CN117026009A - Ti-Nb-Se shape memory alloy and preparation method and application thereof - Google Patents

Ti-Nb-Se shape memory alloy and preparation method and application thereof Download PDF

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CN117026009A
CN117026009A CN202310967488.4A CN202310967488A CN117026009A CN 117026009 A CN117026009 A CN 117026009A CN 202310967488 A CN202310967488 A CN 202310967488A CN 117026009 A CN117026009 A CN 117026009A
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alloy
shape memory
memory alloy
alloy material
tise
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张德闯
黄俊铭
林建国
邓波
花照林
孙全祥
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Xiangtan University
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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
    • 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
    • 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
    • C22F1/006—Resulting in heat recoverable alloys with a memory effect
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

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Abstract

The invention discloses a Ti-Nb-Se shape memory alloy material and a preparation method thereof, wherein the Ti-Nb-Se shape memory alloy material comprises a Ti-Nb alloy matrix and TiSe dispersed in the Ti-Nb alloy matrix 2 Reinforcing phase composition. The preparation method comprises the steps of firstly smelting to obtain an ingot, homogenizing the ingot to obtain a homogenized blank, hot-rolling the alloy blank to obtain a hot rolled blank, and then carrying out solution annealing treatment on the hot rolled blank to obtain the Ti-Nb-Se shape memory alloy material.

Description

Ti-Nb-Se shape memory alloy and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomedical titanium-based alloy, and particularly relates to a Ti-Nb-Se shape memory alloy material, and a preparation method and application thereof.
Background
With the development of time, the aging problem is emphasized by more and more countries, and the situation of increasingly tense areas brings war and diseases. There is also an increasing demand for artificial replacement of tissues such as bones, teeth, heart stents for patients with bone tissue injuries. Pure titanium and titanium alloy have excellent mechanical properties, such as good fatigue resistance, low elastic modulus relative to other metals, and the like; besides, the biological tissue has good biocompatibility and slight human response after being implanted as a biological tissue. Pure titanium and titanium alloys possess these excellent properties and are therefore useful as materials for medical implants. However, clinical experiments show that the commercial pure titanium has good corrosion resistance in different environments of experimental organisms as artificial replacement tissue, but the pure titanium has the defects of obvious low strength, poor wear resistance and the like when being used as an intramedullary nail and a hip joint, and is easy to cause medical accidents such as fracture and the like when being used as an implant of hard tissue in vivo. The Ti-6Al-4V alloy has strong toughness, excellent corrosion resistance and processability, but the Ti-Al-V alloy still has a plurality of problems in clinical application. The V element has potential toxicity to organism, and can cause malignant tissue reaction of animal, while aluminum element accumulates in organism through aluminum salt to cause cartilage, anemia and nerve flocculation. Meanwhile, the research shows that the natural bone of the human body shows a special hysteresis effect under the condition of bearing the loading-unloading cycle of the compressive stress, has the recoverable strain of approximately 3 percent, and can be considered to have shape memory effect and super elasticity. The Ti-Ni alloy can show mechanical behavior very similar to that of bone tissue, has corrosion resistance and relatively low elastic modulus, and is successfully applied to the fields of dentistry, orthopaedics, plastic surgery and the like. Unfortunately, the potential cytotoxicity and hypersensitive response of Ni ions in Ti-Ni alloys can cause biological lesions upon prolonged implantation. Therefore, to fundamentally solve the problem of Ni ion elution, the most effective method is to select biocompatible elements such as Nb, ta, zr, mo, sn, and develop nickel-free titanium-based shape memory alloy with excellent biocompatibility
Selenium (Se) is widely existing in soil, earth water layer, atmosphere and some animals and plants, and is an important trace element in human body. Selenium can be used as an antioxidant at low standard nutritional doses to support cell survival and growth; and at superscalar high nutritional doses, act as pro-oxidants, inducing redox signaling and cell death. The action mechanism of selenium is realized mainly by various selenases and selenoproteins. Selenium has strong binding force with metal, and can resist toxicity of cadmium to kidney, gonad and central nerve. Selenium is combined with heavy metals such as mercury, lead, tin, thallium and the like in the body to form metalloselenoprotein composition for detoxification and detoxification. Selenium is used as a multifunctional life nutrient, and has the functions of scavenging free radicals, resisting oxidation (50-100 times of VE), enhancing immune function (20-30 times), protecting biological cell membranes, enhancing prostate regulating function, preventing blood coagulation, scavenging cholesterol, having the same functions as insulin, obviously promoting the ability of cells to take sugar, preventing skin aging by blood circulation, reducing cancer inducing property of cancerogenic substances, eliminating abnormal cells mutated in vivo, dividing and growing tissue cancer cells, and the like. Selenium-based materials are considered promising anticancer agents because of their specific targeted inhibition of cancer cells without affecting surrounding healthy tissue.
As shown by the phase diagram, the melting point of Ti is 1668 ℃, the melting point of Nb is 2468 ℃, the melting point of Se is 220 ℃, the boiling point of Se is 685 ℃, the boiling point of the melting point is low, the volatility is high, the melting point of Ti, nb and Se is far different, and therefore the prior art does not adopt smelting and rolling to prepare the Ti-Nb-Se material.
