CN111485134B - Deformation-induced high-modulus medical titanium alloy and preparation method thereof - Google Patents

Deformation-induced high-modulus medical titanium alloy and preparation method thereof Download PDF

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CN111485134B
CN111485134B CN202010358555.9A CN202010358555A CN111485134B CN 111485134 B CN111485134 B CN 111485134B CN 202010358555 A CN202010358555 A CN 202010358555A CN 111485134 B CN111485134 B CN 111485134B
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titanium alloy
deformation
modulus
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medical titanium
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CN111485134A (en
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李强
程超
张然
齐强
新家光雄
刘旭燕
周凯
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University of Shanghai for Science and Technology
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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
    • 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
    • C22F1/16—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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Abstract

The invention provides a deformation-induced high-modulus medical titanium alloy and a preparation method thereof, wherein the titanium alloy consists of 20-25% of Nb, 10-15% of Ta, 3-5% of Zr, 1-5% of Mo and the balance of Ti in percentage by mass. The preparation method of the deformation-induced high-modulus medical titanium alloy comprises the steps of preparing an alloy ingot by using a high-vacuum arc melting furnace or a high-vacuum induction melting furnace; carrying out homogenizing annealing on the cast ingot in an argon environment; carrying out solid solution treatment under the vacuum condition and placing the solution in water for quenching; cold working at room temperature without intermediate annealing; carrying out recrystallization annealing for 1-2 hours at 750-950 ℃ under the vacuum condition on the obtained sheet, and then putting the sheet into water for quenching; obtaining the medical titanium alloy with high modulus induced by deformation. The titanium alloy has good plasticity; the deformation is induced by stress to change phase, so that the Young modulus and the strength are obviously improved, the shape is more stable, and the method can be used for manufacturing various orthopedic wires, spinal orthotics and the like.

