CN102899528A - Biomedical beta-titanium alloy material and preparation method - Google Patents

Abstract

The invention relates to a biomedical β-titanium alloy material and a preparation method, and belongs to the technical field of preparation of titanium alloy materials with high niobium content. The composition range of the alloy is (30-40%) Nb-(5-15%) Zr-(1-10%) Sn-(0.1-0.3%) O in mass percentage, and the balance is Ti. The titanium alloy has good comprehensive properties, and the strength and elastic modulus of the alloy can be adjusted through different heat treatment processes. The elastic modulus E of the alloy is 40-68GPa, the yield strength _σ0.2 is 580-800MPa, the tensile strength _σb is 750-1120MPa, the elongation ε is 12-48%, and the reduction of area is 36-65%. . The titanium alloy does not contain toxic elements, has excellent corrosion resistance and biocompatibility, good cold working performance, and can be cold rolled with large deformation. The titanium alloy has a wide range of uses, not only can be used to make oral repair, artificial bone, artificial joints and other tissue repair or replacement materials for the human body, but also can be used to make sports and industrial equipment.

Description

A kind of biomedical β-titanium alloy material and its preparation method

technical field

The invention relates to a biomedical β-titanium alloy material and a preparation method thereof, in particular to a biomedical β-titanium alloy material with high niobium content and a preparation method thereof, belonging to the technical field of titanium alloy material preparation.

Background technique

Compared with traditional medical metal materials such as stainless steel and cobalt-chromium-molybdenum alloys, titanium and titanium alloys have gradually become the most important medical materials for orthopedics, implants, and oral restorations due to their good comprehensive mechanical properties, corrosion resistance, and excellent biocompatibility. material of choice in the field.

The development of biomedical titanium and titanium alloys can be divided into three eras. The first era is represented by pure titanium (α type) and Ti-6A1-4V (α+β type). In the 1950s, people began to use pure titanium to manufacture bone plates and screws, which were used clinically as orthopedic internal fixation materials. Although pure titanium has good corrosion resistance and biocompatibility in physiological environments, its low strength and poor wear resistance limit its application in large load-bearing parts. In contrast, Ti-6A1-4V has higher strength and better processing properties. This alloy was originally designed for aerospace applications and was widely used as a surgical implant material and repair material in the late 1970s, such as hip joints, knee joints, etc. At the same time, Ti-3A1-2.5V is also clinically used as a replacement material for femur and tibia. However, this type of alloy contains two elements V and A1. V is easy to accumulate in bones, liver, kidney, spleen and other organs, and has strong cytotoxicity. In addition, Al element also has potential toxicity. Long-term implantation will cause osteomalacia, symptoms such as anemia and nervous disorders, and this kind of alloy has relatively poor corrosion resistance and high elastic modulus (~110GPa), which is relatively high compared to the elastic modulus of human bone (10~40GPa). The mismatch of the elastic modulus between the implants will prevent the load from being well transmitted from the implant to the adjacent bone tissue, and the phenomenon of "stress shielding" will appear, which will lead to bone resorption around the implant, and eventually cause the implant to loosen or break, resulting in Implant failed. The second era (the mid-1980s) was represented by the (α+β) type Ti-6A1-7Nb and Ti-5Al-2.5Fe alloys successively developed by Switzerland and Germany. This kind of alloy replaces the toxic element V with non-toxic elements Nb and Fe, which eliminates the toxic and side effects of V elements on the human body and improves the strength. However, it still contains Al element, and its elastic modulus is about 105GPa, which is still higher than that of human bone. Therefore, the development and research of new high-strength medical titanium alloys containing non-toxic elements, better biocompatibility, and lower elastic modulus to meet clinical requirements for implants has become the main development of the third-generation medical titanium alloy materials. Target. In the early 1990s, the United States and Japan began to use non-toxic elements such as Nb, Ta, Zr, Mo and Sn to replace V and A1, and developed a series of non-toxic, low elastic modulus medical β-type titanium alloys. The alloys developed in the United States mainly include: Ti-13Nb-13Zr, Ti-12Mo-6Zr-2Fe (TMZF), Ti-15Mo and Ti-35Nb-5Ta-7Zr (TNTZ), etc. The alloys developed in Japan mainly include: Ti-29Nb-13Ta-4.6Zr, Ti-15Zr-4Nb-2Ta-0.2Pd and Ti-15Sn-4Nb-2Ta-0.2Pd. Compared with the first-generation and second-generation medical titanium alloys, the corrosion resistance and biocompatibility of this new type of β-type titanium alloy have been significantly improved, and the elastic modulus has decreased by 30-50GPa, about 55-85GPa within range. Although the elastic modulus of Ti-35Nb-5Ta-7Zr alloy can be reduced to 55GPa, the strength of the alloy is less than 600MPa at this time. And the alloy contains a large amount of refractory metals such as Nb and Ta, especially the melting point of Ta is as high as 2996°C and the density is as high as 16.68g/cm ³ , which brings great difficulties to smelting and processing, and the price of Ta is relatively expensive, so Increased material cost.

