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WO2018176853A1 - 一种含Si高强低模β-型钛合金及其制备方法与应用 - Google Patents

一种含Si高强低模β-型钛合金及其制备方法与应用 Download PDF

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WO2018176853A1
WO2018176853A1 PCT/CN2017/111106 CN2017111106W WO2018176853A1 WO 2018176853 A1 WO2018176853 A1 WO 2018176853A1 CN 2017111106 W CN2017111106 W CN 2017111106W WO 2018176853 A1 WO2018176853 A1 WO 2018176853A1
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titanium alloy
phase
mode
type titanium
strength low
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French (fr)
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李元元
叶伟文
杨超
王芬
张卫文
肖志瑜
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to US16/497,810 priority Critical patent/US11891679B2/en
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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
    • 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
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • C22F1/16—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

Definitions

  • the invention belongs to the field of titanium alloy materials, and particularly relates to a high-strength low-mode ⁇ -type titanium alloy containing Si and a preparation method and application thereof.
  • Titanium alloy has the characteristics of good biocompatibility, excellent comprehensive mechanical properties and good corrosion resistance. It has become the mainstream material for the development of medical products in the international community.
  • the development of titanium and its alloys can be divided into three eras: the first era is represented by pure titanium and Ti-6Al-4V, which have higher strength and better processing properties.
  • the second era is a new type of ⁇ + ⁇ -type titanium alloy represented by Ti-5Al-2.5Fe and Ti-6Al-7Nb. The structure is more controllable and the performance is also greatly improved.
  • the third era is correct.
  • the new beta-type titanium alloy is the most widely studied.
  • novel ⁇ -type titanium alloys generally contain elements such as Nb, Zr, Ta, Mo, Sn, Fe, such as Ti13Nb13Zr, Ti-24Nb-4Zr-8Sn, Ti-12Mo-6Zr-2Fe, Ti-35Nb-7Zr-5Ta, Ti-29Nb-4.6Zr-13Ta, Ti-Nb-Zr-Ta-Fe, etc., they have the advantages of high strength, low modulus of elasticity, good corrosion resistance, and good biocompatibility with human body.
  • the coarse grain size results in lower strength and poor wear resistance.
  • fine-grained materials have unique advantages in terms of biocompatibility. Due to the higher grain boundary surface energy, the nanocrystalline/ultrafine crystal material has better osteoclast adhesion and biocompatibility than the same component coarse crystal material.
  • the purpose is to introduce new elements into the new phase and the traditional titanium alloy phase The interaction occurs, which makes the structure of the titanium alloy more diversified, and the performance regulation also has more space.
  • non-metallic elements can form metallization
  • the compound can enhance the controllability of the performance of the titanium alloy by regulating the morphology and distribution of the metal compound, and provides many possibilities for preparing a titanium alloy with superior performance.
  • non-metallic elements such as Si
  • the introduction of non-metallic elements, such as Si tends to form a weakened phase of the grain boundary containing Si. From the relationship between the microstructure and macroscopic properties of the material and the control mechanism, the performance of the continuous thin layer of the grain boundary is usually relative to the material. To weaken the role.
  • the hypereutectoid steel is first transformed into a single-phase austenite, and the pro-eutectoid cementite precipitated in the subsequent cooling process is a continuous network along the austenite grain boundary.
  • the hypereutectoid steel of this structure has high brittleness and poor plasticity. How to achieve grain refinement and interrupt the grain boundary continuous phase, under normal circumstances, it is impossible to achieve a win-win situation in the above two aspects through heat treatment.
  • Another object of the present invention is to provide a Si-containing high-strength low-mode ⁇ -type titanium alloy prepared by the above method.
  • Still another object of the present invention is to provide an application of the above-described Si-containing high-strength low-mode ⁇ -type titanium alloy in the field of preparing biomedical materials.
  • a preparation method of a Si-containing high-strength low-mode ⁇ -type titanium alloy comprising the following preparation steps:
  • Titanium sponge sponge with Ti 60 ⁇ 70at.%, Nb 10 ⁇ 20at.%, Zr5 ⁇ 15at.%, Ta 1 ⁇ 10at.%, Si 1 ⁇ 5at.% Zirconium, hafnium intermediate alloy, silicon as raw material to prepare alloy components;
  • High temperature plastic deformation the ingot obtained in the step (2) is subjected to high temperature plastic deformation, the deformation temperature is 800 to 900 ° C, the deformation amount is 60 to 80%, and then the sample after high temperature plastic deformation is water quenched to room temperature;
  • the Si element content satisfies the as-cast structure of the alloy component, and the Si-containing metal compound (Ti, Zr) 2 Si (collectively, the S2 phase) is precipitated in the grain boundary and the crystal.
  • the smelting described in the step (2) means smelting using a vacuum consumable arc melting furnace.
  • the ingot microstructure obtained in the step (2) is characterized in that: the acicular S2 phase having a length of 50 to 100 ⁇ m and the spherical S2 phase having a size of 1 to 3 ⁇ m are dispersed inside the ⁇ -Ti crystal grains of 50 to 300 ⁇ m. The grain boundary is distributed with a continuous S2 phase.
  • the high temperature plastic deformation in the step (3) may be any one of hot rolling, hot forging, hot extrusion, hot pier and the like.
  • the microstructure characteristic after the high temperature plastic deformation in the step (3) is: the ⁇ -Ti crystal grains are elongated along the deformation direction, and a distinct slip zone appears, and the continuous S2 phase transition is distributed in the grain boundary in the step (2). It is a lath-shaped S 2 phase of 30 to 60 ⁇ m.
  • the microstructure after the recrystallization in the step (4) is characterized in that the lath-shaped S 2 phase of 30-60 ⁇ m after the high-temperature plastic deformation in the step (3) is divided into the size by the recrystallized grains of the new nucleation.
