生物医用多孔钛镍（铌）合金的制备与性能研究
发布时间：2018-10-13 12:56
【摘要】：近等原子比的TiNi合金,不仅具有与人体骨组织相近的超弹性,还具有特殊的形状记忆效应、良好的生物相容性和耐磨耐蚀性能,这些性能均使TiNi合金有望作为一种优异的骨组织替代材料在生物医学领域得到迅速发展。然而,致密TiNi合金较人体骨组织力学性能偏高,不匹配的弹性模量往往易产生应力屏蔽问题,且致密的植入合金与新生骨组织间接触面积较小,这些都会造成植入物与组织间结合松动,终而导致植入失效。 针对以上问题,本研究设计出具有良好孔隙性能且实现与力学性能最优化组合的仿生多孔TiNi合金。为了进一步发掘多孔TiNi形状记忆合金的其它潜力,本论文围绕材料设计与制备、微观结构、理化性能等方面开展了相应研究,采用真空热压、真空烧结和模板浸渍三种方法分别制备相对致密、中等孔隙度和高孔隙度的TiNi合金,并对各自的工艺影响参数进行了探讨,分别研究了三种方法所制备TiNi合金的物相成分、微观结构特征和力学性能,并评估了TiNi合金的生物学性能。 真空热压烧结能够制备出高致密度的TiNi合金,合金性能和初始原料粉末的选取密切相关,其中预合金粉末烧结合金更为致密,抗拉强度677.34MPa,弹性模量5.348GPa；真空烧结制备出的中等孔隙度的TiNi合金,其性能会随烧结温度有较大范围的调整变化,随着烧结温度升高,物相更为均匀,相对密度由56.36%增至62.99%,抗拉强度由72.43MPa明显提升至160.72MPa；模板浸渍与烧结工艺相结合,可制备出具有与人体松质骨结构相似的三维联通孔隙的高孔隙度TiNi合金,合金保留了原始TiNi预合金粉末中的物相成分。 利用不同方法和不同工艺因素可制备出不同性能的TiNi合金,通过调整孔隙度以获得良好孔隙性能和力学性能适配的多孔TiNi合金,亦可在较大范围内调整多孔TiNi合金力学性能来满足不同植入的需要。尤其是模板浸渍法制备的高孔隙度TiNi合金,不仅易于获得与人体骨组织相似的孔隙性能,也易于通过模板的选取和料浆中粉末含量的调整来实现与骨组织匹配的力学性能。 添加第三组元Nb元素替代部分Ni以降低Ni的含量,利用真空烧结制备多孔TiNiNb合金。Nb元素的加入使TiNiNb合金具有与二元TiNi合金较大不同的性能改变。在添加Nb含量为0-10at.%时,合金主要保证了基体相为TiNi母相,Nb颗粒弥散分布在基体相上。Nb作为Ti的固溶元素,可适度提高TiNiNb合金体系的烧结活性。随Nb含量增加,合金的收缩愈加明显,相对密度由TiNi的71.45%先缓慢增加至Ti5oNi45Nb5的72.89%后,迅速增至Ti50Ni40Nb10的82.96%。在初加入Nb时略有升高,当Nb含量超过5%后迅速增高。抗拉强度和弹性模量均随Nb增加亦得到有效提高。同时,Nb也可适度提高TiNi合金的矿化能力和生物安全性。 生物学性能评估表明,TiNi合金具有良好的生物安全性和相容性。在骨修复支架应用方面,多孔TiNi合金,尤其是模板浸渍法制备的三维通孔TiNi合金具有比致密合金更高的潜质,其多孔结构使体系的表面能大幅度提升,不仅呈现出良好的磷灰石沉积的能力,丰富且优异的仿生三维联通孔隙结构也为营养物质的输送和废物的代谢保证了充足的空间,这对成骨细胞的粘附、分化和增殖、血管化,以及组织的再生与重建都是非常有利的。多孔结构对骨的生长具有优良的引导作用,孔隙通道促使生物组织通过其长入TiNi合金内部,从而加强了合金与组织间的生物力学结合,提高植入的稳定程度,促进愈合过程。
[Abstract]:The TiNi alloy of the near atomic ratio not only has the superelasticity similar to the bone tissue of the human body, but also has special shape memory effect, good biocompatibility and wear resistance and corrosion resistance, These properties lead to rapid development of TiNi alloy as an excellent substitute for bone tissue in the field of biomedicine. However, the high mechanical properties of the compact TiNi alloy are higher than that of the human bone tissue, and the non-matching elastic modulus tends to produce stress shielding problems, and the contact area between the compact implanted alloy and the newly-born bone tissue is small, which can lead to loose joint between the implant and the tissue, and finally lead to implantation failure. In view of the above problems, we designed bionic porous TiNi which has good pore properties and optimized the mechanical properties. In order to further explore the other potential of porous TiNi shape memory alloy, this paper has carried out corresponding research about material design and preparation, microstructure and physical and chemical properties. The TiNi alloy with dense, medium porosity and high porosity was studied. The composition, microstructure and mechanical properties of TiNi alloy prepared by three methods were studied, and the biology of TiNi alloy was evaluated. The results show that the pre-alloyed powder sintered alloy is more compact, the tensile strength is 677. 34MPa, the elastic modulus is 5. 348GPa, the medium porosity prepared by vacuum sintering is T The performance of iNi alloy varies with the sintering temperature. With the increase of the sintering temperature, the phase is more uniform, the relative density is increased from 56. 