不同结构氧化钛薄膜的表面活化及其对生物相容性的影响
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摘要
本文采用非平衡磁控溅射沉积技术制备了具有不同晶体结构的Ti-O薄膜,对所得Ti-O薄膜运用碱活化处理、酸活化处理、NH_3等离子浸没注入活化处理等3种方法进行表面处理,期望在材料表面获得羟基和氨基活性基团。运用X射线衍射(XRD)研究了薄膜的表面晶体结构;利用傅里叶红外技术(FTIR)、X射线光电子能谱仪(XPS)、扫描电子显微镜(SEM)、接触角测量、方块电阻测量等手段对活化处理前后样品表面的进行表征;并对活化前后样品进行了体外人脐静脉血管内皮细胞(HUVEC)培养、血小板黏附实验及LDH实验评价了活化处理对薄膜表面细胞相容性和血液相容性的影响。此外,本文对氧化钛薄膜表面活化机理进行了探讨。
结果表明,运用以上方法可以在锐钛矿型以及金红石与锐钛矿的混晶结构Ti-O薄膜表面形成活性基团,并可长期稳定存在于薄膜表面;相比于金红石型与不饱和Ti-O薄膜,混晶结构和锐钛矿型具有较好的羟基活化能力;活化处理后,Ti-O薄膜表面接触角减小,薄膜表面亲水性提高;SEM结果显示处理前后表面形貌变化不大;生物相容性实验表明,活化处理后样品表面细胞生长数目多于活化前样品,血小板黏附数量少于活化前样品,分析认为表面活性基团的存在有利于提高Ti-O薄膜材料的生物相容性。本文认为,Ti-O薄膜表面酸性羟基的存在是使其表面活化得到碱性羟基的前提;另外,材料的表面形貌、晶体结构等表面性质也会影响其活性化能力。
In this work, Ti-O films with different crystal structure were synthesized by unbalanced magnetron sputtering system. Then the Ti-O films were treated by alkali solution, H_2SO_4 and H_2O_2 solution, and plasma immersion ion implantation (PIII) using ammonia gases to obtain functional groups (hydroxyl and amino). The crystal structures of films were characterized by the X-ray Diffraction (XRD).
Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), contact-angle measurement and sheet resistance measurement were used to investigate the characteristics of Ti-O films and modified Ti-O film surface. Human umbilical vein endothelial cells (HUVEC) were in vitro seeded to the treated and untreated Ti-O films surface to evaluate the cell compatibility. The behavior of blood platelet adhesion were studied by light microscope and SEM after activation treatment to evaluate the blood compatibility. Furthermore, the relationship between the Ti-O film structure and its bioactivity is discussed in this work.
The results revealed that films can produce functional groups activated by the way as mentioned above, and the groups firmly bonded to the surface. Compared to films of rutile, anatase film and film mixed with anatase and rutile possesses the better functional groups bioactivity. The results of SEM suggested that the surface morphology did not change after treated and the contact angle of the film surface decreased. The cell and platelet adhesion tests demonstrated that there were more cells and less platelet adhered to the treated Ti-O films surfaces than untreated ones. This result indicates the functional groups can promote the adhesion and growth of endothelial cells and reduce the number of adherent platelets. This paper thinks that obtaining basic hydroxyl on the premise of the acid hydroxyl existence on the surface of the Ti-0 films. In addition, the surface morphology and crystal structure also affect the films functional groups bioactivity.
结果表明,运用以上方法可以在锐钛矿型以及金红石与锐钛矿的混晶结构Ti-O薄膜表面形成活性基团,并可长期稳定存在于薄膜表面;相比于金红石型与不饱和Ti-O薄膜,混晶结构和锐钛矿型具有较好的羟基活化能力;活化处理后,Ti-O薄膜表面接触角减小,薄膜表面亲水性提高;SEM结果显示处理前后表面形貌变化不大;生物相容性实验表明,活化处理后样品表面细胞生长数目多于活化前样品,血小板黏附数量少于活化前样品,分析认为表面活性基团的存在有利于提高Ti-O薄膜材料的生物相容性。本文认为,Ti-O薄膜表面酸性羟基的存在是使其表面活化得到碱性羟基的前提;另外,材料的表面形貌、晶体结构等表面性质也会影响其活性化能力。
In this work, Ti-O films with different crystal structure were synthesized by unbalanced magnetron sputtering system. Then the Ti-O films were treated by alkali solution, H_2SO_4 and H_2O_2 solution, and plasma immersion ion implantation (PIII) using ammonia gases to obtain functional groups (hydroxyl and amino). The crystal structures of films were characterized by the X-ray Diffraction (XRD).
Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), contact-angle measurement and sheet resistance measurement were used to investigate the characteristics of Ti-O films and modified Ti-O film surface. Human umbilical vein endothelial cells (HUVEC) were in vitro seeded to the treated and untreated Ti-O films surface to evaluate the cell compatibility. The behavior of blood platelet adhesion were studied by light microscope and SEM after activation treatment to evaluate the blood compatibility. Furthermore, the relationship between the Ti-O film structure and its bioactivity is discussed in this work.
The results revealed that films can produce functional groups activated by the way as mentioned above, and the groups firmly bonded to the surface. Compared to films of rutile, anatase film and film mixed with anatase and rutile possesses the better functional groups bioactivity. The results of SEM suggested that the surface morphology did not change after treated and the contact angle of the film surface decreased. The cell and platelet adhesion tests demonstrated that there were more cells and less platelet adhered to the treated Ti-O films surfaces than untreated ones. This result indicates the functional groups can promote the adhesion and growth of endothelial cells and reduce the number of adherent platelets. This paper thinks that obtaining basic hydroxyl on the premise of the acid hydroxyl existence on the surface of the Ti-0 films. In addition, the surface morphology and crystal structure also affect the films functional groups bioactivity.
引文
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