Zirconia (ZrO) is a hard and brittle dental implant material without anti-infective property. This work reports the preparation of a tertiary micro-nano hierarchical structure on a ZrO surface via femtosecond laser texturing combined with magnetron sputtering deposition of an Ag layer (Ag/ZrO), aiming to achieve a superhydrophobic synergistic antibacterial effect. Laser-scanning pitch and Ag layer thickness were systematically optimized for obtaining the tertiary hierarchical structure. The wettabilities, antibacterial properties and durabilities of various ZrO and stearic acid modified Ag/ZrO (S-Ag/ZrO) surfaces were further tested and comparatively analyzed. The results revealed that the optimal process parameters were a laser-scanning pitch of 30 μm and an Ag layer thickness of 100 nm. The as-obtained S-Ag/ZrO sample displayed a tertiary micro-nano hierarchical structure, which was featured by a periodic regular conical micro-convex structure covered with ZrO nano-protrusions and Ag nanoparticles. This structure could not only greatly reduce the solid-liquid contact area to achieve outstanding superhydrophobicity and durability, it could also sustainably release bacteria-killing Ag to obtain an antibacterial ratio of 95.1 % and ensure a long-term antibacterial effect. In addition, the optimal S-Ag/ZrO sample having this structure showed a PC12 cell survival rate of up to 81.75 %, demonstrating its good biocompatibility. This work may be of great inspiration and reference for the expansion of the use of ZrO in dentistry.

中文翻译：

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飞秒激光织构和表面改性制备具有三级结构的超疏水协同抗菌ZrO2基表面


氧化锆（ZrO）是一种硬而脆的牙科种植材料，无抗感染性能。该工作报道了通过飞秒激光织构结合磁控溅射沉积Ag层（Ag/ZrO）在ZrO表面制备三级微纳分级结构，旨在实现超疏水协同抗菌效果。系统地优化了激光扫描间距和银层厚度以获得三级结构。对各种ZrO和硬脂酸改性Ag/ZrO（S-Ag/ZrO）表面的润湿性、抗菌性能和耐久性进行了进一步测试和对比分析。结果表明，最佳工艺参数为激光扫描间距为30μm，Ag层厚度为100nm。所获得的S-Ag/ZrO样品呈现出三级微纳米分级结构，其特征是周期性规则圆锥形微凸结构被ZrO纳米突起和Ag纳米粒子覆盖。这种结构不仅可以大大减少固液接触面积，实现优异的超疏水性和耐用性，还可以持续释放杀菌Ag，获得95.1%的抗菌率，确保长期抗菌效果。此外，具有该结构的最佳S-Ag/ZrO样品的PC12细胞存活率高达81.75%，证明了其良好的生物相容性。这项工作对于扩大ZrO在牙科中的应用可能具有很大的启发和参考意义。