CN106435271B - A kind of low modulus medical titanium alloy and preparation method thereof - Google Patents
A kind of low modulus medical titanium alloy and preparation method thereof Download PDFInfo
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- CN106435271B CN106435271B CN201611160409.5A CN201611160409A CN106435271B CN 106435271 B CN106435271 B CN 106435271B CN 201611160409 A CN201611160409 A CN 201611160409A CN 106435271 B CN106435271 B CN 106435271B
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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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- 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
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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
- C22F1/02—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
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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
Abstract
The invention discloses a kind of low modulus medical titanium alloys, are 10 ~ 25% Nb by Mole percent specific concentration, the Ti of 1 ~ 8% Cr, 0 ~ 2% Sn, surplus is formed.The present invention also provides the preparation methods of above-mentioned low modulus medical titanium alloy, prepare alloy cast ingot with high vacuum arc-melting furnace or high vacuum induction melting furnace；Under the conditions of argon atmosphere, homogenizing annealing is carried out to ingot casting；Solution treatment is carried out in vacuum condition, is subsequently placed at quenching-in water；Then it carries out at room temperature cold-formed；Sample after cold working carries out recrystallization annealing under vacuum conditions；Recrystallization annealing temperature is 700 ~ 900 DEG C, and the time is 0.5 ~ 2 hour, and the type of cooling is water quenching or ice water quenching, obtains low modulus medical titanium alloy.Titanium alloy of the invention has good cold-forming property；The intensity of alloy is high, and Young's modulus is low, corrosion resistance and good biocompatibility, is suitable for the medical domains such as bone implantation.
Description
Technical field
The invention belongs to field of metallurgy, are related to the preparation and processing technology of a kind of metal material, specifically a kind of low
Modulus medical titanium alloy and preparation method thereof.
Background technique
Titanium and titanium alloy have the characteristics that high specific strength, low elastic modulus and good corrosion resistance, especially have excellent
Good biocompatibility is increasingly becoming the ideal functionality structural material that human body hard tissue reparation and substitution are used on clinical medicine.
The titanium alloys such as current medically widely used Ti-6Al-4V and Ni-Ti, Al, V, Ni plasma released after being chronically implanted
There are toxicity or human allergy is caused to react；Their elasticity modulus is excessively high, mismatches with people's bone, and then generates stress shielding
Cause implantation effect undesirable.Beta titanium alloy has lower Young's modulus and better bio-compatible than two phase alloy of alpha+beta
Property, it is the hot spot direction of Recent study.
The elements such as Nb, Mo, Zr, Ta are the common addition element of common titanium alloy at present.To obtain room temperature β phase, existing rank
The titanium alloy of section is properly added the improvement Phase Transformation Characteristic such as Zr, Ta and performance is current master generally with Nb for main beta stable element
The design method wanted.But these elements are expensive, and fusing point is higher, and melting and casting and forming are more difficult.Beta titanium alloy compares alpha+beta
Two phase alloys have lower Young's modulus and better biocompatibility, are the hot spot directions of research.Meanwhile part beta titanium
β → α " the martensite transfor mation and its reverted austenite that one of alloy stress induces can generate super-elasticity, widened titanium alloy and existed
The application range of medicine.Currently, with Nb and Mo for main β phase stable element, the elements such as Zr, Ta are alloy with this feature
Addition element develops a series of with low modulus high strength and certain hyperelastic beta-titanium alloy.However, these titanium alloys are general
Lower all over intensity, super-elasticity reply volume is small, and Ta is expensive；And fusing point is higher, melting and casting processing difficulties, it is difficult to use
The method of induction melting prepares ingot casting, and the preparation and application of agglomerate body material are subject to certain restrictions.
Therefore, by optimizing components and improvement process, the relatively simple and direct method of utilization, preparation has high-intensitive, high
The technical issues of titanium alloy of elastic, low modulus and low melting point is current urgent need to resolve.
Summary of the invention
For above-mentioned technical problem in the prior art, the present invention provides a kind of low modulus medical titanium alloy and its preparations
Method, it is lower that described this low modulus medical titanium alloy and preparation method thereof will solve titanium alloy intensity in the prior art,
Super-elasticity reply volume is small, melting and the technical issues of casting processing difficulties.