my country started relatively late in the research and development of medical titanium alloy materials. In 1972, it began to engage in the research and application of titanium and titanium alloys in medicine, especially in orthopedic surgery. In the 1980s, Ti-Ni functional materials were successfully developed. "During the period, Ti-5Al-2.5Fe and Ti-6A1-7Nb were imitated, and Ti-2.5Al-2.5Mo-2.5Zr (TAMZ) alloy was developed. During the "Tenth Five-Year Plan", the development of β-type titanium alloys began. Among them, the most representative ones are Ti-24Nb-4Zr-7.9Sn (Ti2448) designed and developed by Institute of Metals, Chinese Academy of Sciences and Ti-(15～25)Nb-(3)Mo-(3～5) developed by Northwest Institute of Nonferrous Metals. )Zr (TLE) and Ti-(15~25)Nb-(3~6)Mo-(3~5)Zr-(1~2)Sn(TLM)β-type titanium alloys. The strength of TLM and TLE alloys is 580-1000MPa, and the elastic modulus is between 50-90GPa. Compared with human bone, the elastic modulus is still higher. Ti2448 alloy has a low elastic modulus and good elasticity, and is more suitable for making elastic bone plates and dynamic fixators. Research and development of a new type of β-type titanium alloy biomedical material with adjustable modulus, high strength and multi-functionality and supporting processing technology is an important development direction of medical titanium alloy in the future.

Contents of the invention

Aiming at the shortcomings of the existing biomedical titanium alloys, which have a high elastic modulus, contain toxic elements, and have single uses, the present invention provides a high niobium content with an elastic modulus closer to the elastic modulus of human bones and without toxic elements. Biomedical β-titanium alloy material and preparation method thereof.

A kind of biomedical β-titanium alloy material of the present invention, its alloy composition range is counted as:

Nb 30～40%,

Zr 5～15%,

Sn 1～10%,

O 0.1-0.3%, the balance is Ti, and the mass percent sum of each component is 100%.

The preparation method of a kind of biomedical β-titanium alloy material of the present invention comprises the following steps:

Step 1: Ingredients

Calculated according to the mass percentage of each component: (30-40%) Nb-(5-15%) Zr-(1-10%) Sn-(0.1-0.3%) O, the balance is Ti for batching;

Step 2: Alloy Preparation

The ingredients prepared according to the designed alloy composition are pressed into electrodes on a hydraulic press, and then the electrodes are put into a vacuum consumable electric arc furnace for smelting 2-3 times, cast ingots, and cooled to room temperature to obtain biomedical β-titanium alloys Ingot; the vacuum degree in the furnace is greater than 1.33×10 ^-2 Pa during smelting;

The preparation method of a biomedical β-titanium alloy material of the present invention, Ti is added in the form of zero-level sponge Ti and TiO ₂ , Zr is added in the form of 99.9% sponge Zr, high melting point element Nb, volatile element Sn in the form of Ti-Nb and Ti-Sn are added in the form of master alloy, and the content of oxygen in the alloy is controlled by the content of _TiO2 .

The invention discloses a method for preparing a biomedical β-titanium alloy material. In step 2, the alloy melting temperature is 1600-1700° C., and the melting time is 30-60 minutes.

The invention discloses a method for preparing a biomedical β-titanium alloy material. The biomedical β-titanium alloy ingot is placed in a vacuum furnace with an Ar atmosphere for homogenization annealing. The homogenization annealing temperature is 900-1000° C. and the time is 8-12 Hour.

The invention discloses a method for preparing a biomedical β-titanium alloy material. The surface of the biomedical β-titanium alloy ingot after homogenization annealing is brushed with a layer of high-temperature protective coating, and after natural air drying, it is kept in an electric resistance furnace at 800-900°C for 60 -90min, and then open forging to obtain a forged billet; the forged billet is prepared into a plate by hot rolling or cold rolling; the final forging temperature is controlled above 800°C.

The invention discloses a method for preparing a biomedical β-titanium alloy material. Before hot rolling, a layer of high-temperature protective paint is brushed on the surface of the forged billet. The hot rolling temperature is 800-900°C, the holding time is 1-2 hours, and the hot rolling The total deformation is 60-70%.