  • a Si-containing high-strength low-mode ⁇ -type titanium alloy is prepared by the above method.
  • the microstructure of the Si-containing high-strength low-mode ⁇ -type titanium alloy is characterized by: an acicular ⁇ -Ti phase in an equiaxed ⁇ -Ti grain and an S2 phase having an irregular shape; wherein the equiaxed ⁇ -
  • the size of the Ti crystal grains is in the range of 5 to 15 ⁇ m
  • the size of the S2 phase having an irregular shape is 5 to 20 ⁇ m
  • the length of the needle-shaped ⁇ -Ti phase is 1 to 5 ⁇ m.
  • the structure control principle of the Si-containing high-strength low-mode ⁇ -type titanium alloy according to the present invention is as follows: by the step (1) alloy composition design, a ⁇ -phase stable element such as cerium, zirconium or hafnium is added to the main element component titanium.
  • step (3) slat-like S2
  • the phase is divided by the recrystallized grains of the new nucleation, thereby achieving the purpose of strengthening and toughening the material.
  • the strength and plasticity of the titanium alloy are greatly improved after the step (4) is returned to the recrystallization treatment as compared with the step (2) ingot. Therefore, this patent will solve the bottleneck problem of the mechanical properties of the continuous grain boundary phase in the material science.
  • the preparation method of the invention and the obtained Si-containing high-strength low-mode ⁇ -type titanium alloy have the following advantages and beneficial effects:
  • the invention provides a tissue control method for solving the mechanical properties of continuous grain boundary phase deteriorated alloy materials in the material science based on titanium alloy composition design and casting, plastic deformation and heat treatment;
  • the present invention obtains an as-cast structure in which a Si-containing phase is distributed in a coarse ⁇ -Ti grain boundary, and a dispersed spherical S2 phase is precipitated in a ⁇ -Ti grain by composition design; a spherical dispersed S2 phase interacts with dislocations.
  • a fine and diffusely distributed cell structure recrystallizing greatly refines the grains; at the same time, high temperature plastic deformation causes severe lattice distortion of the material, and the original mesh grain boundary is cut by the incoherence of intergranular slip
  • the precipitated phase, the precipitated phase of the network grain boundary is divided to achieve the strengthening and toughening of the material;
  • the preparation process of the invention is a combination of casting, hot rolling and heat treatment, and the preparation process is relatively mature, and the parameters of each preparation step can be well controlled, and the material properties obtained by multiple preparations are relatively stable, which is favorable for mass production. .
  • Example 2 is an SEM image of the microstructure of the as-rolled titanium alloy after high temperature plastic deformation obtained in the step (3) of Example 1.
  • Example 3 is an SEM image of the microstructure of the recovered recrystallized titanium alloy obtained in the step (4) of Example 1.
  • FIG. 4 is a graph showing tensile stress and strain curves of the as-reduced titanium alloy obtained in the step (2) of the first embodiment and the recrystallized titanium alloy obtained in the step (4).
  • Alloy composition design The composition of the titanium alloy is Ti 60 at.%, Nb 20 at.%, Zr10 at.%, Ta 5 at.%, Si 5 at.%.
  • the alloy is prepared by using titanium sponge, sponge zirconium, niobium intermediate alloy and silicon as raw materials.
  • the casting process is vacuum consumable arc melting.
  • the prepared raw material is pressed into an electrode, the electrode size is controlled to be smaller than 50 to 70 mm; the gap between the electrode and the molten pool is controlled between 60 and 80 mm; the melting speed is 20 kg/min; ingot.
  • Recrystallization The sample after rolling is removed from the jacket and subjected to recrystallization annealing.
  • the sample was placed in a heat treatment furnace, and the temperature was raised to 900 ° C with the furnace, the heating rate was controlled at 10 ° C / min, and the temperature was kept for 4 hours, and recrystallization annealing treatment was performed.
  • the annealed sample was taken out to cool to room temperature to obtain the Si-containing high-strength low-mode ⁇ -type titanium alloy.
  • the SEM image of the microstructure of the as-cast titanium alloy obtained in the step (2) of the present embodiment is shown in Fig. 1. It can be seen from the figure that a spherical S2 phase having a size of about 1 to 3 ⁇ m and a needle-like S2 phase having a length of about 50 to 100 ⁇ m are dispersed on the ⁇ -titanium substrate having a microstructure of 50 to 300 ⁇ m, and the S2 phase is continuous at the grain boundary. phase.
  • the SEM image of the microstructure of the as-rolled titanium alloy obtained after the high-temperature plastic deformation obtained in the step (3) of the present embodiment is shown in FIG. 2, and it can be seen from the figure that after the high-temperature rolling of the bcc ⁇ -Ti, the dislocation accumulation and delivery are performed. , entanglement, a long strip of slip zone, the needle-like S2 phase is shifted along the rolling direction, and the ⁇ -Ti grain is reduced from 50 to 300 ⁇ m. 1 to 2 ⁇ m; at the same time, the unsynchronized intergranular slip cuts the original S2 phase of the grain boundary, and the continuous S2 phase at the grain boundary in the step (2) is transformed into the lath S2 phase of 30 to 60 ⁇ m in length.
  • the SEM image of the microstructure of the recovered recrystallized titanium alloy obtained in the step (4) of the present embodiment is shown in FIG. It can be seen from the figure that the microstructure is an acicular ⁇ -Ti phase in an equiaxed ⁇ -Ti grain and an S2 phase having an irregular shape.
  • the size of the equiaxed ⁇ -Ti crystal grains is 5 to 15 ⁇ m
  • the size of the irregularly shaped S2 phase is 5 to 20 ⁇ m
  • the length of the needle-shaped ⁇ -Ti phase is about 1 to 5 ⁇ m.