Disclosure of Invention
In view of the shortcomings of the prior art, a first object of the present invention is to provide a Ti-Nb-Se shape memory alloy material. The Ti-Nb-Se shape memory alloy material provided by the invention has excellent mechanical property and good superelastic property, and simultaneously has excellent biocompatibility and antibacterial property.
The second aim of the invention is to provide a preparation method of the Ti-Nb-Se shape memory alloy material, which is simple and controllable and is suitable for large-scale industrial production.
A third object of the present invention is to provide an application of a Ti-Nb-Se shape memory alloy material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a Ti-Nb-Se shape memory alloy material, which comprises the following components in percentage by atom: 26at.% of Nb, 0.1 to 0.9at.% of Se and the balance of Ti.
The Ti-Nb-Se shape memory alloy material provided by the invention is based on Ti-26Nb alloy, ti-26Nb has excellent super elasticity, and after a small amount of Se is doped on the basis, not only the mechanical property and super elasticity are further improved, but also the biocompatibility and antibacterial property are greatly improved.
Of course, the content of Se needs to be controlled effectively, if too small, the effect of improving performance cannot be achieved, if too large, the addition of too much Se will cause uneven smelting components and also affect performance because the solid solubility of Se in Ti-Nb alloy is small.
Preferably, the Ti-Nb-Se shape memory alloy material comprises the following components in percentage by atom: 26at.% of Nb, 0.5 to 0.9at.% of Se and the balance of Ti.
Preferably, the Ti-Nb-Se shape memory alloy material consists of a Ti-Nb alloy matrix and TiSe dispersed in the Ti-Nb alloy matrix 2 Reinforcing phase composition.
The Ti-Nb-Se shape memory alloy material provided by the invention adopts a Ti-Nb alloy matrix, wherein TiSe 2 The strengthening phase is dispersed in the Ti-Nb alloy matrix to strengthen the matrix, and the inventor discovers that the microstructure ensures that the Ti-Nb-Se shape memory alloy material has better mechanical property.
The invention relates to a preparation method of Ti-Nb-Se shape memory alloy material, which wraps TiSe with niobium foil or titanium foil 2 Intermediate alloy powderPlacing in vacuum arc melting furnace, and coating Ti particles on TiSe 2 Covering Nb grains on the Ti grains, smelting to obtain cast ingot, homogenizing the cast ingot to obtain homogenized blank, hot rolling the homogenized blank to obtain hot rolled blank, and solution annealing the hot rolled blank to obtain the Ti-Nb-Se shape memory alloy material.
The preparation method of the invention uses TiSe 2 The intermediate alloy powder is used as Se source, on one hand, intermediate alloy is adopted to realize the uniform distribution of Se in the alloy and avoid the mass loss of Se, the Ti-Nb-Se alloy material conforming to the design components is prepared, on the other hand, crushed crystal grains are recrystallized after annealing treatment, so as to obtain TiSe 2 The reinforced phase is dispersed in the Ti-Nb alloy matrix, so that the Ti-Nb-Se shape memory alloy material with excellent mechanical property, good superelastic property, excellent biocompatibility and antibacterial property is obtained. In practice, the inventors have tried other master alloys, but only using TiSe 2 The master alloy powder has optimal final properties as Se source, since it is eventually made of fine TiSe 2 The reinforcing phase is dispersed in the Ti-Nb alloy matrix.
In the invention, because the melting points of Ti, nb and Se are very different, ti, nb and Se are directly adopted for smelting, and when current is introduced into a vacuum arc smelting furnace, se can be completely volatilized due to the fact that the high temperature directly reaches the melting point 2 The intermediate alloy powder, ti and Nb particles are used as raw materials, and the Ti-Nb-Se alloy material is obtained through smelting, so that the uniform distribution of Se in the alloy can be realized in the smelting process, the mass loss of Se is avoided, the Ti-Nb-Se alloy material conforming to the design components is prepared, and the Ti-Nb-Se alloy material is wrapped by adopting a niobium foil or a titanium foil 2 The intermediate alloy powder can prevent TiSe during smelting 2 Volatilizing the intermediate alloy powder, and coating Ti and Nb grains on TiSe 2 The molten Ti-Nb alloy solution can completely wrap the underlying TiSe during the smelting process on the intermediate alloy powder 2 The intermediate alloy is melted to avoid volatilization,thereby obtaining alloy melt conforming to design components through smelting, then obtaining alloy ingot through casting, then carrying out homogenization treatment on the obtained alloy ingot to eliminate segregation uniform structure, then carrying out hot rolling treatment, further refining coarse dendrites in the structure, eliminating segregation, finally eliminating internal stress through solution annealing treatment, and recrystallizing the alloy to separate out TiSe 2 Reinforcing phase and softening, and thus has good plasticity and strength.
Preferably, the thickness of the niobium foil is 0.05mm-1mm. The inventors have found that the thickness of the niobium foil needs to be effectively controlled, and that too thin a niobium foil results in an underlying TiSe coating 2 The intermediate alloy powder is melted too early, so that the molten metal is not wrapped, the volatilization of Se is increased, the alloy components can be influenced to a certain extent, and the excessive thick niobium foil can be heavier, so that the alloy proportion can be influenced to a certain extent.
In a preferred embodiment, the purity of the Nb foil is greater than or equal to 99.95%.
In a preferred scheme, the purity of the Ti and Nb particles is more than or equal to 99.95 percent.
