CN113278860A - Medium-entropy titanium alloy with ultralow elastic modulus and high yield strength, and preparation method and application thereof - Google Patents
Medium-entropy titanium alloy with ultralow elastic modulus and high yield strength, and preparation method and application thereof Download PDFInfo
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- CN113278860A CN113278860A CN202110557848.4A CN202110557848A CN113278860A CN 113278860 A CN113278860 A CN 113278860A CN 202110557848 A CN202110557848 A CN 202110557848A CN 113278860 A CN113278860 A CN 113278860A
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- 229910001069 Ti alloy Inorganic materials 0.000 title description 18
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000956 alloy Substances 0.000 description 31
- 229910045601 alloy Inorganic materials 0.000 description 30
- 238000005728 strengthening Methods 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007943 implant Substances 0.000 description 8
- 238000005097 cold rolling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 229910001040 Beta-titanium Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001325 element alloy Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910017339 Mo—Sn Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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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
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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
- 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
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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
- 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
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- 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
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- 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
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- 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
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- Epidemiology (AREA)
- Veterinary Medicine (AREA)
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- Medicinal Chemistry (AREA)
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Abstract
本发明公开了一种超低弹性模量高屈服强度中熵钛合金、制备方法及应用，其中，所述合金在室温下具有优异综合力学性能，通过冷轧以及后续热处理可获得高性能的合金，所得到的合金的屈服强度可达到1.4GPa以上并具备一定的塑性，杨氏模量低，约为30GPa，与骨相当。该高性能合金可加工成多种形式的产品，在生物植入体等领域内有潜在的应用前景。
The invention discloses a medium-entropy titanium alloy with ultra-low elastic modulus and high yield strength, a preparation method and application, wherein the alloy has excellent comprehensive mechanical properties at room temperature, and a high-performance alloy can be obtained by cold rolling and subsequent heat treatment , the yield strength of the obtained alloy can reach more than 1.4GPa and has a certain plasticity, and the Young's modulus is low, about 30GPa, which is equivalent to bone. The high-performance alloy can be processed into various forms of products, and has potential application prospects in fields such as biological implants.
Description
Technical Field
The invention belongs to the field of preparation of low-modulus high-strength titanium alloy materials, and relates to the field of strengthening and toughening of titanium alloys, in particular to design of low-modulus high-strength materials applied in the fields of biomedical materials and the like and a preparation method thereof.
Background
Commercially pure titanium (c.p.ti) and Ti-6Al-4V alloys are widely used to manufacture body implant devices due to their light weight, corrosion resistance, excellent biocompatibility, and good mechanical properties. However, pure titanium (elastic modulus: 103GPa) and Ti-6Al-4V (elastic modulus: 110GPa) alloys have a higher elastic modulus than human bone (elastic modulus: 30GPa), and so-called stress shielding effect is generated during use.
Therefore, low modulus metastable beta-type titanium alloys, such as Ti-Ta, Ti-Nb-Ta-Zr, Ti-Nb-Mo-Sn, and the like, have been developed in succession. However, the low yield strength of beta titanium alloys has been hampered by the fact that for strengthening beta titanium alloys it is common to introduce a high volume fraction of stable alpha or omega phase for phase strengthening during aging, however, this alpha or omega phase has a much higher modulus of elasticity than the base beta titanium alloy, and therefore there is a clear conflict between strength enhancement and modulus of elasticity reduction. One party is often sacrificed to meet the needs of the other.
Therefore, in order to meet the requirements of the mechanical properties of the implant, the development of an alloy with high yield strength and ultra-low modulus has been the goal pursued by the material scientist.
Disclosure of Invention
In view of the above, the invention aims to provide a medium-entropy titanium alloy with ultralow elastic modulus and high yield strength, a preparation method and an application thereof, so as to solve the problems of the existing titanium alloy.
The invention provides a medium entropy titanium alloy with ultralow elastic modulus and high yield strength, which is characterized by comprising the following components in atomic percentage: ti: 47-48%, Zr: 18-20%, V: 18-20%, Nb: 9-10% of Al: 4.5 to 5.5 percent.
Preferably, the medium entropy titanium alloy with ultralow elastic modulus and high yield strength comprises the following components in atomic percentage: ti: 47.5%, Zr: 19%, V: 19%, Nb: 9.5%, Al: 5 percent.
