属技术领域technical field
本发明涉及一种钛合金材料，尤其涉及一种生物医用β-钛合金材料。The invention relates to a titanium alloy material, in particular to a biomedical β-titanium alloy material.
背景技术Background technique
生物医用材料是材料科学的一个重要分支，是用于诊断、治疗或替代人体组织、器官或增进其功能、具有高技术含量和高经济价值的新型载体材料，是材料科学技术中一个正在发展的新领域。生物医用材料对于探索人类生命奥秘、保障人类健康长寿做出更大贡献。近10多年以来，生物医用材料及制品的市场增长率一直保持在20％-25％左右，预计未来10年-15年内，包括生物医用材料在内的医疗器械产业将达到医药制品市场规模，成为21世纪世界经济的支柱产业。在生物医用金属材料中，钛及其合金凭借优良的综合性能，成为人工关节(髋、膝、肩、踝、肘、腕、指关节等)、骨创伤产品(髓内钉、钢板、螺钉等)、脊柱矫形内固定系统、牙种植体、牙托、牙矫形丝、人工心脏瓣膜、介入性心血管支架等医用内植物产品的首选材料。目前，还没有比钛合金更好的金属材料用于临床。但在医用钛合金的开发上，一方面要研发低弹性模量，高耐磨性能、抗腐蚀性能及高断裂韧性，低裂纹扩展速率、高损伤容限，并具有优良生物相容性的生物医用钛合金材料；另一方面合金的组成元素应以注重无毒元素的添加为前提；另外，应努力提高我国生物医用钛及其合金加工材的质量水平，走材料研究院所或高等院校、材料生产厂及医疗研究机构、临床医学专家联合开发道路，集材料研制、生物相容性试验、临床医学验证于一体，加速开发有广阔应用前景的新型生物医用钛合金材料。Biomedical materials are an important branch of materials science. They are new carrier materials with high technical content and high economic value, which are used to diagnose, treat or replace human tissues, organs or enhance their functions. They are a developing field in materials science and technology. New Field. Biomedical materials have made greater contributions to exploring the mysteries of human life and ensuring human health and longevity. In the past 10 years, the market growth rate of biomedical materials and products has been maintained at around 20%-25%. It is estimated that in the next 10-15 years, the medical device industry, including biomedical materials, will reach the scale of the pharmaceutical product market and become The pillar industry of the world economy in the 21st century. Among biomedical metal materials, titanium and its alloys have become the most popular products for artificial joints (hip, knee, shoulder, ankle, elbow, wrist, knuckles, etc.), orthopedic trauma products (intramedullary nails, plates, screws, etc.) due to their excellent comprehensive properties. ), spinal orthopedic internal fixation systems, dental implants, dental trays, dental orthopedic wires, artificial heart valves, interventional cardiovascular stents and other medical implant products. At present, there is no better metal material than titanium alloy for clinical use. However, in the development of medical titanium alloys, on the one hand, it is necessary to develop biomaterials with low elastic modulus, high wear resistance, corrosion resistance, high fracture toughness, low crack growth rate, high damage tolerance, and excellent biocompatibility. Medical titanium alloy materials; on the other hand, the constituent elements of the alloy should be premised on the addition of non-toxic elements; in addition, efforts should be made to improve the quality level of biomedical titanium and its alloy processing materials in China, and go to materials research institutes or colleges and universities , material production plants, medical research institutions, and clinical medical experts jointly develop a road that integrates material development, biocompatibility testing, and clinical medical verification, and accelerates the development of new biomedical titanium alloy materials with broad application prospects.
发明内容Contents of the invention
本发明所要解决的技术方案是提供一种能提高材料强度、耐磨性和抗蚀性，降低材料弹性模量，保持材料良好加工成形性能的生物医用β-钛合金材料，使钛合金材料具有优良的综合使用性能。The technical solution to be solved by the present invention is to provide a biomedical β-titanium alloy material that can improve the material strength, wear resistance and corrosion resistance, reduce the elastic modulus of the material, and maintain good processing and forming properties of the material, so that the titanium alloy material has Excellent comprehensive performance.
本发明提出了一种生物医用β-钛合金材料，其合金成分范围以质量百分比计为：Ti-Nb(25％～30％)-Zr(1％～5％)-Fe(0.2％～1％)-Mo(10％～15％)。The present invention proposes a biomedical β-titanium alloy material, the alloy composition range of which is calculated by mass percentage: Ti-Nb (25%-30%)-Zr (1%-5%)-Fe (0.2%-1 %)-Mo (10% to 15%).