Preferably, the TiSe 2 The purity of the intermediate alloy powder is more than or equal to 99.95 percent.
The inventors found that using TiSe in powder form 2 The intermediate alloy is used as a raw material, so that the introduced impurities are few, and the purity is higher.
Preferably, the TiSe is wrapped by the niobium foil or the titanium foil 2 The intermediate alloy powder is placed at the bottom of a crucible of a vacuum arc melting furnace, and Ti grains are covered on TiSe 2 Covering Nb grains on Ti grains, closing the furnace door of vacuum arc smelting furnace, and vacuumizing to vacuum degree not higher than 4×10 -3 Pa, filling argon, repeatedly vacuumizing and filling argon for 2-3 times, and opening a tungsten electrode of the vacuum arc melting furnace to initiate arc for melting after the argon is filled finally.
Preferably, the smelting process comprises the following steps: firstly, melting Ti particles and Nb particles by 120-150A current to obtain Ti-Nb metal liquid, and wrapping the underlying TiSe 2 And (3) repeatedly smelting the intermediate alloy powder by increasing the current to 250-350A to obtain an ingot.
The invention adopts a vacuum arc melting furnace, firstly adopts small current, when sparks caused by the small current strike the surface of Nb particles, nb is slowly melted at the moment, and along with the extension of time, the melted Ti-Nb alloy liquid can completely wrap the underlying TiSe 2 Intermediate alloy and make it melt, avoid its volatilization. And then increasing the current and repeatedly smelting to ensure that the two materials are mixed and melted more uniformly.
In the present invention, tiSe is used 2 The invention adopts the vacuum arc melting furnace as the raw materials of the intermediate alloy powder, ti and Nb grains, and can obtain the TiSe which accords with the design components 2 The inventors found that TiSe was critical to alloy ingot casting 2 The melting point of the intermediate alloy powder is 1300 ℃, the difference between the melting point of the intermediate alloy powder and the melting point of Ti and Nb particles is smaller, and simultaneously, a vacuum arc melting furnace is adopted to directly strike the surface of the Nb particles through spark caused by tungsten electrode tip discharge, so that the Nb particles are contacted with current first, thereby melting and forming Ti-Nb alloy liquid which can completely wrap the underlying TiSe 2 Intermediate alloy, and wrapped TiSe by using temperature of alloy liquid 2 The intermediate alloy powder is melted to avoid Se volatilization, so that the current of the vacuum arc melting furnace needs to be effectively controlled, ti and Nb particles cannot be effectively melted slowly and fully if the current is too small, and TiSe can be caused if the current is too large 2 The intermediate alloy powder and Ti grains are simultaneously melted in transition, resulting in evaporation.
Further preferably, the number of times of repeated smelting is 8 to 10 times.
In a preferred scheme, the homogenization treatment temperature is 850-950 ℃ and the homogenization treatment time is 1-2 h.
In the invention, the temperature and time of homogenization treatment need to be effectively controlled, if the temperature and time of homogenization treatment are too high, the recrystallization of crystal grains grows up, if serious, the sample overburning phenomenon is caused, and if the temperature and time are too low, the effect of eliminating segregation cannot be achieved, so that the effect of uniform structure cannot be achieved.
In the actual operation process, the homogenized blank is cut into a plate by adopting a wire, and a thin layer of titanium alloy antioxidation coating is brushed with wool and then hot rolled.
In a preferred scheme, the single-pass pressing amount of the hot rolling is 12% -15%, and the total deformation amount is 80% -85%.
According to the invention, after homogenization, hot rolling is adopted to further refine grains, and the inventor finds that the alloy material of the invention can obtain better mechanical properties compared with an as-cast state by adopting hot rolling, and of course, in the hot rolling process, the hot rolling temperature, single pass reduction and total deformation are required to be effectively controlled, if the sample is easily cracked to generate cracks if the sample is too large, and the deformation is insufficient if the sample is too small, the grain size is uneven, so that the performance of the alloy is reduced. Excessive total deformation can cause portions of the grains to be elongated and broken to form microcracks. If the total deformation is too small, the performance is not improved.
In a preferred scheme, the temperature of the solution annealing treatment is 700-800 ℃, the time of the solution annealing treatment is 10-30 min, and the solution annealing treatment is quickly cooled to room temperature after heat preservation.
After hot rolling, the internal stress is eliminated through solution annealing, the alloy is recrystallized and softened, has good plasticity, is rapidly cooled to room temperature by water, can avoid generating defects, maintains the beta-phase structure, and can improve the hardness of the material.
Of course, the annealing temperature needs to be controlled effectively, and if the annealing temperature is too high, grains formed in the high-temperature beta-phase region are easy to grow. The annealing temperature is too low, alpha phase can appear, residual internal stress is caused, the alloy is not softened enough, and plasticity and super-elasticity are poor.
The invention also provides a titanium-based shape memory alloy material, which is applied to be used as a non-degradable implant biomedical material.
The titanium-based shape memory alloy material provided by the invention has excellent mechanical property and good superelastic property, has excellent biocompatibility and antibacterial property, and has stable alloy performance and no harmful substance dissolution, so that the titanium-based shape memory alloy material can be used as a non-degradable implant biomedical material.