A preparation method of a biomedical β-titanium alloy material according to the invention, the total deformation of cold rolling is 30%-80%; the surface of the cold-rolled plate is brushed with a layer of high-temperature protective coating, and solution treatment is carried out at 800-900°C for 60- Water quenching after 90 minutes, aging treatment at 400-600°C for 10 minutes to 5 hours, and then water cooling.

The invention discloses a method for preparing a biomedical β-titanium alloy material, wherein the high-temperature protective coating is aluminum oxide or boron nitride.

The invention discloses a method for preparing a biomedical β-titanium alloy material. The elastic modulus of the prepared biomedical β-titanium alloy material is E=40～68GPa, the yield strength is _σ0.2 =580～815MPa, and the tensile strength is σ _b =750~1075MPa, elongation ε=12~48%, reduction of area: 36~65%.

The elastic modulus E=40～68GPa of the β-titanium alloy material prepared by the present invention, the yield strength σ _0.2 =580～815MPa, the tensile strength _σb =750～1075MPa, the elongation ε=12～48%, and the section shrinkage Ratio: 36-65%, its elastic modulus is closer to that of human bone, and its strength is higher than that of TLM and TLE alloys.

The alloy of the present invention selects non-toxic elements Ti, Nb, Zr and Sn. The alloying effect of Nb, Zr and Sn elements in Ti is to form a metastable β-type titanium alloy, so that different microstructures can be obtained through different processing and heat treatment processes to control the properties of the alloy, such as strength and elasticity. modulus etc.

Compared with the alloys developed by Europe, America, Institute of Metals, Chinese Academy of Sciences, and Northwest Institute of Nonferrous Metals, the present invention increases the Nb content of the alloy to 30-40%, in order to obtain Ti-Nb solid solution with greater supersaturation. The Ti-based continuous solid solution is a replacement solid solution, and the increase in the content of solute components increases the lattice distortion, which is beneficial to reduce the elastic modulus of the alloy and improve the strength of the alloy through subsequent aging treatment; the purpose of increasing the content of Zr is the same as that of Nb; Replacing Ta with Sn not only reduces the cost, but also reduces the content of Sn, which will reduce the tendency of non-equilibrium phase in the ingot; increase the content of O, and form an interstitial solid solution with titanium, which can further stabilize the β phase and have a body-centered cubic structure. The β phase of the alloy is more easily deformed, and the atomic clusters formed by O and Zr can hinder dislocation proliferation and increase the cold deformation ability of the alloy to achieve large deformation cold working.

Description of drawings

Accompanying drawing 1 is the X-ray diffraction spectrum of the alloy prepared in Example 1 after 900°C homogenization annealing and quenching.

It can be seen from Figure 1 that the alloy is mainly composed of β-phase with body-centered cubic structure.

Detailed ways

In order to make the object, technical scheme and advantages of the present invention clearer, the embodiment of the present invention will be further described in detail below. In the examples of the present invention, the method for testing the microstructure and performance of the alloy is:

Use DSC to measure the phase transition temperature of the alloy;

Using XRD to measure the phase structure;

The microstructure of the alloy was observed by metallographic microscope, scanning electron microscope and transmission electron microscope.

Finally, the tensile mechanical properties and elastic modulus were tested by MTS universal tensile testing machine.

Example 1:

1. Ingredients: Ti-36Nb-10Zr-2Sn-0.2O alloy, in which Ti is sponge titanium, Zr is sponge zirconium, high melting point element Nb and volatile element Sn are all in the form of Ti-52Nb and Ti-80Sn master alloys respectively To add, the content of O is controlled by the content of oxygen in the sponge Ti. Ingredients are formulated according to the mass percentage of the alloy composition.

2. Smelting: The prepared raw materials are pressed into electrodes on a hydraulic press, and smelted twice in a vacuum consumable electric arc furnace. Before each smelting, the vacuum degree is not lower than 10 ^-2 Pa to obtain alloy ingots. After sufficient cooling, samples were taken for differential thermal analysis and metallographic analysis, and the β→α phase transition temperature of the alloy was measured, and chemical methods were used to analyze whether there was composition segregation in the ingot. Then perform homogenization annealing (with Ar gas protection) in a vacuum furnace, the homogenization temperature is 900°C, and the time is 12h. The ingot is then skinned to remove the outer oxide layer.

3. Blank forging: Brush the surface of the ingot with a layer of high-temperature protective paint before forging, and after natural air drying, heat it in a resistance furnace at 900°C for 90 minutes, then carry out blank forging on a free forging machine, and the final forging temperature is controlled at 800 ℃ or more. Obtain a slab of 500mm × 350mm × 50mm, and after the slab is cooled, it is subjected to surface grinding. Use a wire cutting machine to cut the slab into one slab with a size of 100mm×350mm×50mm and two slabs with a size of 200mm×350mm×50mm, and keep the slab with a size of 100mm×350mm×50mm for microstructure and mechanical properties Analysis, the obtained data are shown in Table 1. The other two surfaces are painted with a high-temperature protective coating, air-dried naturally, and kept for further hot-rolling or cold-rolling treatment.