其制备工艺流程为：配料、高真空电弧熔炼加多次搅拌、浇铸、测相变点、真空加氩气保护均匀化、冷轧、固溶、水淬、人工时效、水冷、性能测试(拉伸、显微组织观察、X射线物相结构分析)。β-钛合金具有与人骨近似的弹性模量、优异的生物相容性及在生物环境下优良的耐蚀性等，近年来在临床上得到了越来越广泛的应用，促进了钛合金的研究与发展。在合金成分的元素选择时，考虑到医用材料必需具备生物化学相容性和生物力学相容性。生物化学相容性是指材料必须没有细胞毒性、组织刺激性、遗传毒性、致癌性，不会导致免疫反应、过敏反应等；力学相容性是指材料的力学特性接近修复部的特性，即使长期使用其功能也不发生变化。除此之外，在元素选择时还应注意选用β稳定元素。本发明中，Ti、Nb、Zr、Fe是无毒元素或低细胞毒性元素，生物相容性好，均可在不同程度上改变合金的力学性能与耐磨性能 Nb、Mo是β同晶元素，能与β钛无限互溶 Fe是β慢共析元素，在β钛中的溶解度大于在α钛中的溶解度，在一般冷却速度下能够将β相保存到室温，并对合金产生固溶强化作用。Its preparation process is: batching, high vacuum arc melting plus multiple stirring, casting, phase change point measurement, vacuum plus argon protection homogenization, cold rolling, solid solution, water quenching, artificial aging, water cooling, performance testing (pulling extension, microstructure observation, X-ray phase structure analysis). β-titanium alloy has an elastic modulus similar to that of human bone, excellent biocompatibility, and excellent corrosion resistance in biological environments. In recent years, it has been more and more widely used clinically, promoting the development of titanium alloy research and development. When selecting the elements of the alloy composition, it is considered that medical materials must have biochemical compatibility and biomechanical compatibility. Biochemical compatibility means that the material must have no cytotoxicity, tissue irritation, genotoxicity, carcinogenicity, and will not cause immune reactions, allergic reactions, etc.; mechanical compatibility means that the mechanical properties of the material are close to those of the repaired part, even if Long-term use of its function does not change. In addition, attention should be paid to the selection of β-stable elements when selecting elements. In the present invention, Ti, Nb, Zr, and Fe are non-toxic elements or low cytotoxic elements, have good biocompatibility, and can change the mechanical properties and wear resistance of the alloy to varying degrees. Nb, Mo are β isomorphic elements , can be infinitely miscible with β-titanium Fe is a β-slow eutectoid element, the solubility in β-titanium is greater than that in α-titanium, and the β-phase can be preserved to room temperature at a normal cooling rate, and has a solid-solution strengthening effect on the alloy .
本发明提出的生物医用β-钛合金材料，是在传统的生物医用材料的基础上，添加适量生物相容性好的低毒或无毒性元素及β稳定元素，从而提高材料综合性能，满足生物医用使用要求。The biomedical β-titanium alloy material proposed by the present invention is based on traditional biomedical materials, adding an appropriate amount of low-toxic or non-toxic elements and β-stable elements with good biocompatibility, thereby improving the comprehensive performance of the material and meeting the requirements of biological conditions. Medical use requirements.
本发明的β钛合金采用高真空电弧熔炼加多次搅拌、浇铸、测相变点、真空加氩气保护均匀化、冷轧、固溶、水淬、人工时效、水冷后，将材料加工成2mm厚的板材，制备出具有优良综合性能的β钛合金生物医用材料。The β-titanium alloy of the present invention is processed by high vacuum arc melting, multiple times of stirring, casting, phase change point measurement, vacuum plus argon protection homogenization, cold rolling, solid solution, water quenching, artificial aging, and water cooling. 2mm thick plate, prepared β-titanium alloy biomedical material with excellent comprehensive performance.
材料性能指标分别如下：The material performance indicators are as follows:
弹性模量(GPa)：45-66；断裂强度：650-960；屈服强度(MPa)：510-680；伸长率(％)：16-20；断面收缩率(％)：35-50。Elastic modulus (GPa): 45-66; breaking strength: 650-960; yield strength (MPa): 510-680; elongation (%): 16-20; section shrinkage (%): 35-50.
综上所述，本发明是一种能提高材料强度、耐磨性和抗蚀性，降低材料弹性模量，保持材料良好加工成形性能的生物医用β-钛合金材料，使钛合金材料具有优良的综合使用性能。其生产工艺简单可靠。In summary, the present invention is a biomedical β-titanium alloy material that can improve material strength, wear resistance and corrosion resistance, reduce the elastic modulus of the material, and maintain good processing and forming properties of the material, so that the titanium alloy material has excellent comprehensive performance. Its production process is simple and reliable.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步说明。The present invention will be further described below in conjunction with embodiment.