Principle and advantages
The invention uses TiSe 2 Intermediate alloy powder, ti and Nb grains are used as raw materials, and TiSe is obtained through smelting 2 In order to avoid the mass loss of Se and prepare Ti-Nb-Se alloy material conforming to the design components, the invention firstly adopts niobium foil or titanium foil to wrap TiSe 2 The intermediate alloy powder can prevent TiSe during smelting 2 Volatilizing intermediate alloy powder, and wrapping TiSe with niobium foil or titanium foil in the order of low melting point and high melting point 2 The intermediate alloy powder is placed at the bottom of a crucible of a vacuum arc melting furnace, and Ti and Nb grains are covered on TiSe 2 And (3) the upper surface of the intermediate alloy powder. The invention adopts a vacuum arc melting furnace, firstly adopts small current, when sparks caused by the small current strike the surfaces of Ti and Nb particles, ti and Nb are slowly melted at the moment, and the melted alloy liquid can completely wrap the lower TiSe along with the extension of time 2 Intermediate alloy and make it melt, avoid its volatilization. And then increasing the current and repeatedly smelting to ensure that the two materials are mixed and melted more uniformly. The obtained Ti-Nb-Se alloy ingot is subjected to homogenization treatment, coarse dendrites in a structure are thinned, segregation is eliminated, then grains are further thinned through hot rolling, materials are reinforced, finally internal stress is eliminated through annealing treatment, and the alloy is recrystallized and softened and has good plasticity.
The titanium-based shape memory alloy material provided by the invention has excellent mechanical property and good superelastic property, has excellent biocompatibility and antibacterial property, and has stable alloy performance and no harmful substance dissolution, so that the titanium-based shape memory alloy material can be used as a non-degradable implant biomedical material.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a metallographic microstructure of a Ti-Nb-Se alloy before and after as-cast homogenization and after rolling;
FIG. 2 is a graph showing the tensile deformation of Ti-Nb-Se alloys before and after a rolling process;
FIG. 3 is a graph of Ti-Nb-Se6% loading and unloading before and after rolling treatment.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings, in which:
example 1 (Ti-26 Nb-0.1 Se)
99.95% pure Ti, nb grains and 99.95% pure TiSe 2 The intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, is weighed according to the mass ratio of ternary Ti-26Nb-0.1Se alloy, is smelted for 60g at one time and is divided into three smelting pits and TiSe 2 0.1035g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, and firstly, 150A current is used for melting pure Ti and Nb grains and wrapping the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle. And (3) preserving the heat of the melted Ti-26Nb-0.1Se alloy at 900 ℃ for 2 hours for homogenizing annealing, and then cooling the alloy to room temperature quickly by water cooling.
Cutting the homogenized spindle with the size of 40mm into a plate by using a wire, rolling the sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plate reaches 80%, and the Ti-26Nb-0.1Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. Then placing the sample into a vacuum tube furnace for annealing treatment at 800 ℃ for 30min, taking out the sample, and then placing the sample into water for rapid cooling to room temperature. The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Effect of the invention
The relative mass content of Se element in the Ti-26Nb-0.1Se alloy prepared in the example is 0.09 percent by X-ray fluorescence spectrum (XRF), and the rest is Ti and Nb. After rolling and annealing, along with the increase of Se content, tiSe in the alloy 2 The second phase distribution is also more. After the rolling annealing treatment, the tensile mechanical property and the hardness value of the Ti-26Nb-0.1Se alloy are improved, and the martensite transformation induced stress, the tensile ultimate strength (UTS) and the elongation are respectively 200MPa, 450MPa and 29.5 percent. After being pulled to 6%, it was slowly unloaded with a recovery of 55%. The effect of the rolled annealed Ti-26Nb-0.1Se alloy on cell viability was tested in MG63 human bone cells. Cutting the rolled and annealed Ti-26Nb-0.1Se alloy into blocks with the diameter of 7 multiplied by 7mm, then performing sterilization treatment, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is higher than 100%, which indicates that the alloy has cytotoxicity of 0 and complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-0.1Se alloy after rolling annealing is 25.68 percent. The method has a certain inactivated bone cancer rate, meets the requirements of clinical medical biological materials, and has more excellent biomedical value.
Example 2 (Ti-26 Nb-0.5 Se)
99.95% pure Ti, nb grains and 99.95% pure TiSe 2 The intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, is weighed according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, is smelted for 60g at one time and is divided into three smelting pits and TiSe 2 0.5166g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. During smeltingThe current of the vacuum arc furnace is regulated to control the smelting temperature, and the 150A current is used to melt the pure Ti and Nb grains to wrap the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle. And (3) preserving the heat of the melted Ti-26Nb-0.5Se alloy at 900 ℃ for 2 hours for homogenizing annealing, and then cooling the alloy to room temperature quickly by water cooling.
Cutting the homogenized spindle with the size of 40mm into plates by using a linear cutting method, rolling the sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plates reaches 80%, and the Ti-26Nb-0.5Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. Then placing the sample into a vacuum tube furnace for annealing treatment at 800 ℃ for 30min, taking out the sample, and then placing the sample into water for rapid cooling to room temperature. The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Specific data
1. The relative mass content of the Ti-26Nb-0.5Se alloy Se element prepared in the example is 0.45 percent by X-ray fluorescence spectrum (XRF), and the balance is Ti and Nb.