36% to 62. 99%, the tensile strength is increased from 72. 43MPa to 160. 72MPa, and the template is impregnated and sintered. By combining the process, the TiNi alloy with high porosity similar to the cancellous bone structure of the human body can be prepared, and the alloy retains the original TiNi pre-alloy powder The TiNi alloy with different properties can be prepared by using different methods and different technological factors. By adjusting porosity to obtain porous TiNi alloy with good pore performance and mechanical property, the mechanical properties of porous TiNi alloy can be adjusted in a wide range. The high porosity TiNi alloy prepared by the template impregnation method is not only easy to obtain the pore performance similar to the bone tissue of the human body, but also can be easily realized through the selection of the template and the adjustment of the powder content in the slurry, The mechanical properties of the weaving match are improved. The third element Nb element is added to replace part of Ni to reduce the content of Ni, and a vacuum sintering system is utilized. The addition of Nb element makes TiNiNb alloy possess binary TiNi Alloy has a significantly different performance change. In addition When Nb content is 0-10at.%, the alloy mainly ensures that the matrix phase is TiNi mother phase, Nb The particle dispersion is distributed on the matrix phase. Nb, as a solid soluble element of Ti, can moderately improve the TiNi. The sintering activity of Nb alloy system is increased with the increase of Nb content, the shrinkage of the alloy becomes more obvious, the relative density is increased slowly to 72. 89% of Ti5oNi45Nb5 by 71. 45% of TiNi, then it is rapidly increased to Ti50Ni40. 82. 96% of Nb10. slightly elevated at the beginning of the addition of Nb, when Nb The content of tensile strength and elastic modulus increase rapidly after the content exceeds 5%. Nb addition is also effectively improved, and Nb can also increase the TiNi alloy moderately. mineralization and biological safety. Biological performance evaluation indicates that TiNi alloy In the application of bone repair support, the three-dimensional through-hole TiNi alloy prepared by the porous TiNi alloy, in particular the template impregnation method, has a higher tensile strength than the compact alloy, and the porous structure of the three-dimensional through-hole TiNi alloy can greatly improve the surface of the system, the ability to exhibit good apatite deposition, abundant and excellent bionic three-dimensional communicating pore structure also ensures sufficient space for the transport of nutrients and the metabolism of waste, The regeneration and reconstruction of the tissue are very beneficial. The porous structure has excellent guiding effect on the growth of the bone, and the pore channel causes the biological tissue to pass through the inside of the TiNi alloy so as to strengthen the biomechanical bond between the alloy and the tissue and improve the biomechanical property between the alloy and the tissue.
