阳极氧化法制备氧化锆纳米管阵列的研究

Fabrication of Zirconia Nanotube Arrays by Anodization

采用阳极氧化法分别在1mol/L(NH4)2SO4+0.5%NH4F(质量分数,下同)的无机水溶液(电压20V,氧化时间3h)和甲酰胺+甘油(体积比1:1)+1%NH4F的有机溶液(电压50V,氧化时间24h)中制备高度有序的氧化锆纳米管阵列,并用SEM和TEM对其形貌进行表征。在无机溶液中形成的纳米管长度19μm,直径40nm。有机溶液中形成的纳米管高度有序,长度110μm,直径200nm。XRD衍射谱表明在无机溶液中形成的氧化锆纳米管为正交晶型。在有机溶液中形成的氧化锆纳米管为非晶结构,在400℃退火3h后转换为单斜相和四方相的混合相,在800℃退火后全部转换为单斜相。

Highly-ordered and uniform zirconia （ZrO2） nanotube arrays were fabricated by electrochemical anodic oxidation on a pure zirconium sheet in 1 mol/L （NH4）2SO4＋0.5% （mass fraction） NH4F （20 V, 3 h） inorganic electrolyte and formamide ＋glycerol （volume ratio 1：1）＋ 1% （mass fraction） NH4F （50 V, 24 h） organic electrolyte. SEM and TEM techniques were used to characterize the ZrO2 nanotubes morphology. It is showed that these nanotubes have a length of 19 gm, a diameter of 40nm in inorganic electrolyte and a length of 110μm, a diameter of 200 nm in organic electrolyte. XRD diffraction pattern shows that the zirconia nanotubes are orthorhombic phase in inorganic electrolyte. In the organic electrolyte the zirconia nanotubes have amorphous phase structure. The mixed phase of the monoclinic and tetragonal phase appears after annealed in air at 400℃ for 3 h; while after annealed in air at 800 ℃ for 3 h, the zirconia crystals in monoclinic phase can be obtained.