【摘要】：近等原子比的TiNi合金,不僅具有與人體骨組織相近的超彈性,還具有特殊的形狀記憶效應(yīng)、良好的生物相容性和耐磨耐蝕性能,這些性能均使TiNi合金有望作為一種優(yōu)異的骨組織替代材料在生物醫(yī)學(xué)領(lǐng)域得到迅速發(fā)展。然而,致密TiNi合金較人體骨組織力學(xué)性能偏高,不匹配的彈性模量往往易產(chǎn)生應(yīng)力屏蔽問(wèn)題,且致密的植入合金與新生骨組織間接觸面積較小,這些都會(huì)造成植入物與組織間結(jié)合松動(dòng),終而導(dǎo)致植入失效。 針對(duì)以上問(wèn)題,本研究設(shè)計(jì)出具有良好孔隙性能且實(shí)現(xiàn)與力學(xué)性能最優(yōu)化組合的仿生多孔TiNi合金。為了進(jìn)一步發(fā)掘多孔TiNi形狀記憶合金的其它潛力,本論文圍繞材料設(shè)計(jì)與制備、微觀結(jié)構(gòu)、理化性能等方面開(kāi)展了相應(yīng)研究,采用真空熱壓、真空燒結(jié)和模板浸漬三種方法分別制備相對(duì)致密、中等孔隙度和高孔隙度的TiNi合金,并對(duì)各自的工藝影響參數(shù)進(jìn)行了探討,分別研究了三種方法所制備TiNi合金的物相成分、微觀結(jié)構(gòu)特征和力學(xué)性能,并評(píng)估了TiNi合金的生物學(xué)性能。 真空熱壓燒結(jié)能夠制備出高致密度的TiNi合金,合金性能和初始原料粉末的選取密切相關(guān),其中預(yù)合金粉末燒結(jié)合金更為致密,抗拉強(qiáng)度677.34MPa,彈性模量5.348GPa；真空燒結(jié)制備出的中等孔隙度的TiNi合金,其性能會(huì)隨燒結(jié)溫度有較大范圍的調(diào)整變化,隨著燒結(jié)溫度升高,物相更為均勻,相對(duì)密度由56.36%增至62.99%,抗拉強(qiáng)度由72.43MPa明顯提升至160.72MPa；模板浸漬與燒結(jié)工藝相結(jié)合,可制備出具有與人體松質(zhì)骨結(jié)構(gòu)相似的三維聯(lián)通孔隙的高孔隙度TiNi合金,合金保留了原始TiNi預(yù)合金粉末中的物相成分。 利用不同方法和不同工藝因素可制備出不同性能的TiNi合金,通過(guò)調(diào)整孔隙度以獲得良好孔隙性能和力學(xué)性能適配的多孔TiNi合金,亦可在較大范圍內(nèi)調(diào)整多孔TiNi合金力學(xué)性能來(lái)滿(mǎn)足不同植入的需要。尤其是模板浸漬法制備的高孔隙度TiNi合金,不僅易于獲得與人體骨組織相似的孔隙性能,也易于通過(guò)模板的選取和料漿中粉末含量的調(diào)整來(lái)實(shí)現(xiàn)與骨組織匹配的力學(xué)性能。 添加第三組元Nb元素替代部分Ni以降低Ni的含量,利用真空燒結(jié)制備多孔TiNiNb合金。Nb元素的加入使TiNiNb合金具有與二元TiNi合金較大不同的性能改變。在添加Nb含量為0-10at.%時(shí),合金主要保證了基體相為T(mén)iNi母相,Nb顆粒彌散分布在基體相上。Nb作為T(mén)i的固溶元素,可適度提高TiNiNb合金體系的燒結(jié)活性。隨Nb含量增加,合金的收縮愈加明顯,相對(duì)密度由TiNi的71.45%先緩慢增加至Ti5oNi45Nb5的72.89%后,迅速增至Ti50Ni40Nb10的82.96%。在初加入Nb時(shí)略有升高,當(dāng)Nb含量超過(guò)5%后迅速增高�？估瓘�(qiáng)度和彈性模量均隨Nb增加亦得到有效提高。同時(shí),Nb也可適度提高TiNi合金的礦化能力和生物安全性。 生物學(xué)性能評(píng)估表明,TiNi合金具有良好的生物安全性和相容性。在骨修復(fù)支架應(yīng)用方面,多孔TiNi合金,尤其是模板浸漬法制備的三維通孔TiNi合金具有比致密合金更高的潛質(zhì),其多孔結(jié)構(gòu)使體系的表面能大幅度提升,不僅呈現(xiàn)出良好的磷灰石沉積的能力,豐富且優(yōu)異的仿生三維聯(lián)通孔隙結(jié)構(gòu)也為營(yíng)養(yǎng)物質(zhì)的輸送和廢物的代謝保證了充足的空間,這對(duì)成骨細(xì)胞的粘附、分化和增殖、血管化,以及組織的再生與重建都是非常有利的。多孔結(jié)構(gòu)對(duì)骨的生長(zhǎng)具有優(yōu)良的引導(dǎo)作用,孔隙通道促使生物組織通過(guò)其長(zhǎng)入TiNi合金內(nèi)部,從而加強(qiáng)了合金與組織間的生物力學(xué)結(jié)合,提高植入的穩(wěn)定程度,促進(jìn)愈合過(guò)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.
【學(xué)位授予單位】：中南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類(lèi)號(hào)】：R318.08;TG146.23

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