  • the strip-shaped S2 phase having a length of 30 to 60 ⁇ m is divided into recrystallized grains into an S2 phase having an irregular shape of 5 to 20 ⁇ m; and the ⁇ -Ti crystal grains are subjected to the step ( The 50 to 300 ⁇ m of 2) is reduced to 3 to 4 ⁇ m of the step (4).
  • the tensile stress-strain curve of the as-cast titanium alloy obtained in the step (2) of the present embodiment and the recovered recrystallized titanium alloy obtained in the step (4) is shown in FIG. 4 .
  • the results in Fig. 4 show that the ingot has high brittleness, almost no plasticity, low strength, final breaking strength of 452 MPa, and elastic modulus of 85 ⁇ 1 GPa due to the existence of continuous S2 phase in the grain boundary.
  • the elastic modulus of the alloy is 45 ⁇ 2GPa, which is 40 ⁇ 1GPa lower than that of the as-cast titanium alloy, which is closer to the 30GPa of the human bone elastic modulus.
  • the tensile rupture strength of the recrystallized titanium alloy is 658 ⁇ 2MPa, which is more cast.
  • the titanium alloy has a height of 206 ⁇ 1 MPa; in particular, the tensile strain of the recrystallized titanium alloy is as high as 2.4%, which is obviously superior to the non-plastic cast titanium alloy.
  • the resulting ⁇ -type titanium alloy has higher strength, greater plasticity, lower modulus of elasticity, and finer grain size, and is significantly more suitable for use as a medical implant material, the tissue control method of the present invention. Has great advantages.
  • the composition of the titanium alloy is Ti 70at.%, Nb 10at.%, Zr10at.%, Ta 6at.%, Si 4at.%.
  • the above components are prepared by using titanium sponge, sponge zirconium, niobium intermediate alloy, and silicon as raw materials.
  • the casting process is vacuum consumable arc (VAR) melting.
  • VAR vacuum consumable arc
  • the prepared raw material is pressed into an electrode, and the electrode size is controlled to be smaller than 50 to 70 mm; the gap between the electrode and the molten pool is controlled between 60 and 80 mm; and the melting speed is 20 kg/min.
  • the ingot was obtained by two remelting.
  • Obtained micro A spherical S2 phase having a size of about 1 to 3 ⁇ m and a needle-like S2 phase having a length of about 50 to 100 ⁇ m are dispersed on the dendritic ⁇ -titanium substrate having a structure of 50 to 300 ⁇ m, and a continuous S2 phase is present at the grain boundary.
  • Recrystallization The forged sample was subjected to recrystallization annealing. The sample was placed in a heat treatment furnace, and the temperature was raised to 900 ° C with the furnace, the heating rate was controlled at 10 ° C / min, and the temperature was kept for 4 hours, and recrystallization annealing treatment was performed. The annealed sample was taken out to cool to room temperature to obtain the Si-containing high-strength low-mode ⁇ -type titanium alloy.
  • the microstructure of the Si-containing high-strength low-mode ⁇ -type titanium alloy obtained in this example is an acicular ⁇ -Ti phase in an equiaxed ⁇ -Ti grain and an S2 phase having an irregular shape.
  • the size of the equiaxed ⁇ -Ti crystal grains is 5 to 15 ⁇ m
  • the diameter of the irregularly shaped S2 phase is about 5 to 20 ⁇ m
  • the length of the needle-shaped ⁇ -Ti phase is 1 to 5 ⁇ m.
  • a titanium alloy having properties similar to those of Example 1 was obtained.
  • the composition of the titanium alloy is Ti 65at.%, Nb 15at.%, Zr10at.%, Ta 7at.%, Si 3at.%.
  • the above components are prepared by using titanium sponge, sponge zirconium, niobium intermediate alloy, and silicon as raw materials.
  • the casting process is vacuum consumable arc (VAR) melting.
  • VAR vacuum consumable arc
  • the prepared raw material is pressed into an electrode, and the electrode size is controlled to be smaller than 50 to 70 mm; the gap between the electrode and the molten pool is controlled between 60 and 80 mm; and the melting speed is 20 kg/min.
  • the ingot was obtained by two remelting.
  • the obtained as-cast microstructure is a dendritic ⁇ -titanium matrix of 50 to 300 ⁇ m, and a spherical S2 phase having a size of about 1 to 3 ⁇ m and a needle-like S2 phase having a length of about 50 to 100 ⁇ m are dispersed, and the grain boundary is continuous. S2 phase.
  • Recrystallization The sample after drawing is subjected to recrystallization annealing. Put the sample into heat treatment In the furnace, the temperature was raised to 900 ° C with the furnace, the heating rate was controlled at 10 ° C / min, and the temperature was kept for 4 h, and recrystallization annealing treatment was performed. The annealed sample was taken out to cool to room temperature to obtain the Si-containing high-strength low-mode ⁇ -type titanium alloy.
  • the microstructure of the high-strength low-mode ⁇ -titanium alloy obtained in this example is an acicular ⁇ -Ti phase in an equiaxed ⁇ -Ti grain and an S2 phase having an irregular shape.
  • the size of the equiaxed ⁇ -Ti crystal grains ranges from 5 to 15 ⁇ m, the diameter of the irregularly shaped S2 phase is about 5 to 20 ⁇ m, and the length of the needle-shaped ⁇ -Ti phase is about 5 ⁇ m.
  • the obtained titanium alloy was similar in performance to Example 1.
  • the composition of the titanium alloy is Ti 63at.%, Nb 17at.%, Zr10at.%, Ta 8at.%, Si 2at.%.
  • the above components are prepared by using titanium sponge, sponge zirconium, niobium intermediate alloy, and silicon as raw materials.
  • the casting process is vacuum consumable arc (VAR) melting.
