CN117512400A - Multi-principal element alloy and preparation method and application thereof - Google Patents
Multi-principal element alloy and preparation method and application thereof Download PDFInfo
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- CN117512400A CN117512400A CN202311485303.2A CN202311485303A CN117512400A CN 117512400 A CN117512400 A CN 117512400A CN 202311485303 A CN202311485303 A CN 202311485303A CN 117512400 A CN117512400 A CN 117512400A
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- 229910001325 element alloy Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 239000000956 alloy Substances 0.000 claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 21
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- 238000003723 Smelting Methods 0.000 claims description 11
- 238000005097 cold rolling Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000701 toxic element Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 229910000734 martensite Inorganic materials 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000007943 implant Substances 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000010891 electric arc Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 239000002763 biomedical alloy Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- URXDOZXTRQGRIP-UHFFFAOYSA-N [Hf].[Zr].[Ti] Chemical compound [Hf].[Zr].[Ti] URXDOZXTRQGRIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009763 wire-cut EDM Methods 0.000 description 1
Classifications
-
- 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
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- 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
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
-
- 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
- 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
- C22F1/02—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
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- 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
-
- 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
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
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- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Transplantation (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Inorganic Chemistry (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a multi-principal element alloy, a preparation method and application thereof, which comprises the following components in percentage by atom: 28-37% of zirconium, 18-26% of hafnium, 9-14% of tantalum and the balance of titanium and unavoidable impurities. By setting the atomic percentages of titanium (Ti), zirconium (Zr), hafnium (Hf) and tantalum (Ta) elements within the scope of the present invention, the multi-principal alloy provided by the present invention has a low elastic modulus and high plasticity. The multi-principal element alloy consists of non-biological toxic elements Ti, zr, hf and Ta, and has excellent biocompatibility.
Description
Technical Field
The invention relates to the technical field of alloy materials, in particular to a multi-principal element alloy and a preparation method and application thereof.
Background
Biomedical medical alloys are widely used in the manufacture of biological substitutes, such as artificial joints, implants, dental restorative materials, and the like, to replace damaged or missing tissues and organs. These alloys can restore the function of the affected area and improve the quality of life of the patient. However, the existing biomedical alloy has excessively high elastic modulus compared with human bone, which can cause the phenomenon of stress shielding between the implant and the bone due to the mismatching of the elastic modulus, so that bone absorption occurs around the implant, the implant is loosened or broken, and finally the implant fails. In addition, to adapt to the complex shape requirement of the biological implant, excellent plasticity is also an important mechanical index for the development of biomedical alloy. Therefore, research on novel biomedical alloys with low elastic modulus and high plasticity is a hot spot of current research. However, conventional 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). The elastic modulus of the alloy phases is far higher than that of human bones (elastic modulus: 15-30 GPa), so that the phenomenon of stress shielding is easy to cause. In addition, the alloys contain one or more cytotoxic elements (e.g., co, cr, ni, V, al, etc.) which may be released into the surrounding tissue due to corrosion in harsh in vivo environments, thus presenting a potential health risk.
Therefore, there is a need to develop new non-toxic metallic biomaterials to meet the requirements of biomedical alloy elastic modulus, plasticity and biocompatibility.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, a first aspect of the invention proposes a multi-principal element alloy such that the alloy has a low elastic modulus and a high plasticity.
The second aspect of the invention also provides a method for preparing the multi-principal element alloy.
The third aspect of the invention also provides the use of a multi-principal element alloy.
According to a first aspect of the present invention, there is provided a multi-principal element alloy comprising the following components in atomic percent:
28-37% of zirconium, 18-26% of hafnium, 9-14% of tantalum and the balance of titanium and unavoidable impurities.
