 3X 10 -4 s -1 Tensile experiments were performed at strain rates of (c). To ensure the accuracy of tensile elastic modulus and superelastic strain measurement, strain values were recorded using an extensometer. The elastic modulus was calculated from the line elastic deformation section of the stress-strain curve, and the tensile curves are shown in fig. 4, 6 and 8, respectively. Superelasticity measurements samples of the titanium alloy sheet material prepared and processed in examples 1 and 2 were unloaded before being loaded into plastic yield, and the total strain recovered during unloading was taken as the superelastic strain, as the result of which see fig. 5 and 7.
As can be seen from the results shown in FIG. 4, the alloy Ti-25Nb-0.5Dy of example 1 exhibited a good tensile property, and had an elastic modulus of 35.9GPa and a yield strength of 678MPa.
From the results shown in FIG. 5, it can be seen that the alloy Ti-25Nb-0.5Dy in example 1 exhibited a good superelasticity, and its superelastic strain reached 2.1%.
From the results shown in FIG. 6, it can be seen that the alloy Ti-25Nb-2Dy of example 2 also exhibited a good tensile property, with an elastic modulus of 40.8GPa and a yield strength of 683MPa.
From the results shown in fig. 7, it can be seen that the alloy Ti-25Nb-2Dy of example 2 exhibited a better superelasticity, and its superelastic strain reached 2%.
From the results shown in FIG. 8, it can be seen that the alloy Ti-25Nb-4Dy of example 3 also exhibited a good tensile property, with an elastic modulus of 41.6GPa and a yield strength of 686MPa.

Claims (10)

1. The preparation and processing method of the rare earth doped Ti-Nb-Dy alloy is characterized by comprising the following steps:
(1) Weighing Ti, nb and Dy raw materials according to the component proportion of 23-30 atomic percent of Nb, 0.1-5 atomic percent of Dy and the balance of Ti, and smelting the raw materials into alloy ingots in a vacuum smelting furnace by adopting a non-consumable vacuum arc smelting process;
(2) Carrying out solution treatment on the alloy cast ingot prepared in the step (1) under the protection of argon to obtain a Ti-Nb-Dy alloy doped with rare earth element Dy;
(3) And (3) processing the Ti-Nb-Dy alloy obtained in the step (2) to obtain a processed alloy.
2. The method for producing and processing a Ti-Nb-Dy alloy according to claim 1, wherein the purity of Ti, nb, dy in the raw material is not less than 99.9%.
3. The method of producing and processing a Ti-Nb-Dy alloy according to claim 1, wherein the sum of the atomic percentage contents of Nb and Dy in the alloy is not more than 31%.
4. The method for producing and processing a Ti-Nb-Dy alloy according to claim 1, wherein the heat treatment process is solution treatment at 800 to 1200 ℃ in an argon atmosphere for 1 to 40 hours, and quenching.
5. The method of preparing and processing a Ti-Nb-Dy alloy according to claim 4, wherein the quenching means comprises water quenching or ice salt water quenching.
6. The method of producing and working a Ti-Nb-Dy alloy according to claim 1, wherein the working process is cold working including at least one of cold rolling, cold drawing, cold swaging, or cold heading.
7. The method of preparing and processing a Ti-Nb-Dy alloy according to claim 6, wherein the deformation rate at cold working is greater than 80%.
8. The method for producing and processing a Ti-Nb-Dy alloy according to claim 6, wherein the total deformation ratio after the processing is 80 to 99% and the single deformation amount is 0.1 to 4%.
9. The Ti-Nb-Dy alloy obtained by the production and processing method according to claims 1 to 8.
10. Use of the Ti-Nb-Dy alloy of claim 9 in biomedical devices, aerospace devices, sports equipment.
CN202310250457.7A 2023-03-15 2023-03-15 Rare earth doped Ti-Nb-Dy alloy and preparation and processing methods thereof Pending CN116334445A (en)

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