  • VAR vacuum consumable arc
  • the prepared raw material is pressed into an electrode, and the electrode size is controlled to be smaller than 50 to 70 mm; the gap between the electrode and the molten pool is controlled between 60 and 80 mm; and the melting speed is 20 kg/min.
  • the ingot was obtained by two remelting.
  • the obtained as-cast microstructure is a dendritic ⁇ -titanium matrix of 50 to 300 ⁇ m, and a spherical S2 phase having a size of about 1 to 3 ⁇ m and a needle-like S2 phase having a length of about 50 to 100 ⁇ m are dispersed, and the grain boundary is continuous. S2 phase.
  • Recrystallization The sample after rolling is removed from the jacket and subjected to recrystallization annealing.
  • the sample was placed in a heat treatment furnace, and the temperature was raised to 900 ° C with the furnace, the heating rate was controlled at 10 ° C / min, and the temperature was kept for 4 hours, and recrystallization annealing treatment was performed.
  • the annealed sample was taken out to cool to room temperature to obtain the Si-containing high-strength low-mode ⁇ -type titanium alloy.
  • the microstructure of the high-strength low-mode ⁇ -titanium alloy obtained in this example is an acicular ⁇ -Ti phase in an equiaxed ⁇ -Ti grain and an S2 phase having an irregular shape.
  • the size of the equiaxed ⁇ -Ti grains ranges from 5 to 15 ⁇ m.
  • the diameter of the S2 phase having an irregular shape is about 5 to 20 ⁇ m, and the length of the needle-shaped ⁇ -Ti phase is about 5 ⁇ m.
  • the obtained titanium alloy was similar in performance to Example 1.
  • the composition of the titanium alloy is Ti 67at.%, Nb 15at.%, Zr8at.%, Ta 9at.%, Si 1at.%.
  • the above components are prepared by using titanium sponge, sponge zirconium, niobium intermediate alloy, and silicon as raw materials.
  • the casting process is vacuum consumable arc (VAR) melting.
  • VAR vacuum consumable arc
  • the prepared raw material is pressed into an electrode, and the electrode size is controlled to be smaller than 50 to 70 mm; the gap between the electrode and the molten pool is controlled between 60 and 80 mm; and the melting speed is 20 kg/min.
  • the ingot was obtained by two remelting.
  • the obtained as-cast microstructure is a dendritic ⁇ -titanium matrix of 50 to 300 ⁇ m, and a spherical S2 phase having a size of about 1 to 3 ⁇ m and a needle-like S2 phase having a length of about 50 to 100 ⁇ m are dispersed, and the grain boundary is continuous. S2 phase.
  • Recrystallization The sample after rolling is removed from the jacket and subjected to recrystallization annealing.
  • the sample was placed in a heat treatment furnace, and the temperature was raised to 900 ° C with the furnace, the heating rate was controlled at 10 ° C / min, and the temperature was kept for 4 hours, and recrystallization annealing treatment was performed.