The multi-principal element alloy provided by the embodiment of the invention has at least the following beneficial effects:
by setting the atomic percentages of titanium (Ti), zirconium (Zr), hafnium (Hf) and tantalum (Ta) elements within the scope of the present invention, the multi-principal alloy provided by the present invention has a low elastic modulus and high plasticity. This is because the proportion of Ta can significantly change the beta-phase stability of the alloy, the more Ta content, the stronger the beta-phase stability. The beta-phase stability can be more precisely regulated and controlled by changing the content of Zr and Hf. The multi-principal element alloy is enabled to obtain a single-phase metastable beta-phase matrix, and the metastable beta-phase matrix can generate beta- & gt alpha '-or beta- & gt alpha' martensitic transformation in the deformation process, wherein alpha 'is a martensite phase of a close-packed hexagonal crystal structure, and alpha' is a martensite phase of an orthorhombic crystal structure. The existence of the beta- & gtalpha 'or beta- & gtalpha' martensitic transformation process can further reduce the elastic modulus of the multi-principal element alloy, so that the elastic modulus of the multi-principal element alloy is as low as 29-52 GPa.
Further, the β→α' or β→α "martensitic transformation may introduce transformation induced plasticity and transformation induced work hardening in the multi-master alloy, resulting in the multi-master alloy having more than 20% plasticity.
Further, the multi-principal element alloy of the present invention is composed of non-bio-toxic elements Ti, zr, hf and Ta, and naturally has excellent biocompatibility.
According to some embodiments of the invention, the composition comprises the following in atomic percent:
30-35% of zirconium, 20-25% of hafnium, 10-12% of tantalum and the balance of titanium and unavoidable impurities. Thus, the multi-principal component alloy has a lower modulus of elasticity and a higher plasticity.
According to some embodiments of the invention, the unavoidable impurities are nitrogen and/or oxygen. Wherein the oxygen content is 0.2wt.% or less and the nitrogen content is 0.05wt.% or less, calculated on the total mass of the multi-principal alloy.
According to a second aspect of the present invention, there is provided a method for preparing a multi-principal element alloy, comprising the steps of:
s1, weighing zirconium, hafnium, tantalum and titanium according to atomic percentages of elemental components, and smelting into alloy ingots;
s2, performing cold rolling deformation on the alloy cast ingot obtained in the step S1 to obtain a plate blank;
s3, carrying out solution treatment on the plate, and then quenching and cooling to room temperature.
According to some embodiments of the invention, in step S3, the solution temperature of the solution treatment is 900 ℃ to 1200 ℃.
According to some embodiments of the invention, in step S3, the heat preservation time of the solution treatment is 5min to 60min.
According to some embodiments of the invention, in step S3, the solution treatment is performed in a vacuum environment.
According to some embodiments of the invention, in step S2, the deformation amount of the cold rolling deformation is 50 to 90%.
According to some embodiments of the invention, in step S3, the cooling is performed at a rate of 550 ℃/S to 650 ℃/S.
According to some embodiments of the invention, in step S1, the smelting temperature is 3000 ℃ to 3200 ℃.
According to some embodiments of the invention, in step S1, the smelting is performed several times.
According to some embodiments of the invention, in step S1, the apparatus used for smelting is a non-consumable vacuum arc furnace.
According to some embodiments of the invention, in step S3, the device used for the solution treatment is a heat treatment furnace or a vacuum quenching furnace.
According to some embodiments of the invention, the purity of the zirconium, hafnium, tantalum and titanium elements is greater than or equal to 99.9wt%.
In a third aspect, the present invention provides the use of a multi-principal element alloy as described above in the preparation of biomedical materials.