2. FIG. 1 is a metallographic microstructure of a Ti-26Nb-0.5Se alloy after rolling annealing. After rolling and annealing, se content is uniformly distributed, obvious beta-phase structure appears in the microstructure of the alloy, and TiSe is generated 2 The second phase is widely distributed in the matrix.
3. FIG. 2 is a plot of the tensile deformation of a Ti-26Nb alloy and a Ti-26Nb-0.5Se alloy after rolling annealing. After the rolling annealing treatment, the tensile mechanical property and the hardness value of the rolled Ti-26Nb-0.5Se alloy are obviously improved, and the martensite transformation induced stress, the tensile ultimate strength (UTS) and the elongation are 320MPa, 550MPa and 27 percent respectively.
4. FIG. 3 shows a 6% load/unload curve for a Ti-26Nb alloy and a Ti-26Nb-0.5Se alloy after rolling annealing, where the first yield point has a strength of approximately 320MPa and a corresponding deformation of approximately 3.7%. It is slowly unloaded after being pulled to 6%, and the recovery rate is as high as 60%.
5. Cutting the rolled and annealed Ti-26Nb-0.5Se alloy into blocks with the diameter of 7 multiplied by 7mm, then performing sterilization treatment, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is higher than 100%, which indicates that the alloy has cytotoxicity of 0 and complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-0.5Se alloy after rolling annealing is 6.18 percent. The method has a certain inactivated bone cancer rate, meets the requirements of clinical medical biological materials, and has more excellent biomedical value.
Example 3 (Ti-26 Nb-0.9 Se)
99.95% pure Ti, nb grains and 99.95% pure TiSe 2 The intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, is weighed according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, is smelted for 60g at one time and is divided into three smelting pits and TiSe 2 0.9282g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, and firstly, 150A current is used for melting pure Ti and Nb grains and wrapping the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle. And (3) preserving the heat of the melted Ti-26Nb-0.9Se alloy at 900 ℃ for 2 hours for homogenizing annealing, and then cooling the alloy to room temperature quickly by water cooling.
Cutting the homogenized spindle with the size of 40mm into plates by using a linear cutting method, rolling the sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plates reaches 80%, and the Ti-26Nb-0.9Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. Then placing the sample into a vacuum tube furnace for annealing treatment at 800 ℃ for 30min, taking out the sample, and then placing the sample into water for rapid cooling to room temperature. The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Effect of the invention
The relative mass content of Se element in the Ti-26Nb-0.9Se alloy prepared in the example is 0.45 percent by X-ray fluorescence spectrum (XRF), and the balance is Ti and Nb. After rolling and annealing, along with the increase of Se content, tiSe in the alloy 2 The second phase distribution is also more. After the rolling annealing treatment, the tensile mechanical property and the hardness value of the Ti-26Nb-0.9Se alloy are improved, and the martensite transformation induced stress, the tensile ultimate strength (UTS) and the elongation are respectively 410MPa, 570MPa and 17%. It is slowly unloaded after being pulled to 6%, and the recovery rate is as high as 58%. The effect of the rolled annealed Ti-26Nb-0.9Se alloy on cell viability was tested in MG63 human bone cells. Cutting the rolled and annealed Ti-26Nb-0.9Se alloy into blocks with the diameter of 7 multiplied by 7mm, then performing sterilization treatment, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is higher than 100%, which indicates that the alloy has cytotoxicity of 0 and complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-0.9Se alloy after rolling annealing is 2.01 percent. The method has a certain inactivated bone cancer rate, meets the requirements of clinical medical biological materials, and has more excellent biomedical value.
Comparative example 1 (No homogenization treatment after smelting)
99.95% pure Ti, nb grains and 99.95% pure TiSe 2 The intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, is weighed according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, and is smelted for 60g at one time and divided into three smelting stepsPit, tiSe 2 0.5166g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, and firstly, 150A current is used for melting pure Ti and Nb grains and wrapping the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle.
Cutting a spindle with the size of 40mm obtained after smelting into a plate by using a linear cutting method, rolling a sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plate reaches 80%, and the Ti-26Nb-0.9Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. Then placing the sample into a vacuum tube furnace for annealing treatment at 800 ℃ for 30min, taking out the sample, and then placing the sample into water for rapid cooling to room temperature. The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Effect of the invention
The relative mass content of Se element in the Ti-26Nb-0.5Se alloy prepared in the example is 0.45 percent by X-ray fluorescence spectrum (XRF), and the balance is Ti and Nb. As the microstructure of the spindle without homogenization is observed by a metallographic microscope, tiny holes exist in the microstructure, and after rolling annealing, the Se content in the alloy is increased along with the increase of Se 2 The second phase distribution is also more. After the rolling annealing treatment, the tensile mechanical property and the hardness value of the Ti-26Nb-0.5Se alloy are improved, and the martensite transformation induced stress, the tensile ultimate strength (UTS) and the elongation are respectively 300MPa, 500MPa and 19%. It was slowly unloaded after being pulled to 6% with a recovery of 52%. Testing of Rolling anneals in MG63 human bone cellsInfluence of the subsequent Ti-26Nb-0.5Se alloy on cell viability. Cutting the rolled and annealed Ti-26Nb-0.5Se alloy into blocks with the diameter of 7 multiplied by 7mm, then performing sterilization treatment, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is higher than 100%, which indicates that the alloy has cytotoxicity of 0 and complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-0.5Se alloy after rolling annealing is 6.21 percent. Indicating a certain rate of bone cancer inactivation.