  • the annealed sample was taken out to cool to room temperature to obtain the Si-containing high-strength low-mode ⁇ -type titanium alloy.
  • the microstructure of the high-strength low-mode ⁇ -titanium alloy obtained in this example is an acicular ⁇ -Ti phase in an equiaxed ⁇ -Ti grain and an S2 phase having an irregular shape.
  • the size of the equiaxed ⁇ -Ti crystal grains ranges from 5 to 15 ⁇ m, the diameter of the irregularly shaped S2 phase is about 5 to 20 ⁇ m, and the length of the needle-shaped ⁇ -Ti phase is about 5 ⁇ m.
  • the obtained titanium alloy was similar in performance to Example 1.

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Abstract

属于钛合金材料领域，公开了一种含Si高强低模β-型钛合金及其制备方法与应用。所述制备方法为：以Ti60～70％，Nb10～20％，Zr5～15％，Ta1～10％，Si1～5％的原子百分比，以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金组分，然后合金组分熔炼均匀，得到凝固的铸锭，再将所得铸锭进行高温塑性变形，变形温度800～900℃，变形量为60～80％，水淬至室温；最后将所得试样加热至再结晶温度，保温1～4h，退火处理后空冷至室温，得到所述含Si高强低模β-型钛合金。所得钛合金具有更高的强度、更大的塑性、更低的弹性模量以及更细小的晶粒尺寸，更适合用作医用植入件材料。

Description

一种含Si高强低模β-型钛合金及其制备方法与应用 技术领域
本发明属于钛合金材料领域，具体涉及一种含Si高强低模β-型钛合金及其制备方法与应用。
背景技术
钛合金具有生物相容性好、综合力学性能优异、耐腐蚀性好等特性，现已成为国际社会开发医用产品的主流材料。钛及其合金的发展可分为三个时代：第一个时代以纯钛和Ti-6Al-4V为代表，该类材料具有较高的强度和较好的加工性能。第二个时代是以Ti-5Al-2.5Fe和Ti-6Al-7Nb为代表的新型α+β型钛合金，组织更为可控，在性能亦都有较大提高；第三个时代以对新型β-型钛合金的研究最为广泛。这些新型β-型钛合金一般包含Nb、Zr、Ta、Mo、Sn、Fe等元素，如Ti13Nb13Zr、Ti-24Nb-4Zr-8Sn、Ti-12Mo-6Zr-2Fe、Ti-35Nb-7Zr-5Ta、Ti-29Nb-4.6Zr-13Ta、Ti-Nb-Zr-Ta-Fe等，他们具有强度高、弹性模量低、耐蚀性好、与人体生物相容性好等优点。
对于目前铸造法或塑性成形法制备的β-型钛合金而言，粗大的晶粒尺寸(至少40～60μm以上)导致了其较低的强度和较差的耐磨性。尤其是，对于医用材料而言，除了力学性能更加优异外，细晶材料在生物相容性方面也有其独特优点。由于具有更高的晶界表面能，纳米晶/超细晶材料具有比同成分粗晶材料更好的造骨细胞粘附力和生物相容性。另一方面，随着钛合金的发展，其合金元素越来越多，从刚开始的二元到现在的五元甚至更多，目的是通过引入新元素形成的新相与传统的钛合金相发生相互作用，从而使钛合金的组织更为多元化，性能调控也具备更大的空间。特别是非金属元素的引入，可以形成金属化 合物，通过调控金属化合物的形貌、分布使钛合金的性能可控性增强，为制备性能更优异的钛合金提供了诸多可能性。但是，非金属元素的引入，如Si元素容易生成含Si的晶界弱化相，从材料微观结构与宏观性能的关系与控制机理来看，通常情况下晶界连续薄层脆性相对材料的性能起到弱化的作用。例如，过共析钢在冷却速度较慢的情况下，先转变为单相的奥氏体，在随后的冷却过程中析出的先共析渗碳体沿着奥氏体晶界呈连续的网状分布，这种组织结构的过共析钢脆性高、塑性差。如何实现晶粒细化、且打断晶界连续相，通常情况下无法通过热处理在以上两方面实现双赢。
发明内容
为了解决以上现有技术的缺点和不足之处，本发明的首要目的在于提供一种含Si高强低模β-型钛合金的制备方法。
本发明的另一目的在于提供一种通过上述方法制备得到的含Si高强低模β-型钛合金。
本发明的再一目的在于提供上述含Si高强低模β-型钛合金在制备生物医用材料领域中的应用。
本发明目的通过以下技术方案实现：
一种含Si高强低模β-型钛合金的制备方法，包括如下制备步骤：
(1)合金成分设计：以Ti 60～70at.％，Nb 10～20at.％，Zr5～15at.％，Ta 1～10at.％，Si 1～5at.％的元素比，以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金组分；
(2)铸造：将步骤(1)配制的合金组分熔炼均匀，并得到凝固的铸锭；
(3)高温塑性变形：将步骤(2)所得铸锭进行高温塑性变形，变形温度800～900℃，变形量为60～80％，然后将高温塑性变形后的试样水淬至室温；
(4)回复再结晶：将步骤(3)高温塑性变形的试样加热至再结晶温度，保温1～4h，退火处理后空冷至室温，得到所述含Si高强低模β-型钛合金。
优选地，步骤(1)中所述Si元素含量满足合金组分的铸态组织在晶界及晶内析出含Si金属化合物(Ti，Zr)2Si(统称S2相)。
优选地，步骤(2)中所述的熔炼是指采用真空自耗电弧熔炼炉进行熔炼。
优选地，步骤(2)中获得的铸锭组织特征为：50～300μm的β-Ti晶粒内部弥散分布着长度在50～100μm的针状S2相及尺寸为1～3μm的球状S2相，晶界分布着连续的S2相。
优选地，步骤(3)中所述高温塑性变形可采用热轧、热锻、热挤压、热墩等方法中的任意一种。
优选地，步骤(3)中经高温塑性变形后的组织特征为：β-Ti晶粒沿变形方向拉长、出现明显的滑移带，步骤(2)中晶界分布着连续的S2相转变为30～60μm的板条状S2相。
