医用钛镍形状记忆合金泡沫的制备及其组织与性能研究
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摘要
多孔TiNi形状记忆合金具有优良的力学性能、耐蚀性能以及特有的超弹性和形状记忆能力,并且其多孔的结构有利于组织的长入和结合,因而作为生物移植材料,具有重要的应用前景。本文采用了NH4HCO3作为造孔剂,用粉末烧结法成功制备出了孔洞分布均匀的不同孔率和孔径的多孔TiNi形状记忆泡沫合金,并分析了所制备的多孔TiNi合金的孔结构、相组成,在此基础之上,研究了孔隙率和孔径对多孔TiNi合金的力学性能及其形状记忆性能的影响,同时评估了表面碱处理和热处理对其力学性能及其形状记忆性能的影响。
研究结果表明,用该种方法制备的多孔合金样品具有孔洞分布均匀、各向同性以及开孔率高的特点,其中大孔结构样品平均孔径在200?m左右,微孔样品的平均孔径为31?m左右。合金组织主要由奥氏体NiTi相(B2)和单斜马氏体NiTi相(B19’)组成,同时还可发现有少量的次生相Ni3Ti, Ti2Ni和Ni4Ti3。该泡沫材料的马氏体转变开始和完成温度(Ms和Mf)以及奥氏体转变开始和完成温度(As和Af)分别为:Ms=34?C,Mf=28.5?C,As=50?C,Af=60.5?C。循环加载-卸载实验结果表明,这种具有不同孔率或孔径的泡沫合金能表现出一定的形状记忆效果,但其形状记忆能力均要低于相应成分致密合金,并且随着TiNi泡沫孔隙率的增加,合金的形状记忆性能降低。在相同孔率下,孔径的减小会使多孔TiNi样品的形状记忆性能有所降低,而对合金的强度影响不大。对进行碱处理前后宏孔和微孔样品的力学性能测试结果表明,由于强碱对多孔合金孔壁的腐蚀作用,合金的力学性能和形状记忆性能都有较大幅度的降低。在450?C真空条件下对宏孔样品进行热处理(时间:30min,冰水水淬),合金中B2相体积分数增加,Ni3Ti体积分数减少,热处理后合金的力学性能有所降低。
Porous TiNi shape memory alloys (SMA) have super-elastic and shape memory behaviors. These properties are of great benefits to the healing process because shape memory alloy implants can apply a constant stress to the surrounding and in-growing bone tissues which enhance the regenerating and remodelling process of bone. In this thesis, porous TiNi alloys with a homogenous pore distribution and different pore sizes were successfully fabricated by using powder metallurgy method with NH4HCO3 as space holding particles. The phase constitution and pore structure were characterized. The mechanical properties of the porous alloys, including their shape memory behavior were measured, and the effects of the porosity of the porous and pore size on the mechanical properties and shape memory ability of the porous alloys were investigated. In addition, the degradation of the mechanical properties of the porous alloys caused by the alkali treatment and by heat treatment was evaluated.
The results indicated that the porous alloys exhibited a homogenous and isotropic pore structure with a high open-cell ratio, and the average pore size for the macro-pore samples is about 200?m and 31?m for micro-pore. The microstructure of the as-sintered alloy mainly consisted of Austenitic NiTi phase (B2) and Martensite NiTi (B19’). Some second phases, such as Ti3Ni, Ti2Ni and Ti3Ni4 can be detected. The matensite start (Ms) and finish (Mf) temperatures 34?C and 28.5?C, respectively, and the austenite start (As) and finish (Af) temperatures are 50?C and 60.5?C respectively. The load-unload recovery curves revealed that the porous alloy can exhibit the shape-memory effect, but it is less than dense TiNi. The mechanical properties of the porous alloys are strongly dependent on the porosity. With the increase of the porosity, both the strength and the shape memory ability decrease significantly. Pore size has a little effect on the strength of the porous alloy, but the porous alloys with the micro-pores exhibits a little poorer shape memory effect than that of the macro-pore samples. Surface treatment has an important influence on the mechanical properties. The alkali treatment degrades the strength and the shape memory ability due to the corrosion damages of the struts of the porous alloys. When the porous alloy is heated at 450?C for 30min, and then quenched in ice water, the fraction of B2 in the alloy increases, and the fraction of Ni3Ti decreases. As a result, the strength of the porous alloy decreases.