实施例1：Example 1:
A)合金制备A) Alloy preparation
Ti-25Nb-5 Zr-0.2Fe-15Mo合金，Ti、Nb、Zr、Fe、Mo纯金属按合金成分质量百分比配料，在高真空电弧加热炉中熔炼，充分搅拌，浇铸成100×60×20mm锭坯，充分冷却后取样经DTA分析合金固液相温度，在真空炉内进行均匀化退火(加Ar气保护)，均匀化温度为1000℃，时间为10h。Ti-25Nb-5 Zr-0.2Fe-15Mo alloy, Ti, Nb, Zr, Fe, Mo pure metals are proportioned according to the mass percentage of the alloy composition, melted in a high-vacuum arc heating furnace, fully stirred, and cast into 100×60×20mm The billet is fully cooled and sampled to analyze the solid-liquid phase temperature of the alloy by DTA. Homogenization annealing (with Ar gas protection) is carried out in a vacuum furnace. The homogenization temperature is 1000°C and the time is 10h.
B)冷轧成形B) cold rolled forming
锭坯均匀化退火后，表面经机加工成厚度为19mm板，然后进行多道次冷轧，轧至最终厚度为2mm，总变形量为89％。After the billet is homogenized and annealed, the surface is machined into a plate with a thickness of 19mm, and then multi-pass cold rolling is carried out until the final thickness is 2mm, and the total deformation is 89%.
C)热处理C) heat treatment
冷轧后样品在箱式电阻炉中进行固溶处理，固溶温度为800℃，固溶时间为2小时，固溶后进行水淬，人工时效温度为350℃，时效时间为10小时，时效后用水冷却。After cold rolling, the sample is solution treated in a box-type resistance furnace. The solution temperature is 800°C, and the solution time is 2 hours. After solution, it is water quenched. The artificial aging temperature is 350°C, and the aging time is 10 hours. Then cool with water.
D)材料性能D) Material properties
弹性模量(GPa)：45；断裂强度(MPa)：700；屈服强度(MPa)：550；伸长率(％)：18；断面收缩率(％)：36。Elastic modulus (GPa): 45; breaking strength (MPa): 700; yield strength (MPa): 550; elongation (%): 18;
实施例2：Example 2:
A)合金制备A) Alloy preparation
Ti-28Nb-3 Zr-0.6Fe-12Mo合金，Ti、Nb、Zr、Fe、Mo纯金属按合金成分质量百分比配料，在高真空电弧加热炉中熔炼，充分搅拌，浇铸成100×60×20mm锭坯，充分冷却后取样经DTA分析合金固液相温度，在真空炉内进行均匀化退火(加Ar气保护)，均匀化温度为1000℃，时间为10h。Ti-28Nb-3 Zr-0.6Fe-12Mo alloy, Ti, Nb, Zr, Fe, Mo pure metals are proportioned according to the mass percentage of alloy composition, melted in a high-vacuum arc heating furnace, fully stirred, and cast into 100×60×20mm The billet is fully cooled and sampled to analyze the solid-liquid phase temperature of the alloy by DTA. Homogenization annealing (with Ar gas protection) is carried out in a vacuum furnace. The homogenization temperature is 1000°C and the time is 10h.
B)冷轧成形B) cold rolled forming
锭坯均匀化退火后，表面经机加工成厚度为19mm板，然后进行多道次冷轧，轧至最终厚度为2mm，总变形量为89％。After the billet is homogenized and annealed, the surface is machined into a plate with a thickness of 19mm, and then multi-pass cold rolling is carried out until the final thickness is 2mm, and the total deformation is 89%.
C)热处理C) heat treatment
冷轧后样品在箱式电阻炉中进行固溶处理，固溶温度为800℃，固溶时间为2小时，固溶后进行水淬，人工时效温度为350℃，时效时间为10小时，时效后用水冷却。After cold rolling, the sample is solution treated in a box-type resistance furnace. The solution temperature is 800°C, and the solution time is 2 hours. After solution, it is water quenched. The artificial aging temperature is 350°C, and the aging time is 10 hours. Then cool with water.