优选地，步骤(4)中所述回复再结晶后的组织特征为：步骤(3)中高温塑性变形后30～60μm的板条状S2相被新形核的再结晶晶粒分割为尺寸5～20μm形状不规整的S2相。
一种含Si高强低模β-型钛合金，通过上述方法制备得到。
优选地，所述含Si高强低模β-型钛合金的组织特征为：等轴状β-Ti晶粒内的针状α-Ti相以及形状不规整的S2相；其中等轴状β-Ti晶粒的大小范围为5～15μm，形状不规整的S2相尺寸为5～20μm，针状α-Ti相的长度为1～5μm。
上述含Si高强低模β-型钛合金在制备生物医用材料领域中的应用。尤其是用作医用植入件材料(如股骨柄、髋骨、膝盖骨等人体植入零件)。
本发明所述的含Si高强低模β-型钛合金，其组织控制原理为：通过步骤(1)合金成分设计，在主要元素组分钛中添加铌、锆、钽等β相稳定元素，再添加生物相容性更加优异的微量晶粒细化元素Si；通过步骤(2)铸锭制备获得连续的S2相分布于粗大β-Ti晶界的合金铸锭，晶界连续的S2相导致了合金较低的强度和极低的塑性；在步骤(3)高温塑性变形中，β-Ti和含Si相在高温下发生软化，bccβ-Ti较多的滑移系导致位错塞积、交割、缠结，出现长条状的滑移带， 同时晶粒间滑移的不协同性切割原始的晶界连续的S2相；在步骤(4)回复再结晶中，塑性变形导致的晶格畸变能成为再结晶的驱动力，胞状结构(胞状结构为塑性变形过程中由于位错运动所形成的一种微观结构)成为新晶粒的形核核心。这些能量很高的胞状结构，高温下发生胞壁平直化，形成亚晶，亚晶粒通过亚晶合并机制以及亚晶迁移机制长大形成新晶粒，从而步骤(3)板条状S2相被新形核的再结晶晶粒分割，进而实现材料强韧化的目的。总之，与步骤(2)铸锭相比，步骤(4)回复再结晶处理后，钛合金的强度和塑性均大幅提升。因此，本专利将解决材料科学中连续晶界相恶化合金材料力学性能的瓶颈问题。
本发明的制备方法及所得到的含Si高强低模β-型钛合金具有如下优点及有益效果：
(1)本发明基于钛合金成分设计及铸造、塑性变形和热处理的基础上，提供了一种解决材料科学中连续晶界相恶化合金材料力学性能的组织控制方法；
(2)本发明通过成分设计获得含Si相分布于粗大的β-Ti晶界，β-Ti晶粒内析出弥散球状S2相的铸态组织；球状弥散分布的S2相，与位错相互作用，形成细小且弥散分布的胞状结构，再结晶后大大细化了晶粒；同时高温塑性变形使材料产生严重的晶格畸变，利用晶粒间滑移的不协同性切割原始的网状晶界析出相，网状晶界析出相被分割从而实现材料的强韧化；
(3)本发明的制备工艺为铸造、热轧和热处理相结合，制备工艺较为成熟，能良好的控制每一个制备环节的参数，多次制备获得的材料性能较为稳定，有利于大批量的生产。
附图说明
图1为实施例1步骤(2)中所得铸态钛合金的组织形貌SEM图；
图2为实施例1步骤(3)中所得高温塑性变形后的轧制态钛合金的组织形貌SEM图；
图3为实施例1步骤(4)中所得回复再结晶态钛合金的组织形貌SEM图；
图4为实施例1步骤(2)所得铸态钛合金与步骤(4)所得回复再结晶态钛合金的拉伸应力应变曲线图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
(1)合金成分设计：设计钛合金成分为Ti 60at.％，Nb 20at.％，Zr10at.％，Ta 5at.％，Si5at.％。以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金。
(2)铸造：铸造工艺为真空自耗电弧熔炼。将配制好的原材料压制成电极，电极大小控制在比坩埚小50～70mm之间；电极与熔池之间的间隙控制在60～80mm之间；熔炼速度为20kg/min；两次重熔获得铸锭。
(3)高温塑性变形：将铸造获得的铸锭切割成15×25×80mm的长方体试样。选择Ti-6Al-4V作为包套材料，将包套与试样装配好，加热到900℃，保温30min。多道次热轧。最终获得轧制比为80％的试样，水淬至室温。
(4)回复再结晶：轧制后的试样去除包套，进行再结晶退火。将试样放入热处理炉中，随炉升温至900℃，升温速率控制在10℃/min，保温4h，进行再结晶退火处理。退火后的试样取出空冷至室温，得到所述含Si高强低模β-型钛合金。
本实施例步骤(2)中所得铸态钛合金的组织形貌SEM图如图1所示。由图可见，其微观组织为50～300μm的β-钛基体上弥散分布着尺寸为1～3μm左右的球状S2相和长度在50～100μm左右的针状S2相，晶界处为连续的S2相。
本实施例步骤(3)中所得高温塑性变形后的轧制态钛合金的组织形貌SEM图如图2所示，由图可见，bccβ-Ti在高温轧制后，位错塞积、交割、缠结，出现长条状的滑移带，针状S2相沿轧制方向偏移，β-Ti晶粒由50～300μm减小为 1～2μm；同时晶粒间滑移的不协同性切割原始的晶界连续的S2相，步骤(2)中晶界处连续的S2相转变为长度30～60μm的板条状S2相。
本实施例步骤(4)中所得回复再结晶态钛合金的组织形貌SEM图如图3所示。由图可见其显微组织为等轴状β-Ti晶粒内的针状α-Ti相和形状不规整的S2相。等轴β-Ti晶粒的大小范围为5～15μm，形状不规整的S2相的尺寸为5～20μm，针状α-Ti相的长度为1～5μm左右。尤其是，高温塑性变形后步骤(3)中长度30～60μm的板条状S2相被再结晶晶粒分割成为尺寸5～20μm形状不规整的S2相；同时其β-Ti晶粒由步骤(2)的50～300μm减小为步骤(4)的3～4μm。
本实施例步骤(2)所得铸态钛合金与步骤(4)所得回复再结晶态钛合金的拉伸应力应变曲线图如图4所示。图4结果表明，由于晶界连续的S2相的存在，铸锭的脆性较大，几乎无塑性，强度较低、最终断裂强度为452MPa，且弹性模量为85±1GPa；回复再结晶态钛合金的弹性模量为45±2GPa，较铸造态钛合金低40±1GPa，更加接近人骨弹性模量的30GPa；同时，回复再结晶态钛合金的拉伸断裂强度为658±2MPa，较铸造态钛合金高206±1MPa；尤其是，回复再结晶态钛合金的拉伸应变高达2.4％，明显优于无塑性的铸造态钛合金。最终所得β-型钛合金具有更高的强度、更大的塑性、更低的弹性模量，以及更细小的晶粒尺寸，明显更适合用作医用植入件材料，本发明的组织控制方法具有极大优势。
实施例2
(1)配制合金成分：设计钛合金成分为Ti 70at.％，Nb 10at.％，Zr10at.％，Ta 6at.％，Si 4at.％。以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金上述成分。