4. Hot rolling: One of the 200mm × 350mm × 50mm forging blanks is annealed at 850°C/60min in a resistance furnace, and then hot rolled immediately, the rolling direction is parallel to the 200mm length direction, without intermediate annealing, rolling 6 After one pass, a plate with a thickness of 20mm is obtained. After the hot-rolled sheet was cut, the microstructure and mechanical properties were analyzed, and the obtained data are shown in Table 1.

5. Cold rolling: Cold rolling another piece of 200mm×350mm×50mm forging billet without intermediate annealing treatment until the final thickness is 10mm and the total deformation is 80%. Then the cold-rolled sheet was cut, and a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 1. The rest is used for subsequent solution heat treatment.

6. Solution heat treatment: The cold-rolled sheet is subjected to solution treatment in a box-type resistance furnace, the solution temperature is 800-830°C, the holding time is 0.5-1.5h, and water quenching. After cutting, a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 1. The rest is used for the subsequent aging heat treatment.

7. Aging heat treatment: Artificial aging is carried out in a box-type resistance furnace. Three different aging systems are selected as follows to investigate the effects of aging temperature and aging time on the microstructure and properties of the alloy. The obtained data are also shown in Table 1.

a) The aging temperature is 400°C, the holding time is 10min, 1h, 5h, water quenching.

b) The aging temperature is 500°C, the aging time is 10min, 1h, 5h, water quenching.

c) The aging temperature is 600°C, the aging time is 10min, 1h, 5h, water quenching.

Example 2:

1. Ingredients: Ti-36Nb-10Zr-5Sn-0.3O alloy, in which Ti is sponge titanium, Zr is sponge zirconium, high melting point element Nb and volatile element Sn are all in the form of Ti-52Nb and Ti-80Sn master alloys respectively To add, the content of O is controlled by the content of oxygen in the sponge Ti. Ingredients are formulated according to the mass percentage of the alloy composition.

2. Smelting: The prepared raw materials are pressed into electrodes on a hydraulic press, and smelted twice in a vacuum consumable electric arc furnace. Before each smelting, the vacuum degree is not lower than 10 ^-2 Pa to obtain alloy ingots. After sufficient cooling, samples were taken for differential thermal analysis and metallographic analysis, and the β→α phase transition temperature of the alloy was measured, and chemical methods were used to analyze whether there was composition segregation in the ingot. Then perform homogenization annealing (with Ar gas protection) in a vacuum furnace, the homogenization temperature is 950°C, and the time is 12h. The ingot is then skinned to remove the outer oxide layer.

3. Blank forging: Brush the surface of the ingot with a layer of high-temperature protective paint before forging, and after natural air drying, heat it in a resistance furnace at 900°C for 90 minutes, then carry out blank forging on a free forging machine, and the final forging temperature is controlled at 800 ℃ or more. A slab of 400mm×250mm×40mm is obtained, and the surface of the slab is ground after it is cooled. Use a wire cutting machine to cut the slab into one slab with a size of 100mm×250mm×40mm and two slabs with a size of 200mm×250mm×40mm, and keep the slab with a size of 200mm×250mm×40mm for microstructure and mechanical properties Analysis, the obtained data are shown in Table 2. The other two surfaces are painted with a high-temperature protective coating, air-dried naturally, and kept for further hot-rolling or cold-rolling treatment.

4. Hot rolling: One of the 200mm×250mm×40mm forging blanks is annealed at 850°C/60min in a resistance furnace, and then hot rolled immediately, the rolling direction is parallel to the 200mm length direction, no intermediate annealing, rolling 5 After one pass, a plate with a thickness of 20 mm is obtained. After the hot-rolled plate was cut, the microstructure and mechanical properties were analyzed, and the obtained data are shown in Table 2.

5. Cold rolling: Cold rolling another piece of 200mm×250mm×40mm forging billet without intermediate annealing treatment until the final thickness is 10mm and the total deformation is 75%. Then the cold-rolled sheet was cut, and a part of the sample was taken for analysis of microstructure and mechanical properties. The obtained data are also shown in Table 2. The rest is used for subsequent solution heat treatment.

6. Solution heat treatment: The cold-rolled sheet is subjected to solution treatment in a box-type resistance furnace, the solution temperature is 820-850°C, the holding time is 0.5-1.5h, and water quenched. After cutting, a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 2. The rest is used for the subsequent aging heat treatment.