D)材料性能D) Material properties
弹性模量(GPa)：55；断裂强度(MPa)：800；屈服强度(MPa)：720；伸长率(％)：19；断面收缩率(％)：43。Elastic modulus (GPa): 55; breaking strength (MPa): 800; yield strength (MPa): 720; elongation (%): 19;
实施例3：Example 3:
A)合金制备A) Alloy preparation
Ti-30Nb-1Zr-1Fe-10Mo合金，Ti、Nb、Zr、Fe、Mo纯金属按合金成分质量百分比配料，在高真空电弧加热炉中熔炼，充分搅拌，浇铸成100×60×2 0mm锭坯，充分冷却后取样经DTA分析合金固液相温度，在真空炉内进行均匀化退火(加Ar气保护)，均匀化温度为1000℃，时间为10h。Ti-30Nb-1Zr-1Fe-10Mo alloy, Ti, Nb, Zr, Fe, Mo pure metals are proportioned according to the mass percentage of the alloy composition, melted in a high vacuum arc heating furnace, fully stirred, and cast into a 100×60×2 0mm ingot After fully cooling the blank, samples were taken to analyze the solid-liquid phase temperature of the alloy by DTA, and homogenization annealing (with Ar gas protection) was performed in a vacuum furnace. The homogenization temperature was 1000°C and the time was 10h.
B)冷轧成形B) cold rolled forming
锭坯均匀化退火后，表面经机加工成厚度为19mm板，然后进行多道次冷轧，轧至最终厚度为2mm，总变形量为89％。After the billet is homogenized and annealed, the surface is machined into a plate with a thickness of 19mm, and then multi-pass cold rolling is carried out until the final thickness is 2mm, and the total deformation is 89%.
C)热处理C) heat treatment
冷轧后样品在箱式电阻炉中进行固溶处理，固溶温度为800℃，固溶时间为2小时，固溶后进行水淬，人工时效温度为350℃，时效时间为10小时，时效后用水冷却。After cold rolling, the sample is solution treated in a box-type resistance furnace. The solution temperature is 800°C, and the solution time is 2 hours. After solution, it is water quenched. The artificial aging temperature is 350°C, and the aging time is 10 hours. Then cool with water.
D)材料性能D) Material properties
弹性模量(GPa)：60；断裂强度(MPa)：910；屈服强度(MPa)：650；伸长率(％)：17；断面收缩率(％)：36。Elastic modulus (GPa): 60; breaking strength (MPa): 910; yield strength (MPa): 650; elongation (%): 17;
实施例4：Example 4:
A)合金制备A) Alloy preparation
Ti-30Nb-5Zr-1Fe-15Mo合金，Ti、Nb、Zr、Fe、Mo纯金属按合金成分质量百分比配料，在高真空电弧加热炉中熔炼，充分搅拌，浇铸成100×60×20mm锭坯，充分冷却后取样经DTA分析合金固液相温度，在真空炉内进行均匀化退火(加Ar气保护)，均匀化温度为1000℃，时间为10h。Ti-30Nb-5Zr-1Fe-15Mo alloy, Ti, Nb, Zr, Fe, Mo pure metals are proportioned according to the mass percentage of the alloy composition, melted in a high vacuum arc heating furnace, fully stirred, and cast into a 100×60×20mm ingot , After fully cooling, samples were taken to analyze the solid-liquid phase temperature of the alloy by DTA, and homogenization annealing (with Ar gas protection) was carried out in a vacuum furnace. The homogenization temperature was 1000°C and the time was 10h.
B)冷轧成形B) cold rolled forming
锭坯均匀化退火后，表面经机加工成厚度为19mm板，然后进行多道次冷轧，轧至最终厚度为2mm，总变形量为89％。After the billet is homogenized and annealed, the surface is machined into a plate with a thickness of 19mm, and then multi-pass cold rolling is carried out until the final thickness is 2mm, and the total deformation is 89%.
C)热处理C) heat treatment
冷轧后样品在箱式电阻炉中进行固溶处理，固溶温度为800℃，固溶时间为2小时，固溶后进行水淬，人工时效温度为350℃，时效时间为10小时，时效后用水冷却。After cold rolling, the sample is solution treated in a box-type resistance furnace. The solution temperature is 800°C, and the solution time is 2 hours. After solution, it is water quenched. The artificial aging temperature is 350°C, and the aging time is 10 hours. Then cool with water.