Comparative example 2 (no annealing treatment after rolling)
99.95% pure Ti, nb grains and 99.95% pure TiSe 2 The intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, is weighed according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, is smelted for 60g at one time and is divided into three smelting pits and TiSe 2 0.5166g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, and firstly, 150A current is used for melting pure Ti and Nb grains and wrapping the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle. And (3) preserving the heat of the melted Ti-26Nb-0.5Se alloy at 900 ℃ for 2 hours for homogenizing annealing, and then cooling the alloy to room temperature quickly by water cooling.
Cutting the homogenized spindle with the size of 40mm into a plate by using a linear cutting method, rolling the sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plate reaches 80%, and the Ti-26Nb-0.5Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. . The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Effect of the invention
The relative mass content of Se element in the Ti-26Nb-0.1Se alloy prepared in the example is 0.44 percent by X-ray fluorescence spectrum (XRF), and the balance is Ti and Nb. After rolling and annealing, along with the increase of Se content, tiSe in the alloy 2 The second phase distribution is also more. As the annealing treatment is not carried out, the tensile mechanical property and the hardness value of the Ti-26Nb-0.5Se alloy are improved, but the plasticity is obviously reduced, and the martensite transformation induced stress, the tensile ultimate strength (UTS) and the elongation are respectively 450MPa, 650MPa and 14%. It is slowly unloaded after being pulled to 6%, and the recovery rate is as high as 70%. The effect of the rolled annealed Ti-26Nb-0.5Se alloy on cell viability was tested in MG63 human bone cells. Cutting rolled Ti-26Nb-0.5Se alloy into blocks with the diameter of 7 multiplied by 7mm, then sterilizing, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is higher than 100%, which indicates that the alloy has cytotoxicity of 0 and complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-0.5Se alloy after rolling annealing is 5.98 percent. Indicating a certain rate of bone cancer inactivation.
Comparative example 3 (increase in Se content)
99.95% pure Ti, nb grains and 99.95% pure TiSe 2 The intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, is weighed according to the mass ratio of ternary Ti-Nb-1.5 percent Se alloy, is smelted for 60g at one time and is divided into three smelting pits and TiSe 2 2.0127g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, firstly, the current of 150A is used for smelting pure Ti and Nb particles,wrapping the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle.
Cutting a spindle with the size of 40mm obtained after smelting into a plate by using a linear cutting method, rolling a sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plate reaches 80%, and the Ti-26Nb-1.5Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. Then placing the sample into a vacuum tube furnace for annealing treatment at 800 ℃ for 30min, taking out the sample, and then placing the sample into water for rapid cooling to room temperature. The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Effect of the invention
The relative mass content of Se element in the Ti-26Nb-1.5Se alloy prepared in the example is 1.39 percent by X-ray fluorescence spectrum (XRF), and the balance is Ti and Nb. After rolling and annealing, along with the increase of Se content, tiSe in the alloy 2 The second phase distribution is also more. After the rolling annealing treatment, the tensile mechanical property and the hardness value of the Ti-26Nb-1.5Se alloy are improved, the plasticity is obviously reduced, and the Ultimate Tensile Strength (UTS) and the elongation are 600MPa and 9.5 percent respectively. The effect of the rolled annealed Ti-26Nb-1.5Se alloy on cell viability was tested in MG63 human bone cells. Cutting rolled Ti-26Nb-1.5Se alloy into blocks with the diameter of 7 multiplied by 7mm, then sterilizing, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is lower than 100%, which indicates that the alloy is toxic to cells and does not have complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-1.5Se alloy after rolling annealing is 0.96 percent. Description has a certain Is used for inactivating bone cancer rate.
Comparative example 4 (direct starting from Ti, nb and Se powders)
The method comprises the steps of weighing Ti with the purity of 99.95%, nb particles and Se powder with the purity of 99.95% according to the mass ratio of ternary Ti-26Nb-1.5Se alloy, smelting 60g at a time, dividing the smelting into three furnaces, and weighing 0,9058g of Se powder in each furnace. Smelting in a vacuum arc furnace under the protection of argon, and putting Se powder into the vacuum arc furnace according to the sequence of low melting point and high melting point before smelting, and covering Ti particles and Nb particles on the Se powder. Immediately, current is conducted, and when pure Ti and Nb particles on the surface layer are melted by 150A current, the phenomenon of serious powder liquid splashing appears, volatilization is serious, a cavity is seriously polluted, and the experiment cannot be carried out. After the current is turned off, the furnace door is opened after the furnace is cooled, a layer of Se powder is filled in the cavity, and dark green powder appears at the bottom of the crucible. The experimental phenomenon shows that because the melting points of Ti, nb and Se are too different and Ti and Nb particles are not melted when Se is volatilized, the smelting can not be directly carried out by taking Ti, nb particles and Se powder as raw materials, and the experiment can not be carried out.