7. Aging heat treatment: Artificial aging is carried out in a box-type resistance furnace. Three different aging systems are selected as follows to investigate the effects of aging temperature and aging time on the microstructure and properties of the alloy. The obtained data are also shown in Table 2.

a) The aging temperature is 400°C, the holding time is 10min, 1h, 5h, water quenching.

b) The aging temperature is 500°C, the aging time is 10min, 1h, 5h, water quenching.

c) The aging temperature is 600°C, the aging time is 10min, 1h, 5h, water quenching.

Example 3:

1. Ingredients: Ti-35Nb-10Zr-8Sn-0.2O alloy, in which Ti is sponge titanium, Zr is sponge zirconium, high melting point element Nb and volatile element Sn are all in the form of Ti-52Nb and Ti-80Sn master alloys respectively To add, the content of O is controlled by the content of oxygen in the sponge Ti. Ingredients are formulated according to the mass percentage of the alloy composition.

2. Smelting: The prepared raw materials are pressed into electrodes on a hydraulic press, and smelted twice in a vacuum consumable electric arc furnace. Before each smelting, the vacuum degree is not lower than 10 ^-2 Pa to obtain alloy ingots. After sufficient cooling, samples were taken for differential thermal analysis and metallographic analysis, and the β→α phase transition temperature of the alloy was measured, and chemical methods were used to analyze whether there was composition segregation in the ingot. Then perform homogenization annealing (with Ar gas protection) in a vacuum furnace, the homogenization temperature is 1000°C, and the time is 12h. The ingot is then skinned to remove the outer oxide layer.

3. Blank forging: Brush the surface of the ingot with a layer of high-temperature protective paint before forging, and after natural air drying, heat it in a resistance furnace at 900°C for 90 minutes, then carry out blank forging on a free forging machine, and the final forging temperature is controlled at 800 ℃ or more. A slab of 400mm×250mm×40mm is obtained, and the surface of the slab is ground after it is cooled. Use a wire cutting machine to cut the slab into one slab with a size of 100mm×250mm×40mm and two slabs with a size of 200mm×250mm×40mm, and keep the slab with a size of 200mm×250mm×40mm for microstructure and mechanical properties The data obtained are shown in Table 3. The other two surfaces are painted with a high-temperature protective coating, air-dried naturally, and kept for further hot-rolling or cold-rolling treatment.

4. Hot rolling: One of the 200mm×250mm×40mm forging blanks is annealed at 850°C/60min in a resistance furnace, and then hot rolled immediately, the rolling direction is parallel to the 200mm length direction, no intermediate annealing, rolling 5 After one pass, a plate with a thickness of 20 mm is obtained. After the hot-rolled plate was cut, the microstructure and mechanical properties were analyzed, and the obtained data are shown in Table 3.

5. Cold rolling: Cold rolling another piece of 200mm×250mm×40mm forging billet without intermediate annealing treatment until the final thickness is 10mm and the total deformation is 75%. Then the cold-rolled sheet was cut, and a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 3. The rest is used for subsequent solution heat treatment.

6. Solution heat treatment: The cold-rolled sheet is subjected to solution treatment in a box-type resistance furnace, the solution temperature is 830-860°C, the holding time is 0.5-1.5h, and water quenched. After cutting, a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 3. The rest is used for the subsequent aging heat treatment.

7. Aging heat treatment: Artificial aging is carried out in a box-type resistance furnace. Three different aging systems are selected as follows to investigate the effects of aging temperature and aging time on the microstructure and properties of the alloy. The obtained data are also shown in Table 3.

a) The aging temperature is 400°C, the holding time is 10min, 1h, 5h, water quenching.

b) The aging temperature is 500°C, the aging time is 10min, 1h, 5h, water quenching.

c) The aging temperature is 600°C, the aging time is 10min, 1h, 5h, water quenching.

Example 4:

1) Ingredients: Ti-35Nb-8Zr-5Sn-0.30 alloy, in which Ti is sponge titanium, Zr is sponge zirconium, high melting point element Nb and volatile element Sn are all in the form of Ti-52Nb and Ti-80Sn master alloys respectively Addition, the content of O is controlled by the content of oxygen in the sponge Ti. Ingredients are formulated according to the mass percentage of the alloy composition.

2) Smelting: The prepared raw materials are pressed into electrodes on a hydraulic press, and smelted twice in a vacuum consumable electric arc furnace. Before each smelting, the vacuum degree is not lower than 10 ^-2 Pa to obtain alloy ingots. After sufficient cooling, samples were taken for differential thermal analysis and metallographic analysis, and the β→α phase transition temperature of the alloy was measured, and chemical methods were used to analyze whether there was composition segregation in the ingot. Then perform homogenization annealing (with Ar gas protection) in a vacuum furnace, the homogenization temperature is 1000°C, and the time is 12h. The ingot is then skinned to remove the outer oxide layer.

