纯钛表面立方介孔SiO2薄膜诱导沉积碳磷灰石层

doi:10.15541/jim20150038

摘要/Abstract

摘要：

采用浸渍-提拉法在预处理纯钛表面制备立方介孔SiO₂薄膜, 通过评价体外诱导类骨碳磷灰石层形成能力研究其生物活性。利用小角X射线衍射、傅立叶变换红外光谱、N₂吸附、电镜和能谱等测试技术对模板剂去除前后、模拟体液浸泡前后介孔薄膜结构、组成与形貌进行了研究; 利用固体表面Zeta电位仪研究薄膜表面荷电性质。结果表明, 介孔薄膜具有三维立方介孔结构, 在模拟体液(1.5SBF)中浸泡14 d即能诱导碳磷灰石层在其表面沉积, 显示出良好的生物活性。介孔薄膜独特的孔道结构以及孔表面Si-OH在体液中呈负电性对其生物活性起关键作用。

关键词: 纯钛, 立方相, 介孔SiO2薄膜, 浸渍-提拉, 碳磷灰石

Abstract:

Cubic mesoporous silica thin films were synthesized on pure titanium by dip-coating method and then their bioactivity were evaluated through the induced deposition of bone-like carbonated hydroxyapatite (CHA) layer in vitro. The composition, microstructure and morphology of the films were characterized by small-angel X-ray diffraction, Fourier transform infrared spectrum, nitrogen adsorption, electron microscopes and energy dispersive spectroscopy, etc. The surface Zeta potential of the films was investigated by electrokinetic analyzer for solid surface analysis. The results reveal that the films have three-dimensional cubic mesostructure. The mesoporous silica films are covered with a thin CHA layer after being soaked in a simulated body fluid (1.5 SBF) for 14 d, indicating its good bioactivity. The unique mesostructure and the presence of abundant electronegative silanol groups in physiological solution may be responsible for the bioactivity.

Key words: pure titanium, cubic phase, mesoporous silica thin films, dip-coating, carbonated hydroxyapatite

中图分类号:

TQ127

张珍容, 姚异渊, 罗凯, 万隆, 刘宣勇. 纯钛表面立方介孔SiO₂薄膜诱导沉积碳磷灰石层[J]. 无机材料学报, 2015, 30(7): 725-731.

ZHANG Zhen-Rong, YAO Yi-Yuan, LUO Kai, WAN Long, LIU Xuan-Yong. Cubic Mesoporous Silica Thin Films Coated on Titanium to Induce Carbonated Hydroxyapatite Deposition[J]. Journal of Inorganic Materials, 2015, 30(7): 725-731.

图/表 10

图1 (a) 未去除模板剂, (b) 萃取和(c) 焙烧薄膜样品的小角XRD图谱

Fig. 1 Small-angle X-ray diffraction patterns of the films peeled off from the as-synthesized (a), extracted (b) and calcined (c) samples

图2 (a) 未去除模板剂, (b) 萃取和(c) 焙烧介孔SiO2薄膜样品的FTIR光谱

Fig. 2 FTIR spectra of the mesoporous silica films peeled off from the as-synthesized (a), extracted (b) and calcined (c) samples

图3 萃取后薄膜样品的N2吸附/脱附等温线及孔径分布图

Fig. 3 Nitrogen adsorption-desorption isotherms and the corresponding pore size distribution curve (inset) of the film peeled off from the extracted sample

图4 萃取后薄膜样品的HRTEM照片与傅立叶变换图

Fig. 4 HRTEM images and Fourier transform of the extracted films (a) One-dimensional lattice and diffraction spot; (b) Two-dimensional lattice and hexagonal diffraction spot; (c) Three-dimensional lattice and matrix diffraction spot, and (d) EDS analysis

图5 钛片在SiO2溶胶-凝胶中浸渍-提拉1次(a)、2次(b)和3次(c)所得薄膜表面形貌和EDS图谱(d)

Fig. 5 Surface morphologies of the extracted films on Ti substrate by dip-coating method for one time (a), two times (b), three times (c) and EDS pattern of the sample in (d)

图6 1.5SBF浸泡14d后薄膜表面沉积物的形貌和EDS图谱

Fig. 6 Surface morphologies and EDS analysis of the deposition on the mesoporous silica films after soaking in 1.5SBF for 14 d (a) Surface morphologies of the deposition on the films at low magnification, (a1) The thin layer with needle-like formation covering the films, (a2) The Ca-P layer with spherical formation gathering on the thin layer, (a3) The same surface at higher magnification, a spherical texture with needle-like formation can be observed, and (b) EDS spectrum of spherical formation

图7 (a) 介孔SiO2薄膜、(b) 纳米羟基磷灰石和(c) 薄膜表面沉积物的FTIR光谱

Fig. 7 FTIR spectra of (a) mesoporous silica films peeled off the substrate, (b) nano-hydroxyapatite powder, and (c) the deposition on the films soaked in 1.5SBF for 14 d

图8 (a)介孔SiO2薄膜, (b)纳米羟基磷灰石和(c)薄膜表面沉积物的XRD图谱

Fig. 8 XRD patterns of mesoporous silica films peeled off the substrate (a), nano-hydroxyapatite powder (b), and the deposition peeled off the films (c)

图9 介孔SiO2薄膜表面Zeta电位与电解液pH的关系

Fig. 9 Zeta potential vs. electrolyte’s pH of the mesoporous silica films

图10 介孔SiO2薄膜诱导碳磷灰石层形成过程示意图

Fig. 10 Schematic illustration for the growth of carbonated hydroxyapatite layer on the mesoporous silica films after soaking in a simulated body fluid

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纯钛表面立方介孔SiO₂薄膜诱导沉积碳磷灰石层

Cubic Mesoporous Silica Thin Films Coated on Titanium to Induce Carbonated Hydroxyapatite Deposition

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