(2)铸造：铸造工艺为真空自耗电弧(VAR)熔炼。将配制好的原材料压制成电极，电极大小控制在比坩埚小50～70mm之间；电极与熔池之间的间隙控制在60～80mm之间；熔炼速度为20kg/min。两次重熔获得铸锭。获得的铸态微 观组织为50～300μm的树枝晶β-钛基体上弥散分布着尺寸为1～3μm左右的球状S2相和长度在50～100μm左右的针状S2相，晶界处为连续的S2相。
(3)高温塑性变形：将铸造获得的铸锭切割成50×50×50mm的正方体试样。将切好的试样加热到900℃，保温30min。在900℃下进行恒温热锻，最终获得锻造比为60％的试样，随后试样立即水淬至室温。
(4)回复再结晶：锻造后的试样进行再结晶退火。将试样放入热处理炉中，随炉升温至900℃，升温速率控制在10℃/min，保温4h，进行再结晶退火处理。退火后的试样取出空冷至室温，得到所述含Si高强低模β-型钛合金。
本实施例得到的含Si高强低模β-型钛合金的微观结构显微组织为等轴状β-Ti晶粒内的针状α-Ti相和以及形状不规整的S2相。等轴β-Ti晶粒的大小范围为5～15μm，形状不规整的S2相的直径为5～20μm左右，针状α-Ti相的长度为1～5μm。获得与实施例1性能相近的钛合金。
实施例3
(1)配制合金成分：设计钛合金成分为Ti 65at.％，Nb 15at.％，Zr10at.％，Ta 7at.％，Si 3at.％。以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金上述成分。
(2)铸造：铸造工艺为真空自耗电弧(VAR)熔炼。将配制好的原材料压制成电极，电极大小控制在比坩埚小50～70mm之间；电极与熔池之间的间隙控制在60～80mm之间；熔炼速度为20kg/min。两次重熔获得铸锭。获得的铸态微观组织为50～300μm的树枝晶β-钛基体上弥散分布着尺寸为1～3μm左右的球状S2相和长度在50-100μm左右的针状S2相，晶界处为连续的S2相。
(3)高温塑性变形：将铸造获得的铸锭切割成Φ15×80mm的柱体试样。将试样加热到900℃，保温30min。选着模孔为5mm的拉拔模具，一次性拉拔成型，拉拔后的试样立即水淬至室温。
(4)回复再结晶：将拉拔后的试样，进行再结晶退火。将试样放入热处理 炉中，随炉升温至900℃，升温速率控制在10℃/min，保温4h，进行再结晶退火处理。退火后的试样取出空冷至室温，得到所述含Si高强低模β-型钛合金。
本实施例得到的高强低模β-钛合金的微观结构显微组织为等轴状β-Ti晶粒内的针状α-Ti相和形状不规整的S2相。等轴β-Ti晶粒的大小范围为5～15μm，形状不规整的S2相的直径为5～20μm左右，针状α-Ti相的长度为5μm左右。获得的钛合金与实施例1性能相近。
实施例4
(1)配制合金成分：设计钛合金成分为Ti 63at.％，Nb 17at.％，Zr10at.％，Ta 8at.％，Si 2at.％。以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金上述成分。
(2)铸造：铸造工艺为真空自耗电弧(VAR)熔炼。将配制好的原材料压制成电极，电极大小控制在比坩埚小50～70mm之间；电极与熔池之间的间隙控制在60～80mm之间；熔炼速度为20kg/min。两次重熔获得铸锭。获得的铸态微观组织为50～300μm的树枝晶β-钛基体上弥散分布着尺寸为1～3μm左右的球状S2相和长度在50-100μm左右的针状S2相，晶界处为连续的S2相。
(3)高温塑性变形：将铸造获得的铸锭切割成Φ30×30mm的柱体试样。为了减小最后一步淬火对墩模的损害，选用冷墩机进行墩制。冷镦模具模腔尺寸为10mm，将试样加热到900℃，保温30min，放置于墩模上方漏斗形凹坑内进行墩制成型。墩制结束后，试样及模具立即水淬至室温。
(4)回复再结晶：轧制后的试样去除包套，进行再结晶退火。将试样放入热处理炉中，随炉升温至900℃，升温速率控制在10℃/min，保温4h，进行再结晶退火处理。退火后的试样取出空冷至室温，得到所述含Si高强低模β-型钛合金。
本实施例得到的高强低模β-钛合金的微观结构显微组织为等轴状β-Ti晶粒内的针状α-Ti相和形状不规整的S2相。等轴β-Ti晶粒的大小范围为5～15μm， 形状不规整的S2相的直径为5～20μm左右，针状α-Ti相的长度为5μm左右。获得的钛合金与实施例1性能相近。
实施例5
(1)配制合金成分：设计钛合金成分为Ti 67at.％，Nb 15at.％，Zr8at.％，Ta 9at.％，Si 1at.％。以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金上述成分。
(2)铸造：铸造工艺为真空自耗电弧(VAR)熔炼。将配制好的原材料压制成电极，电极大小控制在比坩埚小50～70mm之间；电极与熔池之间的间隙控制在60～80mm之间；熔炼速度为20kg/min。两次重熔获得铸锭。获得的铸态微观组织为50～300μm的树枝晶β-钛基体上弥散分布着尺寸为1～3μm左右的球状S2相和长度在50-100μm左右的针状S2相，晶界处为连续的S2相。
(3)高温塑性变形：将铸造获得的铸锭切割成50×50×50mm的正方体试样。将切好的试样加热到900℃，保温30min。在900℃下进行恒温热锻，最终获得锻造比为70％的试样，随后试样立即水淬至室温。
(4)回复再结晶：轧制后的试样去除包套，进行再结晶退火。将试样放入热处理炉中，随炉升温至900℃，升温速率控制在10℃/min，保温4h，进行再结晶退火处理。退火后的试样取出空冷至室温，得到所述含Si高强低模β-型钛合金。
本实施例得到的高强低模β-钛合金的微观结构显微组织为等轴状β-Ti晶粒内的针状α-Ti相和形状不规整的S2相。等轴β-Ti晶粒的大小范围为5～15μm，形状不规整的S2相的直径为5～20μm左右，针状α-Ti相的长度为5μm左右。获得的钛合金与实施例1性能相近。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种含Si高强低模β-型钛合金的制备方法，其特征在于包括如下制备步骤：
    (1)合金成分设计：以Ti 60～70at.％，Nb 10～20at.％，Zr5～15at.％，Ta 1～10at.％，Si 1～5at.％的元素比，以海绵钛、海绵锆、钽铌中间合金、硅为原材料配制合金组分；
    (2)铸造：将步骤(1)配制的合金组分熔炼均匀，并得到凝固的铸锭；
    (3)高温塑性变形：将步骤(2)所得铸锭进行高温塑性变形，变形温度800～900℃，变形量为60～80％，然后将高温塑性变形后的试样水淬至室温；
    (4)回复再结晶：将步骤(3)高温塑性变形的试样加热至再结晶温度，保温1～4h，退火处理后空冷至室温，得到所述含Si高强低模β-型钛合金。