The present invention provides a kind of low modulus medical titanium alloys, are made of Nb, Cr, Sn and Ti, the Mole percent of each composition
Than as follows:
Nb 10~25%,
Cr 1~8%,
Sn 0~2%
Surplus is Ti.
Further, purity of the purity of the Ti not less than 99.95%, Nb is not less than the purity of 99.95%, Cr not
Purity lower than 99.95%, Sn is not less than 99.95%；The sum of ratio of Mole percent hundred of two kinds of elements of Nb and Cr is not less than 18%.
Further, the molar percentage of the Nb and Cr is respectively 22% and 2%.
Further, the molar percentage of the Nb and Cr is respectively 10% and 8%.
Further, the molar percentage of each composition is as follows:
Nb 12%,
Cr 2%,
Sn 1%
Surplus is Ti.
Further, the molar percentage of each composition is as follows:
Nb 25%,
Cr 1%,
Sn 2%
Surplus is Ti.
Further, the molar percentage of each composition is as follows:
Nb 18%,
Cr 4%,
Sn 2%
Surplus is Ti.
The present invention also provides a kind of preparation methods of above-mentioned low modulus medical titanium alloy, include the following steps:
1) Nb, Cr, Sn and Ti are weighed according to molar percentage；
2) alloy cast ingot is prepared with high vacuum arc-melting furnace or high vacuum induction melting furnace；
3) under the conditions of argon atmosphere, homogenizing annealing is carried out to ingot casting；Annealing temperature is 1000~1200 DEG C, is moved back
The fiery time is 8~12 hours, cools to room temperature after annealing with the furnace；
4) solution treatment is carried out in vacuum condition, is subsequently placed at quenching-in water；Solid solubility temperature is 750~950 DEG C, when solid solution
Between be 1~2 hour, the type of cooling be water quenching or ice water quenching；
5) it carries out at room temperature cold-formed；Cold-formed means are cold rolling or hand-drawn wire, each the rate of plastic deformation
It is 5~10%；
6) sample after being cold worked carries out recrystallization annealing under vacuum conditions；Recrystallization annealing temperature is 700~900
DEG C, the time is 0.5~2 hour, and the type of cooling is water quenching or ice water quenching, obtains low modulus medical titanium alloy.
Further, in step 3), argon gas used is high-purity argon.
Further, after step 6) recrystallization annealing, the sample after annealing is subjected to timeliness, timeliness temperature under vacuum conditions
Degree is 200~400 DEG C, and the time is 0.5~4 hour, and the type of cooling is water quenching or ice water quenching.
Cr has the function of stronger stable β phase and better solid solution strengthening effect compared to elements such as Nb, Mo and Ta, and
The former is far below the latter by fusing point, closer to Ti, is avoided that the component segregation of alloy graining process, reduces alloy melting point convenient for casting
Cause type；The elements prices such as Cr ratio Nb, Mo and Ta are lower, the cost of medical material advantageously reduced, convenient for medical titanium alloy
It promotes and applies.Sn element is nontoxic element, and strengthening effect is greater than Zr, and fusing point is low, is able to suppress quenched martensite transformation.
In conclusion designing titanium alloy with Cr and Sn element, room temperature β phase is obtained, and be aided with heat treatment appropriate, made
Alloy has lower Young's modulus and higher-strength, while having certain super-elasticity.
The present invention provides Ti-Nb-Cr (- Sn) system titaniums with good cold-forming property and lower processing hardening
Alloy and preparation processing method.The system titanium alloy is applicable in the various cold deformation technique processing of rolling, wire drawing, bending etc. at room temperature
Molding；Alloy has the characteristics that low Young's modulus, and shows super elastic characteristics.It is easy to prepare simple and convenient processing method, is suitable for
Industrial production；Through above-mentioned solid solution --- after ageing treatment, lower Young's modulus is can still be maintained in alloy, but intensity substantially mentions
Height, at the same superelastic properties also be improved significantly.
The present invention is compared with prior art, and technological progress is significant.The present invention is under vacuum conditions, molten with electric arc
The method of refining or induction melting prepares alloy cast ingot；Pass through the means machine-shaping such as forging, rolling and wire drawing；Using solid
It is molten --- the method for timeliness improves alloy property.The titanium alloy that preparation provided by the invention and processing method obtain has good
Cold-forming property；The intensity of alloy is high, and Young's modulus is low, corrosion resistance and good biocompatibility；Alloy super-elasticity up to 2~4%,
It can be used for manufacturing medical product and daily necessity.