研究结果表明,用该种方法制备的多孔合金样品具有孔洞分布均匀、各向同性以及开孔率高的特点,其中大孔结构样品平均孔径在200?m左右,微孔样品的平均孔径为31?m左右。合金组织主要由奥氏体NiTi相(B2)和单斜马氏体NiTi相(B19’)组成,同时还可发现有少量的次生相Ni3Ti, Ti2Ni和Ni4Ti3。该泡沫材料的马氏体转变开始和完成温度(Ms和Mf)以及奥氏体转变开始和完成温度(As和Af)分别为:Ms=34?C,Mf=28.5?C,As=50?C,Af=60.5?C。循环加载-卸载实验结果表明,这种具有不同孔率或孔径的泡沫合金能表现出一定的形状记忆效果,但其形状记忆能力均要低于相应成分致密合金,并且随着TiNi泡沫孔隙率的增加,合金的形状记忆性能降低。在相同孔率下,孔径的减小会使多孔TiNi样品的形状记忆性能有所降低,而对合金的强度影响不大。对进行碱处理前后宏孔和微孔样品的力学性能测试结果表明,由于强碱对多孔合金孔壁的腐蚀作用,合金的力学性能和形状记忆性能都有较大幅度的降低。在450?C真空条件下对宏孔样品进行热处理(时间:30min,冰水水淬),合金中B2相体积分数增加,Ni3Ti体积分数减少,热处理后合金的力学性能有所降低。
Porous TiNi shape memory alloys (SMA) have super-elastic and shape memory behaviors. These properties are of great benefits to the healing process because shape memory alloy implants can apply a constant stress to the surrounding and in-growing bone tissues which enhance the regenerating and remodelling process of bone. In this thesis, porous TiNi alloys with a homogenous pore distribution and different pore sizes were successfully fabricated by using powder metallurgy method with NH4HCO3 as space holding particles. The phase constitution and pore structure were characterized. The mechanical properties of the porous alloys, including their shape memory behavior were measured, and the effects of the porosity of the porous and pore size on the mechanical properties and shape memory ability of the porous alloys were investigated. In addition, the degradation of the mechanical properties of the porous alloys caused by the alkali treatment and by heat treatment was evaluated.
The results indicated that the porous alloys exhibited a homogenous and isotropic pore structure with a high open-cell ratio, and the average pore size for the macro-pore samples is about 200?m and 31?m for micro-pore. The microstructure of the as-sintered alloy mainly consisted of Austenitic NiTi phase (B2) and Martensite NiTi (B19’). Some second phases, such as Ti3Ni, Ti2Ni and Ti3Ni4 can be detected. The matensite start (Ms) and finish (Mf) temperatures 34?C and 28.5?C, respectively, and the austenite start (As) and finish (Af) temperatures are 50?C and 60.5?C respectively. The load-unload recovery curves revealed that the porous alloy can exhibit the shape-memory effect, but it is less than dense TiNi. The mechanical properties of the porous alloys are strongly dependent on the porosity. With the increase of the porosity, both the strength and the shape memory ability decrease significantly. Pore size has a little effect on the strength of the porous alloy, but the porous alloys with the micro-pores exhibits a little poorer shape memory effect than that of the macro-pore samples. Surface treatment has an important influence on the mechanical properties. The alkali treatment degrades the strength and the shape memory ability due to the corrosion damages of the struts of the porous alloys. When the porous alloy is heated at 450?C for 30min, and then quenched in ice water, the fraction of B2 in the alloy increases, and the fraction of Ni3Ti decreases. As a result, the strength of the porous alloy decreases.
引文
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[2]舟久保,熙康.形状记忆合金[M].北京:机械工业出版社,1992.
[3]李丙运,戎利建,李依依.生物医用多孔TiNi形状记忆合金的研究进展[J].材料研究学报, 2000, 14(6): 110.
