生物医用Ti-Mn合金的组织结构与性能研究
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摘要
本文研究了不同Mn元素添加量（2、5、8、10wt.%）的Ti-Mn合金的组织结构、拉伸性能、在模拟口腔环境中的和胆道环境的电化学腐蚀性能、离子溶出行为以及体外细胞毒性等，探讨了其作为牙科修复材料和胆道支架材料的可行性。采用光学金相显微镜、扫描电子显微镜、X射线衍射分析等测试手段分析研究了合金的显微组织及相组成随合金化元素含量变化的规律；利用万能材料试验机，研究了合金的拉伸性能；利用显微硬度计和球盘式摩擦磨损实验机研究了合金的维氏显微硬度和耐磨性；通过开路电位测试、电化学阻抗分析和动电位极化测试研究了合金在模拟唾液环境下的电化学腐蚀行为；利用浸泡法以及扫描电子显微镜和X射线衍射分析技术考察了合金在模拟体液环境下和人体胆汁环境下的耐腐蚀性；通过体外浸提法和四甲基偶氮唑盐（MTT）比色法考察了合金浸提液对L929细胞和MG63细胞的体外细胞毒性。
铸态Ti-Mn合金的显微组织随Mn含量增加，由单一的等轴-Ti相逐渐演变成由-Ti和TiMn相组成的双相组织；当Mn含量达10wt.%时，合金中还会出现Ti0.48Mn0.52相。铸态Ti-Mn合金的屈服强度和断裂延伸率随Mn含量的增加先增加后降低，抗拉强度、维氏硬度和耐磨性能均随Mn含量增加而增加。与干摩擦条件下的磨损失重相比，在以模拟唾液为润滑的湿摩擦条件下，Ti及铸态Ti-Mn合金的磨损失重降低，耐磨性提高。与铸态Ti-5Mn合金相比，轧制态Ti-5Mn合金的晶粒尺寸明显长大，具有较高的显微硬度和耐磨性，但是力学性能明显下降，断裂延伸率下降了约65%。铸态Ti-5Mn合金具有最佳的强度和塑性配合。
在未添加任何成分的模拟唾液中，铸态Ti-Mn合金的电化学腐蚀抗力与纯Ti相近；在含氟的模拟唾液中，纯Ti的耐腐蚀性恶化并发生再钝化，而铸态Ti-Mn合金的耐腐蚀性未明显恶化并未发生再钝化。铸态Ti-Mn合金在几种含有不同添加成分的模拟唾液中浸泡7d后，表面钝化膜发生破坏，引起基体中Ti离子和Mn离子的析出；合金在同时添加NaF和乳酸的模拟唾液中的Ti离子析出量最高。纯钛和铸态Ti-5Mn合金在人体胆汁中呈现钝化现象，维钝电流密度略大于0.1mA/cm2，具有较强的耐腐蚀性。铸态Ti-5Mn合金在pH6.8和pH7.0的人体胆汁中具有与纯钛相当的耐腐蚀性；在pH7.4的弱碱性人体胆汁中，具有较高的自腐蚀电位，耐腐蚀性略优于纯钛。
不同锰含量的Ti-Mn合金与水和丙三醇的表面接触角均小于90°，为亲水表面；随合金中Mn元素含量的增加，Ti-Mn合金与水和丙三醇的表面接触角增加。Ti-5Mn合金的表面能在四种Ti-Mn合金中最小，其值与纯钛的表面能大小相当。Ti和Ti-5Mn合金与胆汁接触后，材料表面未发生游离态胆红素或胆红素钙等的聚集和粘附，对胆汁中胆红素的影响较小。纯钛和Ti-5Mn合金在胆汁中浸泡3d时与胆汁中的磷脂没有明显的相互作用；随着浸泡时间的延长（7d），两种材料与胆汁中的磷脂发生了一定的相互作用，引起红外谱图上磷脂的特征峰位置和强度发生变化。通过喷涂方法在纯Ti和Ti-5Mn合金表面制备的PTX/PLGA载药涂层，涂层表明均匀，具有一定的方向性；其接触角与裸金属表面接触角相近。PTX/PLGA载药涂层在人体胆汁中浸泡3d和7d后，对胆汁中胆红素和磷脂成分没有产生明显的影响。体外细胞毒性测试发现，铸态Ti-Mn合金对小鼠成纤维细胞L929和骨肉瘤细胞MG63的毒性级别为1级，属于微毒范畴。随合金中Mn含量的增加，培养的细胞的存活能力在明显下降，说明Mn离子溶出之后对L929细胞和MG63细胞的存活具有一定的毒性。
Ti-Mn alloys with different Mn content (2,5,8,10wt.%) were developed in the presentwork and various experiments have been carried out to investigate the microstructure andphase composition，tensile properties, in vitro electrochemical corrosion in simulated oralenvironment and bile environment, ion release behavior and the in vitro cytotoxicity, withpure titanium as control. The purpose of the study was to explore the feasibility of Ti-Mnalloys used as potential dental materials and biliray stent materials. Optical microscope,scanning electron microscope (SEM) and X-ray diffraction (XRD) were employed to studythe evolvement of microstructure and phase composition with the alloying element content.Tension property was investigated with universal materials testing machine. Microhardnessand wear resistance had been studied with digital hardness tester and ball-on-flat tribometer.Electrochemical behaviors in the artificial saliva were analyzed by methods of open circuitpotential (OCP), electrochemical impedance spectroscopy and dynamic polarization potential.The immersion corrosion behaviors of the alloys in artificial saliva had also been studied withInductively Coupled Plasma Optical Emission Spectrometer（ICP-OES）, SEM and XRD.Furthermore, the in vitro toxicity of the alloys to L929and MG63cell lines had beenevaluated by MTT method.
