氧化锆陶瓷表面ZrO2纳米阵列的构建及其影响粘接的机制研究

Zirconia is a kind of ceramic materials most widely used in aesthetic repair of dental caries. The adhesive failure rate of zirconia restorations is rather high due to the limitation of its dense structure and chemical inertness. A large number of domestic and foreign research shows that surface modification can improve the bonding property of zirconia. But the existing surface modification methods only focus on surface roughening or chemical activation, there is still a lack of a zirconia surface modification method that can improve both mechanical interlock and chemical bonding at the same time. This study is inspired by the theory of bionic adhesion. In order to simulate the enamel bonding mechanism, this study is designed to construct demineralized enamel structure liked ZrO2 nanowires film on zirconia surface by combination of magnetron sputtering and anodic oxidation, and regulate the structure and morphology of nanoarrays. Moreover, by constructing zirconia-resin bonding “hybrid layer”, bionic zirconia bonding strategy is proposed and the effect of ZrO2 nanowires film on mechanical and chemical bonding between zirconia and resin is studied. This research is of great means for bionic modification of zirconia. It would also provide a new and promising strategy for improving the long-term longevity of adhesive zirconia restorations and the aesthetic repair treatment effect of tooth or dentition defects caused by dental carries.

氧化锆是龋病的美学修复治疗中应用最为广泛的一类陶瓷材料，但受其结构致密且化学活性低等特点的限制，锆瓷修复体临床粘接失败率较高。国内外大量研究通过对锆瓷进行表面改性提高其粘接性能，但现有的改性方法均以侧重表面粗化加强机械固位或化学活化其中一方面，尚缺少一种兼顾机械锁合力和化学结合力共同提升的锆瓷表面改性方法。受仿生粘接理论的启发，本研究模拟牙釉质粘接机制，拟联合应用磁控溅射和阳极氧化技术，在锆瓷表面制备出仿脱矿牙釉质 “蜂窝状”阵列结构的ZrO2纳米丝阵列薄膜涂层，并对其结构形貌进行精细调控，提出利用ZrO2纳米阵列构建锆瓷-树脂粘接“混合层”的氧化锆陶瓷仿生化粘接新策略，探索该薄膜涂层对锆瓷与树脂之间机械-化学结合的影响与相关机制。本研究对氧化锆陶瓷的仿生化功能改性具有重大意义，为有效改善氧化锆修复体粘接强度及长期临床寿命、提高龋病引发的牙体及牙列缺损的美学修复治疗效果提供新思路。

本课题针对牙科氧化锆陶瓷结构致密且化学活性低、现有锆瓷表面改性方法难以兼顾粘接界面的机械锁合力和化学结合力，因而导致锆瓷修复体临床粘接失败率较高的临床难题，从模拟牙釉质粘接机制角度入手，联合应用离子镀膜和阳极氧化技术，在锆瓷表面制备出仿脱矿牙釉质“蜂窝状”阵列结构的ZrO2NTs薄膜涂层，深入研究ZrO2NTs薄膜涂层对氧化锆-树脂粘接强度和耐久性的影响以及相关机制。主要成果如下：（1）成功利用离子镀膜法联合阳极氧化法，在氧化锆陶瓷表面构建出ZrO2NTs薄膜涂层，筛选出最优实验条件，并对该薄膜涂层的表面形貌和晶相结构进行表征。（2）ZrO2NTs薄膜涂层修饰后的氧化锆陶瓷具有良好的生物相容性、能够诱导间充质干细胞的成骨分化，同时具有抑菌和抗细菌黏附的能力。（3）研究了不同功能成分的锆瓷偶联剂涂布于ZrO2NTs薄膜涂层修饰后的氧化锆陶瓷表面，对氧化锆粘接效果的影响，结果证实在一定的纳米管管径范围内，ZrO2NTs薄膜涂层能够显著提高氧化锆陶瓷与树脂之间的粘接强度和粘接耐久性。（4）探索ZrO2NTs薄膜涂层提高氧化锆陶瓷粘接强度的机制，证实ZrO2NTs薄膜涂层能够提高氧化锆陶瓷的表面粗糙度；提高锆瓷偶联剂在氧化锆陶瓷表面的润湿性；偶联剂内功能单体能够渗透至纳米管内，有利于纳米管与树脂单体形成化学结合，从而形成氧化锆纳米管-树脂粘接“混合层”。本课题为有效改善氧化锆修复体粘接强度及长期临床寿命、提高龋病引发的牙体及牙列缺损的美学修复治疗效果具有重要意义。