According to some embodiments of the invention, the biomedical material comprises an artificial joint, a dental restorative material, a fracture external fixator.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a sample of the invention in example 1 (Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 ) An X-ray diffraction pattern of (2);
FIG. 2 shows a composition of example 1 (Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 ) Is a tissue characterization SEM image of (a);
FIG. 3 shows a sample of the invention in example 1 (Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 ) An X-ray diffraction pattern after the stretching deformation;
FIG. 4 shows a sample of the invention in example 1 (Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 ) SEM images of tissue characterization after tensile deformation.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
Example 1 provides a multi-principal element alloy, the atomic percentages of which are shown in table 1, the preparation method of which is as follows:
s1, weighing zirconium, hafnium, tantalum and titanium according to atomic percentages of element components, repeatedly smelting the zirconium, the hafnium, the tantalum and the titanium in a magnetic stirring vacuum non-consumable electric arc furnace for five times (3000 ℃ for one minute each time), and performing vacuum casting to obtain cast ingots with uniform components;
s2, performing cold rolling deformation on the alloy cast ingot obtained in the step S1 to obtain a plate with the thickness of 1.5mm, wherein the deformation is 90%;
s3, carrying out solid solution treatment (30 min at 950 ℃) on the plate, and then quenching and cooling to room temperature to obtain the multi-principal element alloy (named as Ti) 0.35 Zr 0.35 Hf 0.2 Ta 0.1 )。
The multi-principal element alloy of example 1 of the present invention was subjected to X-ray diffraction and SEM for structural characterization before and after deformation, the results are shown in FIGS. 1 to 4, and FIG. 1 is Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 The X-ray diffraction pattern of the alloy in solid solution showed that only the peak of the beta phase was detected, indicating that a single-phase beta phase structure was obtained by the above heat treatment. FIG. 2 is Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 The structure diagram characterized by SEM in the solid solution state of the alloy can be seen to form single-phase beta-phase grains, and further proves that the alloy obtains single-phase beta-phase structure in the heat treatment. FIG. 3 is Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 In the solid solution state of the alloy, the X-ray diffraction pattern after the tensile deformation is performed, and an alpha 'phase peak appears on the X-ray diffraction pattern, so that the beta- & gtalpha' martensitic transformation occurs in the deformation process. FIG. 4 is Ti 0.35 Zr 0.35 Hf 0.2 Ta 0.1 In the solid solution state of the alloy, the alpha 'band can be clearly seen from the structural diagram characterized by SEM after tensile deformation, and the beta- & gtalpha' martensitic transformation is further demonstrated.
Example 2
Example 2 provides a multi-principal element alloy, the atomic percentages of the elements of which are shown in table 1, and the preparation method is as follows:
s1, weighing zirconium, hafnium, tantalum and titanium according to atomic percentages of element components, repeatedly smelting the zirconium, the hafnium, the tantalum and the titanium in a magnetic stirring vacuum non-consumable electric arc furnace for five times (3200 ℃ for one minute each time), and performing vacuum casting to obtain cast ingots with uniform components;
s2, performing cold rolling deformation on the alloy cast ingot obtained in the step S1 to obtain a plate with the thickness of 1.5mm, wherein the deformation is 80%;
s3, carrying out solution treatment (30 min at 950 ℃) on the plate, and then quenching and cooling to room temperature to obtain the multi-principal element alloy (named as Ti) 0.34 Zr 0.34 Hf 0.22 Ta 0.1 )。
Example 3
Example 3 provides a multi-principal element alloy, the atomic percentages of the elements of which are shown in table 1, and the preparation method is as follows:
s1, weighing zirconium, hafnium, tantalum and titanium according to atomic percentages of element components, repeatedly smelting the zirconium, the hafnium, the tantalum and the titanium in a magnetic stirring vacuum non-consumable electric arc furnace for five times (3100 ℃ for one minute each time), and performing vacuum casting to obtain cast ingots with uniform components;
s2, performing cold rolling deformation on the alloy cast ingot obtained in the step S1 to obtain a plate with the thickness of 1.5mm, wherein the deformation is 70%;
s3, carrying out solution treatment (950 ℃ for 20 min) on the plate, and then quenching and cooling to room temperature to obtain the multi-principal element alloy (named as Ti) 0.32 Zr 0.32 Hf 0.25 Ta 0.1 )。
Example 4
Example 4 provides a multi-principal element alloy, the atomic percentages of the elements of which are shown in table 1, and the preparation method is as follows:
s1, weighing zirconium, hafnium, tantalum and titanium according to atomic percentages of element components, repeatedly smelting the zirconium, the hafnium, the tantalum and the titanium in a magnetic stirring vacuum non-consumable electric arc furnace for five times (3000 ℃ for one minute each time), and performing vacuum casting to obtain cast ingots with uniform components;
s2, performing cold rolling deformation on the alloy cast ingot obtained in the step S1 to obtain a plate with the thickness of 1.5mm, wherein the deformation is 90%;
s3, carrying out solution treatment (950 ℃ for 15 min) on the plate, and then quenching and cooling to room temperature to obtain the multi-principal element alloy (named as Ti) 0.31 Zr 0.31 Hf 0.25 Ta 0.13 )。
Example 5
Example 5 provides a multi-principal element alloy, the atomic percentages of the elements of which are shown in table 1, the preparation method is as follows:
s1, weighing zirconium, hafnium, tantalum and titanium according to atomic percentages of element components, repeatedly smelting the zirconium, the hafnium, the tantalum and the titanium in a magnetic stirring vacuum non-consumable electric arc furnace for five times (3000 ℃ for one minute each time), and performing vacuum casting to obtain cast ingots with uniform components;
s2, performing cold rolling deformation on the alloy cast ingot obtained in the step S1 to obtain a plate with the thickness of 1.5mm, wherein the deformation is 90%;
s3, carrying out solution treatment (60 min at 950 ℃) on the plate, and then quenching and cooling to room temperature to obtain the multi-principal element alloy (named as Ti) 0.29 Zr 0.29 Hf 0.25 Ta 0.14 )。
Comparative examples 1 to 2
Comparative examples 1 to 2 provide a multi-principal element alloy whose atomic percentages of the respective elements are shown in table 1, and the preparation method thereof is the same as that of example 1.
