金属特性氧化物负载的Ti-O薄膜制备及其在热带海岛气候下抗菌耐蚀性能研究

The microbial corrosion under Hainan tropical island climate is serious. In previous studies, applicant found that the carbon-doped TiO crystal showed metallic properties, which beneficial to excitation, separation and transport of photo-generated carriers of Ti-O films while it exhibits photocatalytic activity. This application is intended to develop the Ti-O films with metal characteristics oxide load and photocatalytic activity, and make the Ti-O films applied in corrosion and protection of engineering materials at adequate lighting Hainan. Carbon-doped or carbon and nitrogen co-doped Ti-O film (hereinafter referred to as the thin film )will be designed and synthesized by magnetron sputtering at room temperature on carbon steel substrate. Researching and preferring the interface process in order to obtain good adhesion between film and substrate. The property of antimicrobial and corrosion resistance will be evaluated by pasting film method, Electrochemical testing and outdoor soaking under different regions seawater electrolyte. And then the thin film sputtering process will be also optimized. Band structure and electronic density of states of the crystal phase of in the film will be calculated using first-principles. This study aims to: i) Arriving at controllable preparation of the metal load phase. Obtaining the Ti-O film with metal characteristics oxide load, high adhesion, excellent antimicrobial and corrosion resistance under tropical island weather conditions; ii) Clarifying correlation between the prepared process and composition, structure, mechanical properties, photocatalytic, antibacterial corrosion resistance properties of the thin film; iii) Confirming the presence of metal load crystalline phases in the thin-film and proposing the photocatalytic mechanism of the thin film.

海南热带海岛气候条件下微生物腐蚀严重。申请者前期研究中发现C掺杂TiO晶体具有金属特性，利于Ti-O薄膜光生载流子的激发、分离和输运而使其表现出光催化活性。本申请拟开发具有光催化活性的金属特性氧化物负载Ti-O薄膜，应用于光照充足的海南工程材料的腐蚀防护。设计在碳钢基体上磁控溅射法室温制备碳掺杂和碳氮共掺Ti-O薄膜（以下简称薄膜）。研究并优选界面工艺以期获得良好的膜基结合强度。采用贴膜法和不同区域海水电解液下的电化学测试及室外浸泡，评价薄膜的抗菌耐蚀性能并优化溅射工艺。运用第一性原理计算研究薄膜内晶体相的能带结构和电子态密度。本研究旨在：1）实现金属负载相的可控制备。获得膜基结合强度高、在热带海岛气候条件下抗菌耐蚀性能优良的金属特性氧化物负载Ti-O薄膜；2）阐明薄膜制备工艺与成分、结构、力学性能、光催化和抗菌耐蚀性能间的相关性；3）确证薄膜内金属氧化物负载相的存在，提出薄膜光催化机理。

采用了不同的磁控溅射工艺参数制备获得了多个系列的碳掺杂和碳氮共掺杂薄膜。研究发现，采用CO2作为唯一的反应气体提供碳源和氧源时，易于得到含有TiO金属相的碳掺杂Ti-O薄膜。.PEM调控下制备的碳掺杂Ti-O薄膜主要为金红石相，表面多呈现柱状或岛状结构，这种结构有利于提高光催化效率；CO2反应气体流量的增加有利于金属特性氧化物TiO相的形成。.研究在Ti-O薄膜和碳钢基体之间制备的纯Ti过渡层对膜基结合强度的影响，结果发现通过调控Ti过渡层的厚度比使用负偏压更能显著提升膜基结合强度，同时还能提高薄膜硬度和弹性模量。.正交实验设计研究的结果发现，采用直流溅射的方法时保持功率100W、沉积温度300℃、CO2气体流量12sccm条件下制备得到的碳掺杂Ti-O薄膜拥有最佳的综合力学性能，在500-600℃下退火可在提升结合强度的同时获得好的光催化活性。.理论计算研究发现对TiO2禁带宽度改变的能力从P掺杂、C掺杂和Si掺杂TiO2依次减弱，但是由于掺杂C带来的杂质能级出现在价带与导带之间，使得C掺杂TiO2光吸收边缘的红移更加明显；C的掺杂能够从P原子上捕获多余的电子，从而防止由于P的掺杂使得Ti4+向Ti3+的转变而造成禁带宽度的扩大；共掺杂比单掺杂具有更高的可见光催化活性，其中C/Si 共掺杂TiO2的光催化活性最高。.项目执行期间成功获得了具有光催化活性的固载Ti-O薄膜材料，获得了可信的实验数据，对今后继续深入开展该类材料应用于光催化抗菌领域提供了参考。