[4]徐祖耀.相变内耗与伪滞弹性[J].金属学报, 1997, 33: 45-49.
[5]蒂吉斯切,克雷兹特.多孔泡沫金属[M].北京:化学工业出版社, 2005.
[6] Yahia I L, Lombardi S, Hagemeister N, et al. Improvement of cyto-compatibility and biomechanical compatibility of NiTi shape memory alloys[J]. Appl. Biomech, 1995, 6(10):19-24.
[7] Assad M, Lemieux N, Zhu Jun, et al. Comparative in vitro biocompatibility of nickel-titanium, pure nickel, pure titanium, and stainless steel: Genotoxicity and atomic absorption evaluation [J]. Biomed Mater. Eng, 1999, 22(9): l-12.
[8] Gjunter V E. Superelastic shape memory implants in maxillofacial surgery, traumatology, orthopaedics and neurosurgery[J]. Tomsk University Publishing House, 1995, 7:13-19.
[9] Dambaev G Z, Gjunter V E, Radionchenko A, et al, Porous permeable superelastic implants in surgery[M]. Tomsk University Publishing House, 1996, 23:25.
[10] Austin G T. The use of ceramics as an implant material in the cavity[J]. MilitMed, 1981, 46(1): 50.
[11] Dai C S, Zhang L, Wang D L, et al. The Newest Developments of Foam Materials[J]. Rare Metal Materials and Engineering, 2005, 34(3):337-340.
[12] Yuan B, Zhang X P, Chung C Y, et al. The effect of porosity on phase transformation behavior of porous Ti-50.8at.% Ni shape memory alloys prepared by capsule-free hot isostatic pressing[J]. Materials Science and Engineering, 2006, A438-440:585-588.
[13] Zhang Y P, Yuan B, Zeng M Q, et al. High porosity and large size shape memory alloys fabricated by using pore-forming agent (NH4HCO3) and capsule-free hot isostatic pressing [J]. Journal of Materials Processing Technology, 2007, 192-193:439-442.
[14] Yuan B, Chung C Y, Huang P, et al. Superelastic properties of porous TiNi shape memory alloys prepared by hot isostatic pressing [J]. Materials Science and Engineering, 2006, A438-440:657-660.
[15] Yuan B, Chung C Y, Zhu M. Microstructure and martensitic transformation behavior of porous NiTi shape memory alloy prepared by hot isostatic pressing processing [J]. Materials Science and Engineering, 2004, A382(1-2):181-187.
[16] Xiong J Y, Li Y C, Wang X J, et al. Titanium–nickel shape memory alloy foams for bone tissue engineering [J]. Journal of the Mechanical Behavior of Biomedical Materials, 2008, 1(3):269-273.
[17] Ampika B, David D. Shape-memory NiTi foams produced by solid-state replicaion with NaF [J]. Intermetallics, 2007, 15:1612-1622
[18]刘培生.多孔材料引论[M].北京:清华大学出版社, 2004.
[19] Lorna J G, Michael F A.多孔固体结构与性能[M].北京:清华大学出版社, 2003.
[20]刘培生.多孔材料检测方法[M].北京:冶金工业出版社, 2006.
[21]邢树忠,王世栋,杨晓曦等.自蔓延高温合成镍钦形状记忆合金的生物医学基础研究[M],上海:上海生物医学工程出版社, 1999.
[22]牛金龙.多孔轻基磷灰石生物陶瓷的合成和特性研究进展[M].北京:生物医学工程出版社, 2002.
[23]李丙运,戎利建,李依依.多孔合金的微观结构及超弹性[J].中国科学学报, 1999, 29:11-15.
[24]杨杰,吴文华.形状记亿合金及其应用[M].北京:中国科学技术大学出版社, 1993.
[25] Li B Y, Rong L J, Li Y Y, et al. Synthesis of porous NiTi shape-memory alloys by self-propagating high-temperature synthesis: reaction mechanism and anisotropy in pore structure [J]. Acta Materialia, 2000, 48(15): 3895-3904.
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