The microstructure of as-cast Ti-Mn alloys changes from single-Ti phase to-Ti+TiMn precipitation phase with the increase of Mn content, and Ti0.48Mn0.52phase wasobserved when Mn content arrived10wt.%. The yield strength and fracture elongation ofas-cast Ti-Mn alloy first increased and then decreased with the increase of Mn content, whilethe tensile strength, microhardness and wear resistance increased with the increase of Mncontent. Compared with the wear loss under dry condition, the wear loss of Ti and as-castTi-Mn alloy decreased under the wet condition with artificial saliva as lubricant, indicatingthe improved wear resistance. Compared with the as-cast Ti-5Mn alloy, the grain size ofhot-rolled Ti-5Mn alloy increased, and the microhardness and wear resistance of hot rolledTi-5Mn alloy was improved, while the tensile property decreased, especially the fractureelongation of hot-rolled Ti-5Mn alloy decreased by65%. The best combination of tensilestrength and elongation lies in Ti-Mn alloy with the composition point at5wt.%.
The electrochemical tests indicated that Ti-Mn alloys showed similar corrosionresistance like pure Ti in artificial saliva without any addition, while in the fluorinatedartificial saliava, Ti-Mn alloys didn’t show obvious deterioration like pure Ti. However, Ti-Mn alloys, after the breakdown of the passivation at around1.2Volts, fail to repassivatelike pure Ti. After immersion in the different artificial saliva for7d, Ti ions and Mn ionsreleased from the substrate due to the damage of the passivation coating. The released amountof Ti ions was maximum in artificial saliva with addition of NaF and lactic acid. Pure Ti andTi-5Mn alloy were passivated in human bile environment, and the passive current density wasmore than0.1mA/cm2, indicating better corrosion resistance. The corrosion resistance ofas-cast Ti-5Mn alloy was similar to pure Ti in human bile with pH6.8and pH7.0, and it wasbetter than pure Ti in weakly alkaline human bile with pH7.4, which exhibited higher selfcorrosion potential.
The contact anglesof Ti-Mn alloy with different Mn contents were less than90°whencontact with water and glycerol, suggesting hydrophilic property. The contact angle increasedwith increasing Mn content. The surface energy of as-cast Ti-5Mn alloy was least in the fourkinds of Ti-Mn alloys, which was similer to that of pure Ti. After the immersion of Ti andTi-5Mn alloy in human bile, the UV spectra showed the characteristic absorption peak,suggesting that there was no aggregation and adherence of the detached bilirubin and calciumbilirubinte on the surface of Ti and Ti-5Mn alloy and little influence on the composition ofbile. After immersion in human bile for3d, pure Ti and Ti-5Mn alloy had no effect on the thephospholipid of human bile, while with the increase of immersion time (7d), the alloysinteracted with the phospholipid of human bile, resulting in the change of characteristic peakof phospholipid on FT-IR spectra. The drug-loading paclitaxel/PLGA (PTA/PLGA)composite coating was prepared on pure Ti and Ti-5Mn alloy by sprying method, the surfaceof which was uniform and exhibited some directivity. The contact angle of Ti and Ti-5Mnalloy with drug-loading paclitaxel film didn’t change, indicating that there was no influenceof drug-loading film on the hydrophilicity. After immersion in human bile for3d and7d,PTX/PlGA drug loaded coating exhibited no effect on the composition of human bile, such asbilirubin and phospholipid. The in vitro cytotoxicity test shows that the in vitro cytotoxicitygrade of Ti-Mn alloys for L929fibroblast cells and MG63osteosarcoma cells is1grade,namely mild toxicity. Moreover, it has been found that the inhibition of the cell growthaggravates with the increase of Mn content in the testing alloys, which indicates slighttoxicity of Mn to the cultured cells.