Description

Deformation-induced high-modulus medical titanium alloy and preparation method thereof
Technical Field
The invention relates to the field of novel metal medical materials, in particular to a deformation-induced high-modulus medical titanium alloy and a preparation method thereof.
Background
Along with social progress, improvement of living standard of people and aging of population of society, more and more attention is paid to health and medical problems, and higher requirements on medical process and treatment effect are provided for people; the development of science and technology and the progress of medical technology also provide more technical function indexes for materials. Titanium and titanium alloy have high specific strength, low Young's modulus, excellent corrosion resistance and biocompatibility, and are applied to medical clinical fields such as hard tissue substitution, dental orthopedics, cardiovascular stents and the like. Since element V is cytotoxic and element Al may cause Alzheimer's disease, Ti-6Al-4V (TC4) which is widely used at present causes concern about implantation safety, and the Young's modulus of TC4 is still high.
In recent years, designing a β type titanium alloy having a young's modulus more matched to human bone has been a hot spot of research. Researches show that elements such as Zr, Sn, Nb, Ta and Mo are nontoxic elements suitable for developing biomedical titanium alloys, and researchers develop a series of low-modulus beta-type titanium alloys successively. When low modulus titanium alloys are used as spinal orthopedic materials, two requirements need to be met: 1. the implant part, the material needs to have a low young's modulus to avoid stress shielding; 2. the bending orthopedic part is made of materials which are easy to form, stable in shape and low in resilience. However, for a given strength, a material with a low young's modulus has a high spring back, and a low modulus titanium alloy generally has a metastable β phase and exhibits a certain superelasticity. The current low modulus titanium alloy is difficult to satisfy the two requirements simultaneously. Therefore, the development of titanium alloys that satisfy both low modulus and low spring back has important application value.
In metastable beta titanium alloys, twinning, stress induced alpha "phase transformation, stress induced omega phase transformation, and the like may occur during loading. The Young's modulus of the alloy is determined by the phase composition, the Young's modulus of the alpha 'phase is lower, and the Young's modulus of the omega phase is higher. The existing metastable low-modulus beta titanium alloy is mainly a stress-induced alpha' phase, and the stress-induced omega phase transformation is obtained by changing a loading deformation mechanism through component design, so that the deformation-induced high modulus can be obtained, and the requirement of a spinal column orthopedic material is met.
Disclosure of Invention
The invention aims to provide a deformation-induced high-modulus medical titanium alloy and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the deformation-induced high-modulus medical titanium alloy comprises the following components in percentage by mass: nb: 20-25%; ta: 10-15%; zr: 3-5%; mo: 1-5%; the balance being Ti.
Further, the mass percentages xNb, xTa, xzr and xMo of the three elements Nb, Ta, Zr and Mo satisfy the following conditions: 11 is less than or equal to 0.28xNb +0.22xTa +0.12xZr + xMo is less than or equal to 15.
Further, the deformation-induced high-modulus medical titanium alloy comprises the following components in percentage by mass: nb: 28%; ta: 12.5 percent; zr: 4.5 percent; mo: 1% and the balance Ti.
Further, the deformation-induced high-modulus medical titanium alloy comprises the following components in percentage by mass: nb: 25 percent; ta: 11 percent; zr: 4 percent; mo: 3 percent, and the balance being Ti.
Further, the deformation-induced high-modulus medical titanium alloy comprises the following components in percentage by mass: nb: 23 percent; ta: 10.5 percent; zr: 3.5 percent; mo: 5 percent, and the balance being Ti.
A method of making a deformation-inducing high modulus medical titanium alloy comprising:
1) weighing Nb, Ta, Zr, Mo and Ti according to the mass percentage;
2) preparing an alloy ingot by using a high-vacuum arc melting furnace or a high-vacuum induction melting furnace;
3) carrying out homogenizing annealing on the cast ingot under the condition of argon protective atmosphere; annealing at 1000-1200 ℃ for 10-12 hours, and then furnace cooling to room temperature;
4) carrying out solid solution treatment under a vacuum condition, wherein the solid solution temperature is 800-900 ℃, the solid solution time is 0.5-1 hour, and then putting into water for quenching;
5) rolling and forming at room temperature; the plastic deformation rate is 5-10% each time, and intermediate annealing is not needed;
6) carrying out recrystallization annealing on the formed sample under the vacuum condition; and (3) carrying out recrystallization annealing at 750-950 ℃ for 1-2 hours, and then putting the titanium alloy into water for quenching to obtain the expected titanium alloy.
The low-modulus metastable beta-type titanium alloy designed and prepared by taking Nb, Ta and Zr as main alloy elements is easy to generate stress-induced alpha' phase transformation, and has higher resilience after deformation; when the material is used as a spinal column orthopedic and fixing material, the application requirements can not be completely met. According to the invention, a small amount of Mo element is added, and the mass percentages of Nb, Ta and Zr are adjusted, so that the metastable beta-type titanium alloy generates stress-induced omega phase transformation, the Young modulus is greatly increased, and the resilience after deformation is greatly reduced.
Compared with the prior art, the invention has the advantages that: the Mo element provides a certain solid solution strengthening effect, and the yield strength and the tensile strength of the solid solution alloy are improved along with the increase of the content of the Mo element. The omega phase generated by stress induction can also strengthen the alloy, and the strength of the deformed alloy is further obviously improved. Meanwhile, the Young modulus of the deformed alloy is improved, and the shape is more stable under the condition that the rigidity and the strength of the alloy after being processed and deformed are improved, the alloy is not easy to deform again in the using process, and the stability and the reliability of shape correction are ensured.
The titanium alloy provided by the invention is composed of non-toxic elements, has good corrosion resistance, higher strength and stable deformation shape, and can be used for manufacturing various orthopedic wires, spinal orthotics and the like.
Drawings
Fig. 1 is an XRD pattern of the titanium alloy prepared in the first embodiment of the present invention.
Fig. 2 is an optical microscopic image of the titanium alloy produced in the first embodiment of the present invention.
Fig. 3 is an XRD pattern of the titanium alloy prepared in the second embodiment of the present invention.
Fig. 4 is an optical microscopic image of a titanium alloy prepared in a second embodiment of the present invention.
Fig. 5 is a graph comparing a three-point bending spring back curve of a titanium alloy prepared in a second embodiment of the present invention with a conventional beta titanium alloy.
Fig. 6 is a graph comparing a three-point bending spring back curve of a titanium alloy prepared in a third embodiment of the present invention with a general beta titanium alloy.
Detailed Description
The technical solution adopted by the present invention will be further explained with reference to the schematic drawings.
The invention provides a deformation-induced high-modulus medical titanium alloy which comprises the following components in percentage by mass: 28% of Nb, 12.5% of Ta, 4.5% of Zr, 1% of Mo and the balance Ti.
The following details the preparation method of the medical titanium alloy with high modulus induced by deformation, which comprises the following steps: an alloy ingot with the mass percentage of 28 percent of Nb, 12.5 percent of Ta, 4.5 percent of Zr, 1 percent of Mo and the balance of Ti is prepared by a high vacuum arc melting method. Carrying out homogenizing annealing on the cast ingot at 1000 ℃ for 12 hours, and cooling along with the furnace; dissolving in solution at 800 deg.C for 0.5 hr, and quenching in water. Cold rolling at room temperature about 80%. And annealing the sheet obtained by cold rolling at 750 ℃ for 2 hours, and putting the sheet into water for quenching to obtain a final solid solution state sample.
Fig. 1 and fig. 2 show XRD patterns and optical microscopic images of the prepared titanium alloy, respectively, the solid solution alloy obtained by the foregoing method is a single β phase, and young's modulus measured by free resonance method is 58 GPa; the yield strength measured by a static load tensile method is about 550MPa, and the tensile strength is about 660 MPa; the three-point bending depression was 3mm, and the measured spring back was 1.65 mm. The Young modulus of the deformed alloy is 67GPa, the yield strength is about 712MPa, and the tensile strength is 785 MPa.
The second embodiment of the invention provides a deformation-induced high-modulus medical titanium alloy which is composed of the following components in percentage by mass: nb is 25%, Ta is 11%, Zr is 4%, Mo is 3%, and the rest is Ti.
The preparation method of the deformation-induced high-modulus medical titanium alloy comprises the following steps: an alloy ingot with the mass percentage of 25 percent of Nb, 11 percent of Ta, 4 percent of Zr, 3 percent of Mo and the balance of Ti is prepared by adopting a high vacuum arc melting method. Carrying out homogenizing annealing on the cast ingot at 1100 ℃ for 11 hours, and cooling along with the furnace; solid dissolving at 850 deg.C for 0.5 hr, and quenching in water. Cold rolling at room temperature about 80%. The sheet obtained by cold rolling was annealed at 800 ℃ for 1.5 hours, and quenched in water to obtain a final solid solution sample.
Fig. 3 and 4 show XRD patterns and optical microscopic images of the titanium alloy, respectively, and fig. 5 is a comparison graph of a three-point bending spring back curve of the prepared titanium alloy with a general beta titanium alloy. The solid solution alloy is a single beta phase, and the Young modulus measured by a free resonance method is 60 GPa; the yield strength measured by a static load tensile method is about 580MPa, and the tensile strength is about 650 MPa; the three-point bending depression was 3mm, and the measured spring back was 1.55 mm. The Young modulus of the deformed alloy is 74GPa, the yield strength is about 750MPa, and the tensile strength is 837 MPa.
The third embodiment of the invention provides a deformation-induced high-modulus medical titanium alloy which comprises the following components in percentage by mass: 23% of Nb, 10.5% of Ta, 3.5% of Zr, 5% of Mo and the balance of Ti.
The preparation method of the deformation-induced high-modulus medical titanium alloy comprises the following steps: an alloy ingot with the mass percentage of 23 percent of Nb, 10.5 percent of Ta, 3.5 percent of Zr, 5 percent of Mo and the balance of Ti is prepared by adopting a high vacuum arc melting method. Carrying out homogenizing annealing on the cast ingot at 1200 ℃ for 10 hours, and cooling along with the furnace; dissolving in solution at 900 deg.C for 0.5 hr, and quenching in water. Cold rolling at room temperature about 80%. And annealing the sheet obtained by cold rolling at 850 ℃ for 1 hour, and putting the sheet into water for quenching to obtain a final solid solution state sample.
FIG. 6 is a comparison of three-point bending spring-back curves of prepared titanium alloys and common beta titanium alloys, wherein the solid solution alloy is a single beta phase, and the Young modulus measured by a free resonance method is 64 GPa; the yield strength measured by a static load tensile method is about 650MPa, and the tensile strength is about 670 MPa; the three-point bending depression was 3mm, and the measured spring back was 1.45 mm. The Young modulus of the deformed alloy is 75.5GPa, the yield strength is about 750MPa, and the tensile strength is 813 MPa.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (3)

