F含量对ZrO2纳米管形貌和相组成的影响

doi:10.3724/SP.J.1077.2011.11411

摘要/Abstract

摘要：

采用阳极氧化法在丙三醇+NH₄F+5vol% H₂O的电解液中制备了高度有序的ZrO₂纳米管阵列, 详细考察了溶液中F含量(0.1~1.1 mol/L)对纳米管形貌﹑相结构和化学组成的影响. 利用扫描电子显微镜(SEM), X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)对不同条件下制备的管径约90~130 nm, 管长约4.8~9.1 μm的纳米管形貌和结构进行了表征. 结果显示, 在含有0.7 mol/L NH₄F的电解液中获得了高度有序且垂直导向的四方相ZrO₂纳米管阵列, 而在较低浓度的电解液中制备的纳米管阵列为无定形结构, 较高浓度下纳米管阵列出现坍塌. 此外, 纳米管近表层处F/O原子比也随F^-浓度的变化而变化.

关键词: ZrO₂, 纳米管阵列, 氟, 四方相, 阳极氧化

Abstract:

The present research demonstrates the significant influence of fluoride content on the morphology, phase structure and chemical composition of ZrO₂ nanotube arrays which were prepared via a direct electrochemical anodization of zirconium foil in glycerol-based electrolytes composed of 5vol% H₂O and different contents of NH₄F from 0.1 mol/L to 1.1 mol/L. The as-prepared nanotube arrays with external diameter of 90-130 nm and length of 4.8- 9.1 μm were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectrum (XPS). The results show that the highly ordered and vertically aligned tetragonal ZrO₂ nanotube arrays can be obtained in the electrolyte containing 0.7 mol/L NH₄F, and they become amorphous at lower NH₄F concentration and collapse at higher NH₄F concentration. Moreover, the F/O atomic ratio near the top surface of nanotubes is also dependent on the F^- concentration in the electrolyte.

Key words: ZrO₂, nanotube arrays, fluoride, tetragonal phase, anodization

中图分类号:

TQ153

徐颖, 刘宣勇, 丁传贤. F含量对ZrO₂纳米管形貌和相组成的影响[J]. 无机材料学报, 2012, 27(1): 107-112.

XU Ying, LIU Xuan-Yong, DING Chuan-Xian. Effect of Fluoride Content on Morphology and Phase Composition of ZrO₂ Nanotubes[J]. Journal of Inorganic Materials, 2012, 27(1): 107-112.

图/表 6

Fig. 1 SEM images of zirconium anodized in glycerol + 5vol% H2O electrolyte with (a) 0.1 mol/L, (b) 0.5 mol/L, (c) 0.7 mol/L and (d) 1.1 mol/L NH4F at 80 V for 30 min

Fig. 2 Cross-sectional images of ZrO2 nanotube arrays formed in glycerol with: (a) 0.1 mol/L, (b) 0.5 mol/L, (c) 0.7 mol/L NH4F and (d) bottom view image of ZrO2 nanotube arrays formed in 0.7 mol/L NH4F containing electrolyte at 80 V for 30 min

Fig. 3 Current density to time curve of ZrO2 nanotube formed in different electrolytes at 80 V for 30 min

Fig. 4 Typical surface morphologies of nanotubes anodized in 0.7 mol/L NH4F electrolyte at 80 V for different time

Fig. 5 XRD patterns of ZrO2 nanotube layers formed in glycerol with different contents of NH4F

Fig. 6 XPS spectra of anodic ZrO2 nanotubular arrays obtained in glycerol-based electrolyte containing different concentration of NH4F

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F含量对ZrO₂纳米管形貌和相组成的影响

Effect of Fluoride Content on Morphology and Phase Composition of ZrO₂ Nanotubes

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