铸态Ti-Mn合金的显微组织随Mn含量增加，由单一的等轴-Ti相逐渐演变成由-Ti和TiMn相组成的双相组织；当Mn含量达10wt.%时，合金中还会出现Ti0.48Mn0.52相。铸态Ti-Mn合金的屈服强度和断裂延伸率随Mn含量的增加先增加后降低，抗拉强度、维氏硬度和耐磨性能均随Mn含量增加而增加。与干摩擦条件下的磨损失重相比，在以模拟唾液为润滑的湿摩擦条件下，Ti及铸态Ti-Mn合金的磨损失重降低，耐磨性提高。与铸态Ti-5Mn合金相比，轧制态Ti-5Mn合金的晶粒尺寸明显长大，具有较高的显微硬度和耐磨性，但是力学性能明显下降，断裂延伸率下降了约65%。铸态Ti-5Mn合金具有最佳的强度和塑性配合。
在未添加任何成分的模拟唾液中，铸态Ti-Mn合金的电化学腐蚀抗力与纯Ti相近；在含氟的模拟唾液中，纯Ti的耐腐蚀性恶化并发生再钝化，而铸态Ti-Mn合金的耐腐蚀性未明显恶化并未发生再钝化。铸态Ti-Mn合金在几种含有不同添加成分的模拟唾液中浸泡7d后，表面钝化膜发生破坏，引起基体中Ti离子和Mn离子的析出；合金在同时添加NaF和乳酸的模拟唾液中的Ti离子析出量最高。纯钛和铸态Ti-5Mn合金在人体胆汁中呈现钝化现象，维钝电流密度略大于0.1mA/cm2，具有较强的耐腐蚀性。铸态Ti-5Mn合金在pH6.8和pH7.0的人体胆汁中具有与纯钛相当的耐腐蚀性；在pH7.4的弱碱性人体胆汁中，具有较高的自腐蚀电位，耐腐蚀性略优于纯钛。
不同锰含量的Ti-Mn合金与水和丙三醇的表面接触角均小于90°，为亲水表面；随合金中Mn元素含量的增加，Ti-Mn合金与水和丙三醇的表面接触角增加。Ti-5Mn合金的表面能在四种Ti-Mn合金中最小，其值与纯钛的表面能大小相当。Ti和Ti-5Mn合金与胆汁接触后，材料表面未发生游离态胆红素或胆红素钙等的聚集和粘附，对胆汁中胆红素的影响较小。纯钛和Ti-5Mn合金在胆汁中浸泡3d时与胆汁中的磷脂没有明显的相互作用；随着浸泡时间的延长（7d），两种材料与胆汁中的磷脂发生了一定的相互作用，引起红外谱图上磷脂的特征峰位置和强度发生变化。通过喷涂方法在纯Ti和Ti-5Mn合金表面制备的PTX/PLGA载药涂层，涂层表明均匀，具有一定的方向性；其接触角与裸金属表面接触角相近。PTX/PLGA载药涂层在人体胆汁中浸泡3d和7d后，对胆汁中胆红素和磷脂成分没有产生明显的影响。体外细胞毒性测试发现，铸态Ti-Mn合金对小鼠成纤维细胞L929和骨肉瘤细胞MG63的毒性级别为1级，属于微毒范畴。随合金中Mn含量的增加，培养的细胞的存活能力在明显下降，说明Mn离子溶出之后对L929细胞和MG63细胞的存活具有一定的毒性。
Ti-Mn alloys with different Mn content (2,5,8,10wt.%) were developed in the presentwork and various experiments have been carried out to investigate the microstructure andphase composition，tensile properties, in vitro electrochemical corrosion in simulated oralenvironment and bile environment, ion release behavior and the in vitro cytotoxicity, withpure titanium as control. The purpose of the study was to explore the feasibility of Ti-Mnalloys used as potential dental materials and biliray stent materials. Optical microscope,scanning electron microscope (SEM) and X-ray diffraction (XRD) were employed to studythe evolvement of microstructure and phase composition with the alloying element content.Tension property was investigated with universal materials testing machine. Microhardnessand wear resistance had been studied with digital hardness tester and ball-on-flat tribometer.Electrochemical behaviors in the artificial saliva were analyzed by methods of open circuitpotential (OCP), electrochemical impedance spectroscopy and dynamic polarization potential.The immersion corrosion behaviors of the alloys in artificial saliva had also been studied withInductively Coupled Plasma Optical Emission Spectrometer（ICP-OES）, SEM and XRD.Furthermore, the in vitro toxicity of the alloys to L929and MG63cell lines had beenevaluated by MTT method.