【学位授予单位】：中南大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：R318.08;TG146.23
本文编号：2268715
[Abstract]:The TiNi alloy of the near atomic ratio not only has the superelasticity similar to the bone tissue of the human body, but also has special shape memory effect, good biocompatibility and wear resistance and corrosion resistance, These properties lead to rapid development of TiNi alloy as an excellent substitute for bone tissue in the field of biomedicine. However, the high mechanical properties of the compact TiNi alloy are higher than that of the human bone tissue, and the non-matching elastic modulus tends to produce stress shielding problems, and the contact area between the compact implanted alloy and the newly-born bone tissue is small, which can lead to loose joint between the implant and the tissue, and finally lead to implantation failure. In view of the above problems, we designed bionic porous TiNi which has good pore properties and optimized the mechanical properties. In order to further explore the other potential of porous TiNi shape memory alloy, this paper has carried out corresponding research about material design and preparation, microstructure and physical and chemical properties. The TiNi alloy with dense, medium porosity and high porosity was studied. The composition, microstructure and mechanical properties of TiNi alloy prepared by three methods were studied, and the biology of TiNi alloy was evaluated. The results show that the pre-alloyed powder sintered alloy is more compact, the tensile strength is 677. 34MPa, the elastic modulus is 5. 348GPa, the medium porosity prepared by vacuum sintering is T The performance of iNi alloy varies with the sintering temperature. With the increase of the sintering temperature, the phase is more uniform, the relative density is increased from 56. 36% to 62. 99%, the tensile strength is increased from 72. 43MPa to 160. 72MPa, and the template is impregnated and sintered. By combining the process, the TiNi alloy with high porosity similar to the cancellous bone structure of the human body can be prepared, and the alloy retains the original TiNi pre-alloy powder The TiNi alloy with different properties can be prepared by using different methods and different technological factors. By adjusting porosity to obtain porous TiNi alloy with good pore performance and mechanical property, the mechanical properties of porous TiNi alloy can be adjusted in a wide range. The high porosity TiNi alloy prepared by the template impregnation method is not only easy to obtain the pore performance similar to the bone tissue of the human body, but also can be easily realized through the selection of the template and the adjustment of the powder content in the slurry, The mechanical properties of the weaving match are improved. The third element Nb element is added to replace part of Ni to reduce the content of Ni, and a vacuum sintering system is utilized. The addition of Nb element makes TiNiNb alloy possess binary TiNi Alloy has a significantly different performance change. In addition When Nb content is 0-10at.%, the alloy mainly ensures that the matrix phase is TiNi mother phase, Nb The particle dispersion is distributed on the matrix phase. Nb, as a solid soluble element of Ti, can moderately improve the TiNi. The sintering activity of Nb alloy system is increased with the increase of Nb content, the shrinkage of the alloy becomes more obvious, the relative density is increased slowly to 72. 89% of Ti5oNi45Nb5 by 71. 45% of TiNi, then it is rapidly increased to Ti50Ni40. 82. 96% of Nb10. slightly elevated at the beginning of the addition of Nb, when Nb The content of tensile strength and elastic modulus increase rapidly after the content exceeds 5%. Nb addition is also effectively improved, and Nb can also increase the TiNi alloy moderately. mineralization and biological safety. Biological performance evaluation indicates that TiNi alloy In the application of bone repair support, the three-dimensional through-hole TiNi alloy prepared by the porous TiNi alloy, in particular the template impregnation method, has a higher tensile strength than the compact alloy, and the porous structure of the three-dimensional through-hole TiNi alloy can greatly improve the surface of the system, the ability to exhibit good apatite deposition, abundant and excellent bionic three-dimensional communicating pore structure also ensures sufficient space for the transport of nutrients and the metabolism of waste, The regeneration and reconstruction of the tissue are very beneficial. The porous structure has excellent guiding effect on the growth of the bone, and the pore channel causes the biological tissue to pass through the inside of the TiNi alloy so as to strengthen the biomechanical bond between the alloy and the tissue and improve the biomechanical property between the alloy and the tissue.
【学位授予单位】：中南大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：R318.08;TG146.23
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