Comparative example 5 (Rolling by suction casting)
99.95% pure Ti, nb grains and 99.95% pure TiSe 2 Intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, weighing according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, smelting 10g at one time, weighing 0.0861g of TiSe2 powder, wherein when Nb particles are weighed, wrapping TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, firstly, 100A current is used for melting pure Ti and Nb grains, and the lower TiSe is wrapped 2 The powder was then repeatedly smelted 8 times by increasing the current to 200A. And after smelting, 10g of Ti-26Nb-0.5Se alloy is put into a water-cooled copper die for rapid cooling suction casting, so that component segregation is further avoided, and the flaky Ti-26Nb-0.5Se alloy with the thickness of 6mm and 12mm and 2mm is obtained. It was found to break directly into two parts when it was removed from the mouldAfter multiple tests, the alloy subjected to suction casting is found to be very brittle, and the next test cannot be performed.
Comparative example 6 (Cold Rolling Process)
Ti with purity of 99.95%, nb particles, tiSe2 intermediate alloy powder with purity of 99.95%, nb foil with purity of 99.95% and thickness of 0.1mm, weighing according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, smelting 60g at a time, and dividing into three smelting pits and TiSe 2 0.5166g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, and firstly, 150A current is used for melting pure Ti and Nb grains and wrapping the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle. And (3) preserving the heat of the melted Ti-26Nb-0.5Se alloy at 900 ℃ for 2 hours for homogenizing annealing, and then cooling the alloy to room temperature quickly by water cooling.
And (3) cutting the homogenized spindle with the size of 40mm into a plate by using a linear cutting method, rolling the sample on a small two-roll mill, wherein the rolling deformation process is cold rolling, the reduction of each pass is 5%, and when the deformation of the plate reaches 20%, the plate is found to have cracks, so that the next experiment cannot be performed.
Comparative example 7 (annealing temperature was too high)
Ti with purity of 99.95%, nb particles, tiSe2 intermediate alloy powder with purity of 99.95%, nb foil with purity of 99.95% and thickness of 0.1mm, weighing according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, smelting 60g at a time, and dividing into three smelting pits and TiSe 2 0.5166g of powder is weighed, wherein when Nb particles are weighed, the coating of TiSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and coating the coated TiSe before smelting in the order of low melting point and high melting point 2 The powder and Ti pellets are placed into a crucible tank. The current of the vacuum arc furnace is regulated to control the smelting temperature during smelting, 15 is firstly usedThe current of 0A melts the pure Ti and Nb grains and wraps the underlying TiSe 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle. And (3) preserving the heat of the melted Ti-26Nb-0.5Se alloy at 900 ℃ for 2 hours for homogenizing annealing, and then cooling the alloy to room temperature quickly by water cooling.
Cutting the homogenized spindle with the size of 40mm into plates by using a linear cutting method, rolling the sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plates reaches 80%, and the Ti-26Nb-0.5Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. Then placing the sample into a vacuum tube furnace for annealing treatment at 1000 ℃ for 30min, taking out the sample, and then placing the sample into water for rapid cooling to room temperature. The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Effect of the invention
The relative mass content of Se element in the Ti-26Nb-0.5Se alloy prepared in the example is 0.38 percent by X-ray fluorescence spectrum (XRF), and the balance is Ti and Nb. After annealing at 1000 ℃ for 30min, the sample is subjected to overburning phenomenon, and after rolling annealing treatment, the tensile mechanical property and hardness value of the Ti-26Nb-0.5Se alloy are improved, and the double yield phenomenon disappears, the tensile ultimate strength (UTS) and the elongation are 520MPa and 17 percent respectively. It was slowly unloaded after being pulled to 6% with a recovery of 50. The effect of the rolled annealed Ti-26Nb-0.9Se alloy on cell viability was tested in MG63 human bone cells. Cutting the rolled and annealed Ti-26Nb-0.5Se alloy into blocks with the diameter of 7 multiplied by 7mm, then performing sterilization treatment, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is higher than 100%, which indicates that the alloy has cytotoxicity of 0 and complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-0.5Se alloy after rolling annealing is 6.11 percent.
Comparative example 8 (using NbSe 2 As a Se source
Ti with purity of 99.95%, nb grains and NbSe with purity of 99.95% 2 The intermediate alloy powder, nb foil with the purity of 99.95 percent and the thickness of 0.1mm, is weighed according to the mass ratio of ternary Ti-26Nb-0.5Se alloy, is smelted for 60g at one time and is divided into three smelting pits, nbSe 2 0.5382g of powder is weighed, wherein when Nb particles are weighed, the coating NbSe needs to be removed 2 Nb foil mass of the powder. Smelting in vacuum arc furnace under the protection of argon, and wrapping NbSe according to the sequence of low melting point and high melting point before smelting 2 The powder and Ti pellets are placed into a crucible tank. The current of a vacuum arc furnace is regulated to control the smelting temperature during smelting, firstly, the current of 150A is used for smelting pure Ti and Nb grains, and the lower NbSe is wrapped 2 The powder was then increased to 300A and repeatedly smelted 8 times, and finally 3 20 g samples were fused into a finished spindle. And (3) preserving the heat of the melted Ti-26Nb-0.5Se alloy at 900 ℃ for 2 hours for homogenizing annealing, and then cooling the alloy to room temperature quickly by water cooling.