D)材料性能D) Material properties
弹性模量(GPa)：66；断裂强度(MPa)：960；屈服强度(MPa)：680；伸长率(％)：16；断面收缩率(％)：35。Elastic modulus (GPa): 66; breaking strength (MPa): 960; yield strength (MPa): 680; elongation (%): 16;
实施例5：Example 5:
A)合金制备A) Alloy preparation
Ti-25Nb-1 Zr-0.2Fe-10Mo合金，Ti、Nb、Zr、Fe、Mo纯金属按合金成分质量百分比配料，在高真空电弧加热炉中熔炼，充分搅拌，浇铸成100×60×20mm锭坯，充分冷却后取样经DTA分析合金固液相温度，在真空炉内进行均匀化退火(加Ar气保护)，均匀化温度为1000℃，时间为10h。Ti-25Nb-1 Zr-0.2Fe-10Mo alloy, Ti, Nb, Zr, Fe, Mo pure metals are proportioned according to the mass percentage of the alloy composition, melted in a high-vacuum arc heating furnace, fully stirred, and cast into 100×60×20mm The billet is fully cooled and sampled to analyze the solid-liquid phase temperature of the alloy by DTA. Homogenization annealing (with Ar gas protection) is carried out in a vacuum furnace. The homogenization temperature is 1000°C and the time is 10h.
B)冷轧成形B) cold rolled forming
锭坯均匀化退火后，表面经机加工成厚度为19mm板，然后进行多道次冷轧，轧至最终厚度为2mm，总变形量为89％。After the billet is homogenized and annealed, the surface is machined into a plate with a thickness of 19mm, and then multi-pass cold rolling is carried out until the final thickness is 2mm, and the total deformation is 89%.
C)热处理C) heat treatment
冷轧后样品在箱式电阻炉中进行固溶处理，固溶温度为800℃，固溶时间为2小时，固溶后进行水淬，人工时效温度为350℃，时效时间为10小时，时效后用水冷却。After cold rolling, the sample is solution treated in a box-type resistance furnace. The solution temperature is 800°C, and the solution time is 2 hours. After solution, it is water quenched. The artificial aging temperature is 350°C, and the aging time is 10 hours. Then cool with water.
D)材料性能D) Material properties
弹性模量(GPa)：45；断裂强度(MPa)：650；屈服强度(MPa)：510；伸长率(％)：20；断面收缩率(％)：50。Elastic modulus (GPa): 45; breaking strength (MPa): 650; yield strength (MPa): 510; elongation (%): 20;
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710035286CN101081312A (en) | 2007-07-05 | 2007-07-05 | Beta-titanium alloy material in biology medical application |
| Application Number | Priority Date | Filing Date | Title |
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| CN 200710035286CN101081312A (en) | 2007-07-05 | 2007-07-05 | Beta-titanium alloy material in biology medical application |
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| CN101081312Atrue CN101081312A (en) | 2007-12-05 |
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| CN 200710035286PendingCN101081312A (en) | 2007-07-05 | 2007-07-05 | Beta-titanium alloy material in biology medical application |
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| CN (1) | CN101081312A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724764B (en)* | 2009-12-10 | 2011-07-20 | 中南大学 | Process for preparing biomedical beta-titanium alloy |
| CN108103354A (en)* | 2018-02-02 | 2018-06-01 | 贾红琴 | A kind of medical titanium alloy bone implant and preparation method thereof |
| CN112159913A (en)* | 2020-08-25 | 2021-01-01 | 中国石油天然气集团有限公司 | 135 ksi-grade titanium alloy, titanium alloy drill rod and preparation method thereof |
| CN115305385A (en)* | 2022-08-17 | 2022-11-08 | 暨南大学 | A low-cost, low-modulus, high-strength, and high-wear-resistant bio-titanium alloy and its preparation method and application |
| CN115652238A (en)* | 2022-10-26 | 2023-01-31 | 成都先进金属材料产业技术研究院股份有限公司 | Heat treatment method for improving cold heading performance of TB14 alloy wire for fastener |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724764B (en)* | 2009-12-10 | 2011-07-20 | 中南大学 | Process for preparing biomedical beta-titanium alloy |
| CN108103354A (en)* | 2018-02-02 | 2018-06-01 | 贾红琴 | A kind of medical titanium alloy bone implant and preparation method thereof |
| CN112159913A (en)* | 2020-08-25 | 2021-01-01 | 中国石油天然气集团有限公司 | 135 ksi-grade titanium alloy, titanium alloy drill rod and preparation method thereof |
| CN112159913B (en)* | 2020-08-25 | 2022-03-01 | 中国石油天然气集团有限公司 | 135 ksi-grade titanium alloy, titanium alloy drill rod and preparation method thereof |
| CN115305385A (en)* | 2022-08-17 | 2022-11-08 | 暨南大学 | A low-cost, low-modulus, high-strength, and high-wear-resistant bio-titanium alloy and its preparation method and application |
| CN115652238A (en)* | 2022-10-26 | 2023-01-31 | 成都先进金属材料产业技术研究院股份有限公司 | Heat treatment method for improving cold heading performance of TB14 alloy wire for fastener |
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