Titanium alloy system and its processing method provided by the invention can be widely applied to medical instrument and industrial products.If
The titanium alloy of meter is made of nontoxic element, and corrosion resistance is good, and the characteristic of low modulus is suitable for manufacture medicine and is implanted into relevant bone
Replacing part, joint prosthesis, the plantation hard tissue repairing materials such as tooth root and bone plate bone nail；Its super elastic characteristics and shape memory
Effect can be used for manufacturing the medical instruments such as wire for correcting shape of tooth, intravascular stent, manipulator, it can also be used to manufacture the production such as superlastic spectacle frame
Product.
Detailed description of the invention
Fig. 1 is the XRD spectrum of titanium alloy prepared by the embodiment of the present invention 1.
Fig. 2 is the metallograph of titanium alloy prepared by the embodiment of the present invention 1.
Fig. 3 is the tensile loads unloading curve of titanium alloy prepared by the embodiment of the present invention 1.
Fig. 4 is the XRD spectrum of titanium alloy prepared by the embodiment of the present invention 3.
Fig. 5 is the metallograph of titanium alloy prepared by the embodiment of the present invention 3.
Fig. 6 is the stress strain curve of titanium alloy prepared by the embodiment of the present invention 3.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
It is only a part of the embodiments of the present invention, the contents of the present invention are not limited only to the following examples.
Embodiment 1:
The Ti of purity >=99.95%, the Cr of purity >=99.95% and the Nb of purity >=99.95% are raw material, using height
The method of vacuum arc melting prepares the alloy cast ingot that molar percentage is 22%Nb, 2%Cr, surplus is Ti.Ingot casting is through 1000
DEG C homogenizing annealing 10 hours, subsequent 850 DEG C were dissolved 1 hour, at room temperature cold rolling about 90%.The thin slice that cold rolling is obtained exists
800 DEG C annealing 1 hour after quenching be used as final test sample state.Alloy is single β phase under the state, is surveyed with nano impress
The Young's modulus obtained is 56.4GPa, is about 568MPa with the tensile strength that static tension method measures, and super-elasticity reply is about
2.8%.
Embodiment 2:
The Ti of purity >=99.95%, the Cr and purity >=99.95%Nb of purity >=99.95% are raw material, using Gao Zhen
It is the alloy cast ingot that 10%Nb and 8%Cr surplus is Ti that the method for empty electric arc melting, which prepares molar percentage,.Ingot casting is equal through 950 DEG C
Annealing 10 hours is homogenized, subsequent 850 DEG C are dissolved 1 hour, drawing at room temperature, obtain the titanium that final diameter is 1.0mm or so and close
Spun gold material, final test sample state after 800 DEG C of silk material are annealed 1 hour.The tension that the temper alloy extension test obtains is strong
Degree is about 761MPa, and elongation percentage is about 18%, Young's modulus 56.4GPa.
Embodiment 3:
The Ti of purity >=99.95%, Cr, purity >=99.95%Nb and the purity >=99.95%Sn of purity >=99.95%
For raw material, the method for using high vacuum electric arc melting prepares molar percentage as 12%Nb, 2%Cr, 1%Sn, surplus Ti
Alloy cast ingot.Ingot casting through 1000 DEG C homogenizing annealing 10 hours, subsequent 900 DEG C are dissolved 1 hour, cold rolling 90% at room temperature.
For the thin slice that cold rolling is obtained after 800 DEG C are annealed 1 hour, 200 DEG C are used as final test sample state in timeliness 1 hour.The state
Alloy is 65.3GPa with the Young's modulus that nano impress measures, and tensile strength is about 710MPa, and elongation percentage is about 14%.
Embodiment 4:
The Ti of purity >=99.95%, Cr, purity >=99.95%Nb and the purity >=99.95%Sn of purity >=99.95%
For raw material, the method for using high vacuum electric arc melting prepares molar percentage as 25%Nb, 1%Cr, 2%Sn, surplus Ti
Alloy cast ingot.Ingot casting through 1000 DEG C homogenizing annealing 10 hours, subsequent 850 DEG C are dissolved 1 hour, cold rolling 90% at room temperature.