The microstructure of as-cast Ti-Mn alloys changes from single-Ti phase to-Ti+TiMn precipitation phase with the increase of Mn content, and Ti0.48Mn0.52phase wasobserved when Mn content arrived10wt.%. The yield strength and fracture elongation ofas-cast Ti-Mn alloy first increased and then decreased with the increase of Mn content, whilethe tensile strength, microhardness and wear resistance increased with the increase of Mncontent. Compared with the wear loss under dry condition, the wear loss of Ti and as-castTi-Mn alloy decreased under the wet condition with artificial saliva as lubricant, indicatingthe improved wear resistance. Compared with the as-cast Ti-5Mn alloy, the grain size ofhot-rolled Ti-5Mn alloy increased, and the microhardness and wear resistance of hot rolledTi-5Mn alloy was improved, while the tensile property decreased, especially the fractureelongation of hot-rolled Ti-5Mn alloy decreased by65%. The best combination of tensilestrength and elongation lies in Ti-Mn alloy with the composition point at5wt.%.
The electrochemical tests indicated that Ti-Mn alloys showed similar corrosionresistance like pure Ti in artificial saliva without any addition, while in the fluorinatedartificial saliava, Ti-Mn alloys didn’t show obvious deterioration like pure Ti. However, Ti-Mn alloys, after the breakdown of the passivation at around1.2Volts, fail to repassivatelike pure Ti. After immersion in the different artificial saliva for7d, Ti ions and Mn ionsreleased from the substrate due to the damage of the passivation coating. The released amountof Ti ions was maximum in artificial saliva with addition of NaF and lactic acid. Pure Ti andTi-5Mn alloy were passivated in human bile environment, and the passive current density wasmore than0.1mA/cm2, indicating better corrosion resistance. The corrosion resistance ofas-cast Ti-5Mn alloy was similar to pure Ti in human bile with pH6.8and pH7.0, and it wasbetter than pure Ti in weakly alkaline human bile with pH7.4, which exhibited higher selfcorrosion potential.
The contact anglesof Ti-Mn alloy with different Mn contents were less than90°whencontact with water and glycerol, suggesting hydrophilic property. The contact angle increasedwith increasing Mn content. The surface energy of as-cast Ti-5Mn alloy was least in the fourkinds of Ti-Mn alloys, which was similer to that of pure Ti. After the immersion of Ti andTi-5Mn alloy in human bile, the UV spectra showed the characteristic absorption peak,suggesting that there was no aggregation and adherence of the detached bilirubin and calciumbilirubinte on the surface of Ti and Ti-5Mn alloy and little influence on the composition ofbile. After immersion in human bile for3d, pure Ti and Ti-5Mn alloy had no effect on the thephospholipid of human bile, while with the increase of immersion time (7d), the alloysinteracted with the phospholipid of human bile, resulting in the change of characteristic peakof phospholipid on FT-IR spectra. The drug-loading paclitaxel/PLGA (PTA/PLGA)composite coating was prepared on pure Ti and Ti-5Mn alloy by sprying method, the surfaceof which was uniform and exhibited some directivity. The contact angle of Ti and Ti-5Mnalloy with drug-loading paclitaxel film didn’t change, indicating that there was no influenceof drug-loading film on the hydrophilicity. After immersion in human bile for3d and7d,PTX/PlGA drug loaded coating exhibited no effect on the composition of human bile, such asbilirubin and phospholipid. The in vitro cytotoxicity test shows that the in vitro cytotoxicitygrade of Ti-Mn alloys for L929fibroblast cells and MG63osteosarcoma cells is1grade,namely mild toxicity. Moreover, it has been found that the inhibition of the cell growthaggravates with the increase of Mn content in the testing alloys, which indicates slighttoxicity of Mn to the cultured cells.
引文
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