Preparation and anti-corrosion properties of photoresponsive titanium based nano-films
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摘要: 基于企业生产研究背景与优势，提出利用廉价且易得的钛源（例如：TiOSO4）材料为原料，采用反应简单、操作便捷的sol-gel法在基材表面制备一层或多层纳米级钛基薄膜，研究镀膜后基材在紫外光光照和暗态条件下的耐腐蚀能力，意图通过镀膜大幅度提高基材的耐腐蚀能力。通过选择钛源、沉淀剂、水溶胶的钛浓度、络合剂比例和反应温度优化水溶胶制备工艺；同时研究不同浓度水溶胶的粘温特性及采用水溶胶浓缩为干凝胶的方法对水溶胶中颗粒粒径和形貌进行观测，溶胶粒径均小于50 nm。后期采用匀速提拉法在基板表面进行不同层数薄膜的制备，采用相应热处理得到纳米钛基薄膜，并研究纳米薄膜的形貌。最后将基片制作成电极浸渍在3.5%氯化钠溶液中测试其防腐性能，制备纳米薄膜表面颗粒粒径均小于50 nm，五层膜厚度在1 μm左右。防腐性能测试结果表明在基材表面制备防腐薄膜提高了基材腐蚀电位、降低其腐蚀电流，在暗态条件下，相较基板的防护效率最高可达99.73%；在紫外光照下，相较基板的防护效率最高可达99.14%。同时通过暗态和紫外光照下的基板的开路电位分析，在紫外光照射下相对于暗态下的开路电位出现不同程度负移的情况，展现出薄膜具有光响应性。Abstract: Based on the research background and advantages of enterprise production, cheap and easily available titanium sources (such as TiOSO4) were used as raw materials to prepare one or more nano-titanium-based films on the substrate surface by sol-gel method with simple reaction and convenient operation. The corrosion resistance of substrate after coating was studied under ultraviolet light and dark state conditions, with the intention of greatly improving the corrosion resistance of the substrate through the coating. The preparation process of hydrosol was optimized by selecting titanium source, precipitant, titanium concentration of hydrosol, proportion of complexing agent and reaction temperature. At the same time, the viscosity and temperature characteristics of hydrosol at different concentrations were studied, and the size and morphology of the particles were observed by the sol-gel method. The particle size of the sol was less than 50 nm. In the later stage, the films with different layers were prepared on the substrate surface by uniform pulling method, the nano titanium based films were obtained by corresponding heat treatment, and the morphology of the nano films was studied. Finally, the substrate was made into an electrode and immersed in a 3.5% sodium chloride solution to test its anti-corrosion performance. The particle size on the surface of the nano-film was less than 50 nm, and the thickness of the five layers of film was 1 μm. The results show that the corrosion resistance of the substrate can be improved by anti-corrosive film on the substrate surface. The protection efficiency is up to 99.73% and 99.14% respectively in dark state and under ultraviolet light, compared with that of the substrate. Meanwhile, through the analysis of the open circuit potential of the substrate under dark state and ultraviolet light, the negative shift of the open circuit potential of the substrate under ultraviolet light is different from that of the dark state, which shows the light response of the film.