The thin slice that cold rolling is obtained anneals 1 hour at 800 DEG C and is used as final test sample state.What the temper alloy extension test obtained
Tensile strength is about 622MPa, and Young's modulus 62.7GPa, it is about 3.1% that super-elasticity, which is replied,.
Embodiment 5:
The Ti of purity >=99.95%, Cr, purity >=99.95%Nb and the purity >=99.95%Sn of purity >=99.95%
For raw material, the method for using high vacuum electric arc melting prepares molar percentage as 18%Nb, 4%Cr, 2%Sn, surplus Ti
Alloy cast ingot.Ingot casting through 1000 DEG C homogenizing annealing 10 hours, subsequent 850 DEG C are dissolved 1 hour, obtain in room temperature drawing final
Diameter is the silk material of 1.5mm.Silk material is annealed 1 hour at 800 DEG C and is used as final test sample state.The temper alloy, which stretches, to be surveyed
The tensile strength for trying to obtain is about 672MPa, and elongation percentage is about 11%, Young's modulus 63.4GPa.
Claims (3)
1. a kind of low modulus medical titanium alloy, it is characterised in that be made of Nb, Cr, Sn and Ti, the Mole percent of each composition is such as
Under:
Nb 10 ~ 25%,
Cr 1 ~ 8%,
Sn 1~2%
Surplus is Ti；Purity of purity of the purity of the Ti not less than 99.95%, Nb not less than 99.95%, Cr is not less than
The purity of 99.95%, Sn are not less than 99.95%；
A kind of preparation method of above-mentioned low modulus medical titanium alloy includes the following steps:
1) Nb, Cr, Sn and Ti are weighed according to molar percentage；
2) alloy cast ingot is prepared with high vacuum arc-melting furnace or high vacuum induction melting furnace；
3) under the conditions of argon atmosphere, homogenizing annealing is carried out to ingot casting；Annealing temperature is 1000 ~ 1200 DEG C, annealing
Time is 8 ~ 12 hours, cools to room temperature after annealing with the furnace；
4) solution treatment is carried out in vacuum condition, is subsequently placed at quenching-in water；Solid solubility temperature is 750 ~ 950 DEG C, solution time 1
~ 2 hours, the type of cooling was water quenching；
5) it carries out at room temperature cold-formed；Cold-formed means be cold rolling or hand-drawn wire, each the rate of plastic deformation be 5 ~
10%；
6) sample after being cold worked carries out recrystallization annealing under vacuum conditions；Recrystallization annealing temperature is 700 ~ 900 DEG C, the time
It is 0.5 ~ 2 hour, the type of cooling is water quenching, obtains low modulus medical titanium alloy.
2. a kind of low modulus medical titanium alloy according to claim 1, it is characterised in that: in step 3), argon gas used is
High-purity argon.
3. a kind of low modulus medical titanium alloy according to claim 1, it is characterised in that: after step 6) recrystallization annealing,
Sample after annealing is subjected to timeliness under vacuum conditions, aging temp is 200 ~ 400 DEG C, and the time is 0.5 ~ 4 hour, cold
But mode is water quenching.
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| CN107974653B (en) * | 2017-12-01 | 2019-05-21 | 中国航空工业标准件制造有限责任公司 | A kind of underproof optimization method of titanium-niobium alloy part annealing heat-treatment |
| CN111485134B (en) * | 2020-04-29 | 2021-10-01 | 上海理工大学 | Deformation-induced high-modulus medical titanium alloy and preparation method thereof |
| CN112176220A (en) * | 2020-10-23 | 2021-01-05 | 河北工业大学 | High-strength-toughness corrosion-resistant beta-type titanium-zirconium-based alloy and preparation method thereof |
| CN112553552B (en) * | 2020-11-18 | 2021-11-05 | 浙江大学 | Processing technology for improving mechanical property of titanium-zirconium alloy, titanium-zirconium alloy and implant |
| CN112899597B (en) * | 2021-01-25 | 2021-09-28 | 东南大学 | Heat treatment method of two-phase titanium alloy |
| CN115369285A (en) * | 2022-07-11 | 2022-11-22 | 中南大学 | Low-modulus metastable beta titanium alloy, preparation method thereof and metal implant |
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| US8512486B2 (en) * | 2006-04-04 | 2013-08-20 | Daido Tokushuko Kabushiki Kaisha | Beta-type titanium alloy and product thereof |
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