The invention also provides a preparation method of the medium entropy titanium alloy with ultralow elastic modulus and high yield strength, which comprises the following steps:
(1) preparing alloy according to the components and the atomic percentage thereof, and casting the alloy into an ingot;
(2) and sequentially carrying out solid solution treatment, cold rolling treatment and aging heat treatment on the cast ingot to obtain the ultralow-elastic-modulus high-yield-strength medium-entropy titanium alloy.
Preferably, in the step (2), the temperature of the solution treatment is 1000-1100 ℃ and the time is 2-3 h.
More preferably, in the step (2), the cold rolling treatment has a deformation amount of 80 to 90%.
Further preferably, in the step (2), the temperature of the aging heat treatment is 300-400 ℃, and the time is 4-5 hours.
More preferably, in the step (2), the temperature of the solution treatment is 1050 ℃ for 2 hours, the rolling deformation of the cold rolling treatment is 80%, and the temperature of the aging heat treatment is 350 ℃ for 4.5 hours.
The invention also provides application of the medium entropy titanium alloy with ultralow elastic modulus and high yield strength in a biological implant, specifically: and manufacturing the ultralow-elastic-modulus high-yield-strength medium-entropy titanium alloy into a preset biological implant shape, and applying the preset biological implant shape as a biological implant.
The ultralow-elastic-modulus high-yield-strength intermediate-entropy titanium alloy provided by the invention can regulate and control the stability of the beta phase of the alloy by adding high-fraction Nb, V, Zr and Al elements, and can obtain a metastable beta-phase structure, so that the alloy has the comprehensive strengthening and toughening effect of a small amount of strengthening phases which are dispersed and distributed and generated by solid solution strengthening, deformation strengthening and subsequent low-temperature aging treatment, and finally obtains ideal comprehensive mechanical properties: the tensile plasticity reaches more than 10 percent, the yield strength is higher than 1.4GPa, and the Young modulus is very low, about 30GPa, and is equivalent to that of bone. The high-performance alloy can be processed into products in various forms, and has potential application prospects in the fields of biological implants and the like.
Drawings
The invention is described in further detail below with reference to the following figures and embodiments:
FIG. 1 is an XRD (X-ray diffraction) morphology chart before and after deformation of the ultralow-elastic-modulus high-yield-strength medium-entropy titanium alloy after aging heat treatment;
FIG. 2 is a mechanical property curve diagram of the medium entropy titanium alloy with ultra-low elastic modulus and high yield strength provided by the invention under the room temperature condition.
Detailed Description
Recently, multi-principal element high-entropy alloys become a research hotspot, due to the action of high entropy, the alloy can still be in single-phase solid solution due to the addition of high-content elements, and due to the increase of the types and the number of the alloys, the performance of the alloys can be more easily regulated and controlled. The invention forms metastable multi-principal-element beta-type titanium alloy through the design of multi-principal-element alloy, and comprehensively strengthens a small amount of dispersed omega phase generated by strong solid solution strengthening, deformation strengthening and subsequent low-temperature aging treatment of multi-principal-element alloy elements, thereby achieving the advantage of ultrahigh yield strength without damaging the advantage of low elastic modulus of the alloy. The alloy also generates phase change in the deformation engineering to generate the effect of phase change toughening, so the alloy also has high toughness. Is a promising candidate material for biological implantation material.
Example 1
Is prepared into Ti47Zr20V20Nb9Al4.5(at.%) alloy is smelted into 5Kg ingot by vacuum suspension furnace, and solution treatment is carried out at 1000 deg.C/3 h. Then, cold rolling was performed for a plurality of passes with a deformation of 80%, and a corresponding sheet was prepared. Finally, performing aging heat treatment at 300 ℃/5h to obtain the alloy sheet.
At room temperature at 10 deg.C-3s-1The resulting alloy sheet was stretched at a yield strength of 1.42GPa, a nominal tensile plasticity of 7% and a Young's modulus of about 30 GPa.
