阳极氧化电压对钛合金TC4阳极氧化TiO<sub>2</sub>膜层表面的影响*

doi:10.11901/1005.3093.2015.12.895

材料研究学报

2015, Vol. 29

Issue (12): 895-903 DOI: 10.11901/1005.3093.2015.12.895

本期目录 | 过刊浏览

阳极氧化电压对钛合金TC4阳极氧化TiO₂膜层表面的影响*

严继康^1,²,杨钢¹(

),唐婉霞^1,²,吴云峰¹,方树铭¹,施哲³

1. 昆明冶金研究院昆明 650031
2. 昆明理工大学材料科学与工程学院昆明 650093
3. 昆明理工大学冶金与能源工程学院昆明 650093

Effect of Applied Voltage on Performance of Anodic Oxidation Films of TiO₂ on TC4 Alloy

Jikang YAN^1,²,Gang YANG^1,^**(

),Wanxia TANG^1,²,Yunfeng WU¹,Shuming FANG¹,Zhe SHI³

1. Kunming Metallurgical Research Institute, Kunming 650031, China
2. Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China
3. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China

引用本文:

严继康,杨钢,唐婉霞,吴云峰,方树铭,施哲. 阳极氧化电压对钛合金TC4阳极氧化TiO₂膜层表面的影响*[J]. 材料研究学报, 2015, 29(12): 895-903.
Jikang YAN, Gang YANG, Wanxia TANG, Yunfeng WU, Shuming FANG, Zhe SHI. Effect of Applied Voltage on Performance of Anodic Oxidation Films of TiO₂ on TC4 Alloy[J]. Chinese Journal of Materials Research, 2015, 29(12): 895-903.

全文: PDF(5738 KB) HTML

摘要:

在草酸盐、硅酸盐和磷酸盐电解液体系中, 在钛合金Ti-6Al-4V(TC4)表面制备阳极氧化TiO₂膜层, 研究了TiO₂膜层的表面显微结构、化学组成和生物活性。在室温用恒压阳极氧化法制备TC4表面阳极氧化TiO₂膜, 以TC4为阳极, 不锈钢为阴极, 电解液组成为: 20 g/L的Na₂C₂O₄、10 g/L的Na₂SiO₃9H₂O、9.25 g/L的NaH₂PO₄和2 g/L的NaOH, 阳极氧化电压为10-120 V, 氧化时间50 min, 电源频率200 Hz。用XRD、AFM、SEM及XPS等手段分别测量了膜层的物相、三维形貌、氧化膜层表面的显微结构及化学组成。结果表明: 氧化电压对TiO₂膜层的物相组成基本没有影响, 氧化膜层呈非晶态TiO₂。当氧化电压为30 V时, TiO₂膜层表面由孔径1.3 μm左右的孔和凸起颗粒组成的粗糙结构, 随着氧化电压增加表面凸起颗粒逐渐减少, 粗糙度降低, 当氧化电压为100 V时场致溶解的作用使TiO₂膜层表面凸起颗粒不明显, TiO₂膜层表面的粗糙度低于TC4基体, 表面孔径为240 nm。TC4阳极氧化TiO₂膜层表面的微纳米结构和大量的羟基—OH, 有利于提高TiO₂膜层的生物活性和骨生长特性。

关键词 ：无机非金属材料, TC4钛合金, 阳极氧化, 表面处理, TiO2膜层

Abstract：

Anodic oxidation films of TiO₂ were prepared on titanium alloys Ti-6Al-4V(TC4) in an electrolyte system of oxalate, silicate and phosphate hybrid by means of anodic oxidation with TC4 as anode and stainless steel as cathode. Then the crystallographic structure, three-dimensional topography, microstructure and bioactivity of the prepared TiO₂ films were characterized by means of X-ray diffractometer, X-ray photoelectron spectroscopy, AFM and scanning electron microscope etc. The results show that the applied voltage has almost no effect on the crystal structure of TiO₂ films which are amorphous. There exist certain amount of pores and convex particles with ca.1.3 μm in diameter on the surface of rough TiO₂ film prepared by an applied voltage of 30 V. With the increasing applied voltage, the convex particles on TiO₂ films are slowly dismissed due to the field assisted dissolution. There are many nanopores of ca. 240 nm in diameter on the films without convex particles when the applied voltage is 100 V. There are many hydroxyls and micro/nano structures on the surface of anodic oxidation films on TC4 titanium alloy, which is useful for the enhancement of bioactivities and bone growth characteristics of the formed TiO₂ oxide films.

Key words： inorganic non-metallic materials TC4 titanium alloy anodic oxidation surface treatment TiO2 oxide film

收稿日期: 2014-12-05

基金资助:* 国家自然科学基金51362017和云南省重大科技专项2012ZE008资助项目

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https://www.cjmr.org/CN/10.11901/1005.3093.2015.12.895 或 https://www.cjmr.org/CN/Y2015/V29/I12/895

图1 不同氧化电压阳极氧化钛合金TC4样品的XRD谱

表1 氧化电压为80 V的TC4阳极氧化表面膜层O1s的化学态和原子分数

图2 氧化电压为80 V的TC4膜层表面成分XPS全谱

图3 TC4阳极氧化膜层的高分辨率XPS谱

图4 不同氧化电压TC4阳极氧化膜表面的SEM像

图5 TC4阳极氧化膜表面孔结构SEM像

图6 不同氧化电压TC4阳极氧化膜层三维形貌的AFM像

图7 氧化电压为30 V时TC4阳极氧化表面氧化膜层的二次电子像和点分析位置、背散射电子像和点分析位置、氧化钛膜层的能谱以及氧化钛膜层上凸起颗粒的能谱

表2 TC4阳极氧化表面膜层的化学组成

图8 不同氧化电压阳极氧化TC4植入兔股骨24周后的X光照片

图9 不同氧化电压TC4植入体24周后表面结构和化学组成

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