3) Open billet forging: before forging, brush the surface of the ingot with a layer of high-temperature protective coating, after natural air drying, keep it in a resistance furnace at 900°C for 90 minutes, and then perform open billet forging on a free forging machine, and the final forging temperature is controlled at 800 °C ℃ or more. A slab of 400mm×250mm×40mm is obtained, and the surface of the slab is ground after it is cooled. Use a wire cutting machine to cut the slab into one slab with a size of 100mm×250mm×40mm and two slabs with a size of 200mm×250mm×40mm, and keep the slab with a size of 200mm×250mm×40mm for microstructure and mechanical properties The data obtained are shown in Table 4. The other two surfaces are painted with a high-temperature protective coating, air-dried naturally, and kept for further hot-rolling or cold-rolling treatment.

4) Hot rolling: One of the 200mm×250mm×40mm forging blanks is annealed at 850°C/60min in a resistance furnace, and then hot rolled immediately, the rolling direction is parallel to the 200mm length direction, without intermediate annealing, rolling 5 After one pass, a plate with a thickness of 20mm is obtained. After the hot-rolled sheet was cut, the microstructure and mechanical properties were analyzed, and the obtained data are shown in Table 4.

5) Cold rolling: Cold rolling another piece of 200mm×250mm×40mm forging billet without intermediate annealing treatment until the final thickness is 10mm and the total deformation is 75%. Then the cold-rolled sheet was cut, and a part of the sample was taken for analysis of microstructure and mechanical properties. The obtained data are also shown in Table 4. The rest is used for subsequent solution heat treatment.

6) Solution heat treatment: The cold-rolled sheet is subjected to solution treatment in a box-type resistance furnace, the solution temperature is 850-880°C, the holding time is 0.5-1.5h, and water quenching. After cutting, a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 4. The rest is used for the subsequent aging heat treatment.

7) Aging heat treatment: Artificial aging is carried out in a box-type resistance furnace, and three different aging systems are selected as follows to investigate the effects of aging temperature and aging time on the microstructure and properties of the alloy. The obtained data are also shown in Table 4.

a) The aging temperature is 400°C, the holding time is 10min, 1h, 5h, water quenching.

b) The aging temperature is 500°C, the aging time is 10min, 1h, 5h, water quenching.

c) The aging temperature is 600°C, the aging time is 10min, 1h, 5h, water quenching.

Example 5:

1) Ingredients: Ti-35Nb-5Zr-10Sn-0.2O alloy, in which Ti is sponge titanium, Zr is sponge zirconium, high melting point element Nb and volatile element Sn are all in the form of Ti-52Nb and Ti-80Sn master alloys respectively To add, the content of O is controlled by the content of oxygen in the sponge Ti. Ingredients are formulated according to the mass percentage of the alloy composition.

2) Smelting: The prepared raw materials are pressed into electrodes on a hydraulic press, and smelted twice in a vacuum consumable electric arc furnace. Before each smelting, the vacuum degree is not lower than 10 ^-2 Pa to obtain alloy ingots. After sufficient cooling, samples were taken for differential thermal analysis and metallographic analysis, and the β→α phase transition temperature of the alloy was measured, and chemical methods were used to analyze whether there was composition segregation in the ingot. Then perform homogenization annealing (with Ar gas protection) in a vacuum furnace, the homogenization temperature is 1000°C, and the time is 12h. The ingot is then skinned to remove the outer oxide layer.

3) Open billet forging: before forging, brush the surface of the ingot with a layer of high-temperature protective coating, after natural air drying, keep it in a resistance furnace at 900°C for 90 minutes, and then perform open billet forging on a free forging machine, and the final forging temperature is controlled at 800 °C ℃ or more. A slab of 400mm×250mm×40mm is obtained, and the surface of the slab is ground after it is cooled. Use a wire cutting machine to cut the slab into one slab with a size of 100mm×250mm×40mm and two slabs with a size of 200mm×250mm×40mm, and keep the slab with a size of 200mm×250mm×40mm for microstructure and mechanical properties The data obtained are shown in Table 5. The other two surfaces are painted with a high-temperature protective coating, air-dried naturally, and kept for further hot-rolling or cold-rolling treatment.

4) Hot rolling: One of the 200mm×250mm×40mm forging blanks is annealed at 850°C/60min in a resistance furnace, and then hot rolled immediately, the rolling direction is parallel to the 200mm length direction, without intermediate annealing, rolling 5 After one pass, a plate with a thickness of 20mm is obtained. After the hot-rolled plate was cut, the microstructure and mechanical properties were analyzed, and the obtained data are shown in Table 5.