Example 2
Is prepared into Ti48Zr18V18Nb10Al5.5(at.%) alloy is smelted into 5Kg ingot by vacuum suspension furnace, and solution treatment is carried out at 1100 deg.C/2 h. Then, cold rolling is carried out for multiple times, the deformation is 90%, and the corresponding sheet is prepared. Finally, performing aging heat treatment at 400 ℃/4h to obtain the alloy sheet.
At room temperature at 10 deg.C-3s-1The resulting alloy sheet was stretched at a yield strength of 1.35GPa, a nominal tensile plasticity of 11%, and a Young's modulus of about 30 GPa.
Example 3
Is prepared into Ti47.5Zr19V19Nb9.5Al5(at.%) alloy is smelted into 5Kg ingot by vacuum suspension furnace, and solution treatment is carried out at 1050 deg.C/2 h. Then, cold rolling was performed for a plurality of passes with a deformation of 80%, and a corresponding sheet was prepared. Finally, the alloy sheet is obtained after aging heat treatment at 350 ℃/4.5 h.
At room temperature at 10 deg.C-3s-1The resulting alloy sheet was stretched at a yield strength of 1.4GPa, a nominal tensile plasticity of 10% and a Young's modulus of about 30 GPa.
The ultralow-elastic-modulus high-yield-strength intermediate-entropy titanium alloy provided by the invention can regulate and control the stability of the beta phase of the alloy by adding high-fraction Nb, V, Zr and Al elements, and can obtain a metastable beta-phase structure, so that the alloy has the comprehensive strengthening and toughening effect of a small amount of strengthening phases which are dispersed and distributed and generated by solid solution strengthening, deformation strengthening and subsequent low-temperature aging treatment, and finally obtains ideal comprehensive mechanical properties: as shown in FIG. 1, the obtained alloy sheet after aging heat treatment mainly has a BCC structure beta phase, and as shown in FIG. 2, the obtained alloy sheet has tensile plasticity of more than 10%, yield strength higher than 1.4GPa, and Young's modulus of about 30GPa, and is equivalent to that of bone at room temperature. The high-performance alloy can be processed into products in various forms, and has potential application prospects in the fields of biological implants and the like.
Claims (8)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0437079A1 (en) * | 1989-12-21 | 1991-07-17 | SMITH & NEPHEW RICHARDS, INC. | Biocompatible low modulus titanium alloy for medical implants |
| JP2006183100A (en) * | 2004-12-28 | 2006-07-13 | Aichi Steel Works Ltd | High-strength titanium alloy having excellent cold workability |
| US20070227628A1 (en) * | 2006-04-04 | 2007-10-04 | Daido Tokushuko Kabushiki Kaisha | Beta-type titanium alloy and product thereof |
| CN107805740A (en) * | 2017-10-10 | 2018-03-16 | 东南大学 | The medical embedded titanium alloy and preparation method of a kind of low elastic modulus high-fatigue strength |
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- 2021-05-21 CN CN202110557848.4A patent/CN113278860B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0437079A1 (en) * | 1989-12-21 | 1991-07-17 | SMITH & NEPHEW RICHARDS, INC. | Biocompatible low modulus titanium alloy for medical implants |
| JP2006183100A (en) * | 2004-12-28 | 2006-07-13 | Aichi Steel Works Ltd | High-strength titanium alloy having excellent cold workability |
| US20070227628A1 (en) * | 2006-04-04 | 2007-10-04 | Daido Tokushuko Kabushiki Kaisha | Beta-type titanium alloy and product thereof |
| CN107805740A (en) * | 2017-10-10 | 2018-03-16 | 东南大学 | The medical embedded titanium alloy and preparation method of a kind of low elastic modulus high-fatigue strength |
Non-Patent Citations (4)
| Title |
|---|
| FEI ZHANG等: ""Martensitic transformations and the shape memory effect in Ti-Zr-Nb-Al high-temperature shape memory alloys"", 《MATERIALS SCIENCE & ENGINEERING A》 * |
| 孟超: "《深入探讨新型金属材料-超级合金的性能与应用》", 31 May 2018, 电子科技大学出版社 * |
| 王选理: ""Ti-V系β钛合金结构稳定性及其塑性变形机制"", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技I辑》 * |
| 雷霆: "《钛及钛合金》", 30 April 2018, 冶金工业出版社 * |
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