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Chinese Journal of Materials Research  2020, Vol. 34 Issue (7): 489-494    DOI: 10.11901/1005.3093.2019.577
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Preparation and Formation Mechanism of a Novel TiO2 Nano Bowl Array with Large Hole Diameter
YU Zexin, SANG Lixia()
Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education and Key Laboratory of Heat Transfer and Energy Conversion, Beijing Municipality, Beijing University of Technology, Beijing, 100124, China
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YU Zexin, SANG Lixia. Preparation and Formation Mechanism of a Novel TiO2 Nano Bowl Array with Large Hole Diameter. Chinese Journal of Materials Research, 2020, 34(7): 489-494.

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Abstract  

In order to simplify the complex process of preparing TiO2 nano bowl array by traditional method, the basic principle of two-step anodizing method was adopted. Namely, during the first and second anodizing process, oxidation voltage and electrolyte concentration all keep as before, but varying the anodizing time. The first anodizing time is 1 hour, and the second anodizing time changes from 0 s to 140 s. After the first anodizing, as the initial oxide layer for the second anodization, the residual bowl like pits on the surface of Ti-sheet may undergo three stages of growth. Firstly, the TiO2 barrier began to grow longitudinally at the bottom of the pit. Then the dissolution of the electrolyte at the edge of the bowl took effect, and nano pores appeared in the bowl. Secondly, the longitudinal growth rate of the barrier layer and the dissolution rate of the electrolyte reached a relative balance. The bottom center of the TiO2 barrier layer was first corroded, then the corrosion position changed around the bowl edge, and other nanopores were corroded laterally. Thirdly, the relationship between the longitudinal corrosion rate and the transverse corrosion rate was constantly changing, which showed that the depth of the nanopore in the bowl increased all the time, but the diameter of the bowl and the pore first increased and then decreased. Under the condition of the growth rate of TiO2 barrier layer was in relative equilibrium with the chemical dissolution rate of electrolyte, and the longitudinal corrosion rate was relatively consistent with the transverse corrosion rate, TiO2 nano bowl array with large pore diameter was synthesized. The optimal second anodizing time was 110 s, and the diameter of bowl was 133 nm.

Key words:  surface and interface of materials      TiO2 nano bowl      two-step anodizing method      TiO2 nanopore      corrosion      TiO2 barrier layer     
Received:  10 December 2019     
ZTFLH:  TB383  
Fund: National Natural Science Foundation of China(51776009)

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https://www.cjmr.org/EN/10.11901/1005.3093.2019.577     OR     https://www.cjmr.org/EN/Y2020/V34/I7/489

Fig.1  Current-time curves of TiO2 nano bowl array in the second anodizing process (a) and schematic diagram of the second anodizing process (b)
Fig.2  SEM images of TiO2 surface when the second anodizing time is 10 s (a) and 20 s (b)
Fig.3  SEM images of TiO2 surface when the second anodizing time is 40 s (a, b) and 60 s (c, d)
Fig.4  SEM images of TiO2 surface when the second anodizing time is 80 s (a, b) and 90 s (c, d)
Fig.5  SEM images of TiO2 surface when the second anodizing time is 100 s (a, b), 110 s (c, d) and 130 s (e, f)
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