5) Cold rolling: Cold rolling another piece of 200mm×250mm×40mm forging billet without intermediate annealing treatment until the final thickness is 10mm and the total deformation is 75%. Then the cold-rolled sheet was cut, and a part of the sample was taken for analysis of microstructure and mechanical properties. The obtained data are also shown in Table 5. The rest is used for subsequent solution heat treatment.

6) Solution heat treatment: The cold-rolled sheet is subjected to solution treatment in a box-type resistance furnace, the solution temperature is 860-890°C, the holding time is 0.5-1.5h, and water quenching. After cutting, a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 5. The rest is used for the subsequent aging heat treatment.

7) Aging heat treatment: Artificial aging is carried out in a box-type resistance furnace, and three different aging systems are selected as follows to investigate the effects of aging temperature and aging time on the microstructure and properties of the alloy. The obtained data are also shown in Table 5.

a) The aging temperature is 400°C, the holding time is 10min, 1h, 5h, water quenching.

b) The aging temperature is 500°C, the aging time is 10min, 1h, 5h, water quenching.

c) The aging temperature is 600°C, the aging time is 10min, 1h, 5h, water quenching.

Embodiment 6:

1) Ingredients: Ti-35Nb-5Zr-5Sn-0.3O alloy, in which Ti is sponge titanium, Zr is sponge zirconium, high melting point element Nb and volatile element Sn are all in the form of Ti-52Nb and Ti-80Sn master alloys respectively To add, the content of O is controlled by the content of oxygen in the sponge Ti. Ingredients are formulated according to the mass percentage of the alloy composition.

2) Smelting: The prepared raw materials are pressed into electrodes on a hydraulic press, and smelted twice in a vacuum consumable electric arc furnace. Before each smelting, the vacuum degree is not lower than 10 ^-2 Pa to obtain alloy ingots. After sufficient cooling, samples were taken for differential thermal analysis and metallographic analysis, and the β→α phase transition temperature of the alloy was measured, and chemical methods were used to analyze whether there was composition segregation in the ingot. Then perform homogenization annealing (with Ar gas protection) in a vacuum furnace, the homogenization temperature is 1000°C, and the time is 12h. The ingot is then skinned to remove the outer oxide layer.

3) Open billet forging: before forging, brush the surface of the ingot with a layer of high-temperature protective coating, after natural air drying, keep it in a resistance furnace at 900°C for 90 minutes, and then perform open billet forging on a free forging machine, and the final forging temperature is controlled at 800 °C ℃ or more. A slab of 400mm×250mm×40mm is obtained, and the surface of the slab is ground after it is cooled. Use a wire cutting machine to cut the slab into one slab with a size of 100mm×250mm×40mm and two slabs with a size of 200mm×250mm×40mm, and keep the slab with a size of 200mm×250mm×40mm for microstructure and mechanical properties Analysis, the obtained data are shown in Table 6. The other two surfaces are painted with a high-temperature protective coating, air-dried naturally, and kept for further hot-rolling or cold-rolling treatment.

4) Hot rolling: One of the 200mm×250mm×40mm forging blanks is annealed at 850°C/60min in a resistance furnace, and then hot rolled immediately, the rolling direction is parallel to the 200mm length direction, without intermediate annealing, rolling 5 After one pass, a plate with a thickness of 20mm is obtained. After the hot-rolled plate was cut, the microstructure and mechanical properties were analyzed, and the obtained data are shown in Table 6.

5) Cold rolling: Cold rolling another piece of 200mm×250mm×40mm forging billet without intermediate annealing treatment until the final thickness is 10mm and the total deformation is 75%. Then the cold-rolled sheet was cut, and a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 6. The rest is used for subsequent solution heat treatment.

6) Solution heat treatment: The cold-rolled sheet is subjected to solution treatment in a box-type resistance furnace, the solution temperature is 870-900°C, the holding time is 0.5-1.5h, and water quenched. After cutting, a part of the sample was taken for analysis of microstructure and mechanical properties, and the obtained data are also shown in Table 6. The rest is used for the subsequent aging heat treatment.

7) Aging heat treatment: Artificial aging is carried out in a box-type resistance furnace, and three different aging systems are selected as follows to investigate the effects of aging temperature and aging time on the microstructure and properties of the alloy. The obtained data are also shown in Table 6.

a) The aging temperature is 400°C, the holding time is 10min, 1h, 5h, water quenching.

b) The aging temperature is 500°C, the aging time is 10min, 1h, 5h, water quenching.

c) The aging temperature is 600°C, the aging time is 10min, 1h, 5h, water quenching.