1. The deformation-induced high-modulus medical titanium alloy is characterized by comprising the following components in percentage by mass:
Nb：20～25％；
Ta：10～15％；
Zr：3～5％；
Mo：1～5％；
the balance being Ti;
the mass percentage x of the four elements of Nb, Ta, Zr and MoNb、xTa、xzrAnd xMoThe following conditions are satisfied: 11 is less than or equal to 0.28xNb+0.22xTa+0.12xZr+xMo≤15；
A method of deformation inducing high modulus medical titanium alloy, comprising:
1) weighing Nb, Ta, Zr, Mo and Ti according to the mass percentage;
2) preparing an alloy ingot by using a high-vacuum arc melting furnace or a high-vacuum induction melting furnace;
3) carrying out homogenizing annealing on the cast ingot under the condition of argon protective atmosphere; annealing at 1000-1200 ℃ for 10-12 hours, and then furnace cooling to room temperature;
4) carrying out solid solution treatment under a vacuum condition, wherein the solid solution temperature is 800-900 ℃, the solid solution time is 0.5-1 hour, and then putting into water for quenching;
5) rolling and forming at room temperature; the plastic deformation rate is 5-10% each time, and intermediate annealing is not needed;
6) carrying out recrystallization annealing on the formed sample under the vacuum condition; and (3) carrying out recrystallization annealing at 750-950 ℃ for 1-2 hours, and then putting the titanium alloy into water for quenching to obtain the expected titanium alloy.
2. The deformation-induced high modulus medical titanium alloy according to claim 1, wherein the deformation-induced high modulus medical titanium alloy consists of the following components in percentage by mass:
Nb：25％；
Ta：11％；
Zr：4％；
mo: 3 percent, and the balance being Ti.
3. The deformation-induced high modulus medical titanium alloy according to claim 1, wherein the deformation-induced high modulus medical titanium alloy consists of the following components in percentage by mass:
Nb：23％；
Ta：10.5％；
Zr：3.5％；
mo: 5 percent, and the balance being Ti.
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