  2. 根据权利要求1所述的一种含Si高强低模β-型钛合金的制备方法，其特征在于：步骤(1)中所述Si元素含量满足合金组分的铸态组织在晶界及晶内析出含Si金属化合物S2相。
  3. 根据权利要求1所述的一种含Si高强低模β-型钛合金的制备方法，其特征在于：步骤(2)中所述的熔炼是指采用真空自耗电弧熔炼炉进行熔炼。
  4. 根据权利要求1所述的一种含Si高强低模β-型钛合金的制备方法，其特征在于：步骤(2)中获得的铸锭组织特征为：50～300μm的β-Ti晶粒内部弥散分布着长度在50～100μm的针状S2相及尺寸为1～3μm的球状S2相，晶界分布着连续的S2相。
  5. 根据权利要求1所述的一种含Si高强低模β-型钛合金的制备方法，其特征在于：步骤(3)中所述高温塑性变形采用热轧、热锻、热挤压、热墩方法中的任意一种。
  6. 根据权利要求4所述的一种含Si高强低模β-型钛合金的制备方法，其特征在于：步骤(3)中经高温塑性变形后的组织特征为：β-Ti晶粒沿变形方向 拉长、出现明显的滑移带，步骤(2)中晶界分布着连续的S2相转变为30～60μm的板条状S2相。
  7. 根据权利要求6所述的一种含Si高强低模β-型钛合金的制备方法，其特征在于：步骤(4)中所述回复再结晶后的组织特征为：步骤(3)中高温塑性变形后30～60μm的板条状S2相被新形核的再结晶晶粒分割为尺寸5～20μm形状不规整的S2相。
  8. 一种含Si高强低模β-型钛合金，其特征在于：通过权利要求1～7任一项所述的方法制备得到。
  9. 根据权利要求8所述的一种含Si高强低模β-型钛合金，其特征在于：所述含Si高强低模β-型钛合金的组织特征为：等轴状β-Ti晶粒内的针状α-Ti相以及形状不规整的S2相；其中等轴状β-Ti晶粒的大小范围为5～15μm，形状不规整的S2相尺寸为5～20μm，针状α-Ti相的长度为1～5μm。
  10. 权利要求8或9所述的一种含Si高强低模β-型钛合金在制备生物医用材料领域中的应用。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003873A (zh) * 2007-01-19 2007-07-25 上海交通大学医学院附属第九人民医院 低弹性模量β型Ti－Nb－Zr合金、制备方法及应用
US20070227628A1 (en) * 2006-04-04 2007-10-04 Daido Tokushuko Kabushiki Kaisha Beta-type titanium alloy and product thereof
CN101724764A (zh) * 2009-12-10 2010-06-09 中南大学 一种生物医用β-钛合金的制备工艺
CN103060609A (zh) * 2011-10-21 2013-04-24 北京航空航天大学 一种低弹性模量、高强度的近β钛合金及制备方法
CN103320734A (zh) * 2013-06-26 2013-09-25 西安赛特金属材料开发有限公司 医用细晶钛/钛合金棒材的生产方法
CN103509959A (zh) * 2013-07-30 2014-01-15 中国船舶重工集团公司第七二五研究所 一种生物医用低弹性模量钛钽铌锆硅合金的制备方法
CN104263996A (zh) * 2014-09-26 2015-01-07 华南理工大学 一种超高塑性、高强低模医用超细晶钛合金及其制备方法
CN107034383A (zh) * 2017-03-27 2017-08-11 华南理工大学 一种含Si高强低模β‑型钛合金及其制备方法与应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6767418B1 (en) * 1999-04-23 2004-07-27 Terumo Kabushiki Kaisha Ti-Zr type alloy and medical appliance formed thereof
KR100977801B1 (ko) * 2007-12-26 2010-08-25 주식회사 포스코 강도 및 연성이 우수한 저탄성 티타늄 합금 및 그 제조방법
CN101760669A (zh) * 2009-12-29 2010-06-30 沈阳铸造研究所 一种低弹性模量的铸造钛合金
CN101921929B (zh) * 2010-09-02 2012-07-18 上海交通大学 用于骨科植入的含氧医用β钛合金及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070227628A1 (en) * 2006-04-04 2007-10-04 Daido Tokushuko Kabushiki Kaisha Beta-type titanium alloy and product thereof
CN101003873A (zh) * 2007-01-19 2007-07-25 上海交通大学医学院附属第九人民医院 低弹性模量β型Ti－Nb－Zr合金、制备方法及应用
CN101724764A (zh) * 2009-12-10 2010-06-09 中南大学 一种生物医用β-钛合金的制备工艺
CN103060609A (zh) * 2011-10-21 2013-04-24 北京航空航天大学 一种低弹性模量、高强度的近β钛合金及制备方法
CN103320734A (zh) * 2013-06-26 2013-09-25 西安赛特金属材料开发有限公司 医用细晶钛/钛合金棒材的生产方法
CN103509959A (zh) * 2013-07-30 2014-01-15 中国船舶重工集团公司第七二五研究所 一种生物医用低弹性模量钛钽铌锆硅合金的制备方法
CN104263996A (zh) * 2014-09-26 2015-01-07 华南理工大学 一种超高塑性、高强低模医用超细晶钛合金及其制备方法
CN107034383A (zh) * 2017-03-27 2017-08-11 华南理工大学 一种含Si高强低模β‑型钛合金及其制备方法与应用

Cited By (10)

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CN115889812B (zh) * 2022-11-23 2024-04-02 上海交通大学 一种增材制造高强塑钛合金及其制备方法和应用
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