Table 1 atomic percent content of examples 1 to 5 and comparative examples 1 to 2
Titanium | Zirconium | Hafnium (Hf) | Tantalum (Ta) | |
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% |
Performance testing
The multi-principal component alloys prepared in examples 1 to 5 and comparative examples 1 to 2 above were subjected to elastic modulus and elongation test:
the test method is as follows: a plurality of drawn dog bone samples, with gauge sizes of 12 x 4 x 1.5mm, were prepared from the original samples by wire-cut electrical discharge machining. Tensile testing (MTS E45.504) was performed at room temperature using a strain rate of 10 -3 s -1 . Digital image correlation (DIC; correlated Solution, inc.) instruments and their onboard video extensometers are synchronized with the tensile tester to directly receive stress-strain data during the stretching process at a frame capture rate of 1Hz, resulting in a stress-strain curve. The modulus of elasticity was obtained by fitting the slope of the elastic segment of the curve, and the elongation was obtained from the stress-strain curve, the results of which are shown in Table 2.
Table 2 examples 1 to 5 and comparative examples 1 to 2
As can be seen from the data in table 2, the multi-principal element alloys provided by the present invention have a low elastic modulus and high plasticity (the greater the elongation, the higher the plasticity). While the elemental compositions of comparative examples 1 and 2, although consistent with the present invention, are outside the scope of the present invention, they have a high modulus of elasticity, low plasticity, and are undesirable.
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A multi-principal element alloy comprising the following components in atomic percent:
28-37% of zirconium, 18-26% of hafnium, 9-14% of tantalum and the balance of titanium and unavoidable impurities.
2. The multi-principal element alloy of claim 1, comprising the following components in atomic percent:
30-35% of zirconium, 20-25% of hafnium, 10-12% of tantalum and the balance of titanium and unavoidable impurities.
3. The method of preparing a multi-master alloy according to claim 1 or 2, comprising the steps of:
s1, weighing zirconium, hafnium, tantalum and titanium according to atomic percentages of elemental components, and smelting into alloy ingots;
s2, performing cold rolling deformation on the alloy cast ingot obtained in the step S1 to obtain a plate blank;
s3, carrying out solution treatment on the plate, and then quenching and cooling to room temperature.
4. The method of producing a multi-element alloy according to claim 3, wherein in step S3, the solution temperature of the solution treatment is 900 ℃ to 1200 ℃.
5. The method of producing a multi-component alloy according to claim 3, wherein in step S3, the heat-retaining time of the solution treatment is 5min to 60min.
6. A method of producing a multi-master alloy according to claim 3, wherein in step S2, the deformation amount of the cold rolling deformation is 50 to 90%.
7. A method of producing a multi-master alloy according to claim 3, wherein in step S3, the cooling rate is 550 ℃/S to 650 ℃/S.
8. A method of producing a multi-master alloy according to claim 3, wherein in step S1, the melting temperature is 3000 ℃ to 3200 ℃.
9. A method of producing a multi-master alloy according to claim 3, wherein in step S1, the apparatus used for smelting is a non-consumable vacuum arc furnace.
10. Use of a multi-principal element alloy according to claim 1 or 2 for the preparation of biomedical materials.
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