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Key words:
- nano-titanium-based film /
- sol-gel /
- titanium-based hydrosol /
- anti-corrosive /
- TiOSO4 /
- light response
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图 3 以硫酸氧钛为钛源的水溶胶粘温特性
Figure 3. Viscosity-temperature characteristics of the hydrosol using titanium oxysulfate as titanium source
图 4 以硫酸氧钛为原料的水溶胶
Figure 4. Hydrosol using TiOSO4 as raw material
(a) 0.05 mol/L；(b) 0.1 mol/L；(c) 0.15 mol/L；(d) 0.2 mol/L
图 5 以硫酸氧钛为原料的干凝胶SEM形貌
Figure 5. SEM images of dry-gel using TiOSO4 as raw material
(a) 0.05 mol/L；(b) 0.1 mol/L；(c) 0.15 mol/L；(d) 0.2 mol/L
图 6 Ti浓度0.05 mol/L的以TiOSO4为原料的水溶胶制备薄膜的SEM形貌（1～5层）
Figure 6. SEM images of films prepared by TiOSO4 hydrosol with 0.05 mol/L Ti (layers 1～5)
图 7 Ti浓度0.1 mol/L 的以TiOSO4为原料的水溶胶制备薄膜的SEM形貌（1～5层）
Figure 7. SEM images of films prepared by TiOSO4 hydrosol with 0.1 mol/L Ti (layers 1～5)
图 8 Ti浓度0.15 mol/L 的以TiOSO4为原料的水溶胶制备薄膜的SEM形貌（1～5层）
Figure 8. SEM images of films prepared by TiOSO4 hydrosol with 0.15 mol/L Ti (layers 1～5)
图 9 Ti浓度0.2 mol/L 的以TiOSO4为原料的水溶胶制备薄膜的SEM形貌（1～5层）
Figure 9. SEM images of films prepared by TiOSO4 hydrosol with 0.2 mol/L Ti (layers 1～5)
图 10 不同Ti浓度时以TiOSO4为原料的水溶胶制备五层薄膜的EDS谱
Figure 10. EDS spectra of five-layer thin films prepared with TiOSO4 hydrosol at different Ti concentrations
(a) 0.05 mol/L；(b) 0.1 mol/L；(c) 0.15 mol/L；(d) 0.2 mol/L
图 11 不同Ti浓度时以TiOSO4为原料的水溶胶制备五层薄膜侧视图
Figure 11. Side view images of five-layer thin films prepared with TiOSO4 hydrosol at different Ti concentrations
(a) 0.05 mol/L；(b) 0.1 mol/L；(c) 0.15 mol/L；(d) 0.2 mol/L
图 13 不同钛浓度水溶胶制备薄膜覆盖的基板在暗态下测试的Tafel曲线
钛浓度：（a） 0.05 mol/L；（b） 0.1 mol/L；（c） 0.15 mol/L；（d） 0.2 mol/L
Figure 13. Tafel curves of thin film-covered substrates prepared with TiOSO4 hydrosol at different Ti concentrations in dark state
图 14 不同钛浓度水溶胶制备薄膜覆盖的基板在紫外光下测试的Tafel曲线
钛浓度：（a） 0.05 mol/L；（b） 0.1 mol/L；（c） 0.15 mol/L；（d） 0.2 mol/L
Figure 14. Tafel curves of thin film-covered substrates prepared with TiOSO4 hydrosol at different Ti concentrations under UV light
表 1 试验试剂
Table 1. Experimental reagents
试剂名称 分子式 生产厂家 纯度 硫酸氧钛 TiOSO4·H2O 天津市光复精细化工研究所 分析纯 氨水 NH4OH 成都市科隆化学品有限公司 分析纯 硝酸 HNO3 重庆川东化工集团有限公司 分析纯 无水乙醇 C2H5OH 成都金山化学试剂有限公司 分析纯 
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表 2 以硫酸氧钛为原料的薄膜覆盖的基片对应暗态和紫外光下开路电位
Table 2. Open circuit potentials of thin film-covered substrates prepared with TiOSO4 in dark state and under UV light
样品编号 暗态OCP/V 紫外光照态OCP/V A-1 −0.173 −0.224 A-2 −0.165 −0.187 A-3 −0.18 −0.191 A-4 −0.129 −0.163 A-5 −0.149 −0.187 B-1 −0.168 −0.175 B-2 −0.155 −0.155 B-3 −0.14 −0.166 B-4 −0.17 −0.173 B-5 −0.195 −0.197 C-1 −0.211 −0.218 C-2 −0.197 −0.212 C-3 −0.202 −0.219 C-4 −0.194 −0.209 C-5 −0.176 −0.205 D-1 −0.26 −0.273 D-2 −0.219 −0.227 D-3 −0.163 −0.197 D-4 −0.178 −0.205 D-5 −0.216 −0.235
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