The obtained elastic modulus elastic modulus E=40～68GPa, the yield strength _σ0.2 is 580～815MPa, the tensile strength _σb =750～1075MPa, the elongation ε=12～48%, the reduction of area: 38～65 %.

Table 1 The performance data of the titanium alloy prepared in Example 1 under different processing and heat treatment states

Table 2 The performance data of the titanium alloy prepared in Example 2 under different processing and heat treatment states

Table 3 Example 3 The performance data of the titanium alloy prepared in different processing and heat treatment states

Table 4 Example 4 The performance data of the titanium alloy prepared in different processing and heat treatment states

Table 5 Example 5 The performance data of the titanium alloy prepared in different processing and heat treatment states

Table 6 Example 6 The performance data of the titanium alloy prepared in different processing and heat treatment states

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (10)

1. beta-titanium alloy material in biology medical application, it is characterized in that: its alloy component range is by percentage to the quality:

Nb 30～40%，

Zr 5～15%，

Sn 1～10%，

O 0.1～0.3%, and surplus is Ti, each constituent mass percent and be 100%.

2. according to the preparation method of the beta-titanium alloy material in biology medical application of the described a kind of high content of niobium of claim 1, may further comprise the steps:

Step 1: batching

Mass percent according to each component is counted: (30～40%) Nb-(5～15%) Zr-(1～10%) Sn-(0.1～0.3%) O, and surplus is that Ti prepares burden;

Step 2: alloy preparation

The batching that will prepare according to the alloying constituent of design is pressed into electrode at hydropress, electrode is put into vacuum consumable electrode arc furnace melting 2-3 time again, and ingot casting is cooled to room temperature, makes the preparing biomedical beta-titanium alloy ingot; The interior vacuum tightness of stove is greater than 1.33 * 10 during melting ^-2Pa.

3. according to the preparation method of the described a kind of beta-titanium alloy material in biology medical application of claim 2, it is characterized in that: Ti is with other sponge Ti of zero level and TiO ₂Form add, Zr adds with 99.9% sponge Zr form, high-melting-point element nb, Volatile Elements Sn add with Ti-Nb, Ti-Sn master alloy form, the content of oxygen passes through TiO in the alloy ₂Content control.

4. according to preparation method's method of the described a kind of beta-titanium alloy material in biology medical application of claim 2, it is characterized in that: in the step 2, alloy melting temp is 1600-1700 ℃, and smelting time is 30-60min.

5. according to the preparation method of claim 3 or 4 described a kind of beta-titanium alloy material in biology medical application, it is characterized in that: the vacuum oven that the preparing biomedical beta-titanium alloy ingot is put into Ar atmosphere carries out homogenizing annealing, the homogenizing annealing temperature is 900-1000 ℃, and the time is 8-12 hour.

6. according to the preparation method of the described a kind of beta-titanium alloy material in biology medical application of claim 5, it is characterized in that: the preparing biomedical beta-titanium alloy ingot surface behind the homogenizing annealing is brushed one deck high temp. protective coating, behind the natural air drying, 800-900 ℃ of insulation 60-90min in resistance furnace, then cogging is forged, and obtains forging stock; Described forging stock is through hot rolling or the cold rolling sheet material that is prepared into; Final forging temperature is controlled at more than 800 ℃.

7. according to the preparation method of the described a kind of beta-titanium alloy material in biology medical application of claim 6; it is characterized in that: before the hot rolling, one deck high temp. protective coating is brushed on the forging stock surface, hot-rolled temperature is 800-900 ℃; soaking time is 1-2 hour, and the hot rolling total deformation is 60-70%.

8. according to the preparation method of the described a kind of beta-titanium alloy material in biology medical application of claim 6, it is characterized in that: cold rolling total deformation is 30%-80%; One deck high temp. protective coating is brushed on cold-reduced sheet surface, in 800～900 ℃ carry out solution treatment 60-90min after shrend, in 400-600 ℃ carry out ageing treatment 10min～5h after water-cooled.

9. according to the preparation method of claim 6, the 7 or 8 described a kind of beta-titanium alloy material in biology medical application of any one, it is characterized in that: described high temp. protective coating is aluminum oxide or boron nitride.

10. according to the preparation method of claim 6, the 7 or 8 described a kind of beta-titanium alloy material in biology medical application of any one, it is characterized in that: the Young's modulus of the beta-titanium alloy material in biology medical application of preparation is E=40～68GPa, and yield strength is σ _0.2=580～815MPa, tensile strength is σ _b=750～1075MPa, elongation are ε=12～48%, and relative reduction in area is: 36～65%.

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