Cutting the homogenized spindle with the size of 40mm into a plate by using a linear cutting method, rolling the sample on a small two-roll mill, wherein the rolling deformation process is 800 degrees of hot rolling, the pressing amount of each pass is 16%, rolling is finished when the deformation amount of the plate reaches 80%, and the Ti-26Nb-0.5Se alloy with the final thickness of about 1.5mm is obtained after 5 times of repeated rolling. . The pattern is cut into a stretched sample with the gauge length of 8mm by wire cutting, the wire cutting corrosive liquid on the surface of the sample is ground during stretching, and the speed in the stretching process is controlled to be 0.08mm/min. In the process of cyclic loading and unloading, the loading rate is kept to be uniformly controlled at 0.08mm/min, and the unloading rate is controlled at 0.002KN/s.
Effect of the invention
The relative mass content of Se element in the Ti-26Nb-0.1Se alloy prepared in the example is 0.45 percent by X-ray fluorescence spectrum (XRF), and the balance is Ti and Nb. After rolling annealing, the second phase distribution of NbSe2 in the alloy is more along with the increase of Se content. Due to no warpAfter annealing treatment, the tensile mechanical property and the hardness value of the Ti-26Nb-0.5Se alloy are improved, but the plasticity is obviously reduced, and the martensite transformation induced stress, the tensile ultimate strength (UTS) and the elongation are respectively 300MPa, 520MPa and 22%. It is slowly unloaded after being pulled to 6%, and the recovery rate is as high as 67%. It can be seen that NbSe 2 As a Se source, relative to the use of TiSe 2 The mechanical properties of the alloy are reduced.
The effect of the rolled annealed Ti-26Nb-0.5Se alloy on cell viability was tested in MG63 human bone cells. Cutting rolled Ti-26Nb-0.5Se alloy into blocks with the diameter of 7 multiplied by 7mm, then sterilizing, directly culturing MG63 cells on the surface of the alloy, culturing for 4 days, and detecting the cell viability of the surface of the alloy. The detection result shows that the cell activity is higher than 100%, which indicates that the alloy has cytotoxicity of 0 and complete biocompatibility. In the platelet-derived plasma (PPP) of mice containing bone cancer cells, the survival rate of the bone cancer cells inactivated by the Ti-26Nb-0.5Se alloy after rolling annealing is 5.98 percent. Indicating a certain rate of bone cancer inactivation.

Claims (10)

1. A Ti-Nb-Se shape memory alloy material characterized in that: the Ti-Nb-Se shape memory alloy material comprises the following components in percentage by atom: 26at.% of Nb, 0.1 to 0.9at.% of Se0.1 and the balance of Ti.
2. The Ti-Nb-Se shape memory alloy material according to claim 1, wherein: the Ti-Nb-Se shape memory alloy material comprises the following components in percentage by atom: 26at.% of Nb, 0.5 to 0.9at.% of Se and the balance of Ti.
3. A Ti-Nb-Se shape memory alloy material according to claim 1 or 2, wherein: the Ti-Nb-Se shape memory alloy material consists of a Ti-Nb alloy matrix and TiSe dispersed in the Ti-Nb alloy matrix 2 Reinforcing phase composition.
4. A Ti-Nb-Se shape memory as in any one of claims 1-3The preparation method of the memory alloy material is characterized by comprising the following steps: wrapping TiSe with niobium foil or titanium foil 2 The intermediate alloy powder is placed in a vacuum arc melting furnace, and then Ti grains are covered on TiSe 2 Covering Nb grains on the Ti grains, smelting to obtain cast ingot, homogenizing the cast ingot to obtain homogenized blank, hot rolling the homogenized blank to obtain hot rolled blank, and solution annealing the hot rolled blank to obtain the Ti-Nb-Se shape memory alloy material.
5. The method for preparing a Ti-Nb-Se shape memory alloy material in accordance with claim 4, wherein: the thickness of the niobium foil is 0.05mm-1mm;
the purity of the Nb foil is more than or equal to 99.95 percent;
the purity of Ti and Nb particles is more than or equal to 99.95 percent;
the TiSe 2 The purity of the intermediate alloy powder is more than or equal to 99.95 percent.
6. The method for preparing a Ti-Nb-Se shape memory alloy material in accordance with claim 4, wherein: the smelting process comprises the following steps: firstly melting Ti particles and Nb particles by using 120-150A of current to obtain Ti-Nb metal liquid, and then increasing the current to 250-350A for repeated smelting to obtain cast ingots; the number of times of repeated smelting is 8-10.
7. The method for preparing a Ti-Nb-Se shape memory alloy material in accordance with claim 4, wherein: the homogenization treatment temperature is 850-950 ℃, and the homogenization treatment time is 1-2 h.
8. The method for preparing a Ti-Nb-Se shape memory alloy material in accordance with claim 4, wherein: the single-pass pressing amount of the hot rolling is 12% -15%, and the total deformation amount is 80% -85%.
9. The method for preparing a Ti-Nb-Se shape memory alloy material in accordance with claim 4, wherein: the temperature of the solution annealing treatment is 700-800 ℃, the time of the solution annealing treatment is 10-30 min, and the solution annealing treatment is quickly cooled to room temperature after heat preservation.
10. A titanium-based shape memory alloy material according to any one of claims 1 to 3, characterized in that: the titanium-based shape memory alloy material is applied to a non-degradable implant biomedical material.
CN202310967488.4A 2023-08-03 2023-08-03 Ti-Nb-Se shape memory alloy and preparation method and application thereof Pending CN117026009A (en)

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