仿生纳米含硅羟基磷灰石的合成与表征

doi:10.3724/SP.J.1077.2013.12292

摘要/Abstract

摘要：

为了探究仿生纳米含硅羟基磷灰石的合成条件及含硅量对其结晶性能的影响, 以Ca(NO₃)₂、(NH₄)₂HPO₄和Si(OCH₂CH₃)₄(TEOS)为原料, 采用化学沉淀法制备了不同含硅量的羟基磷灰石, 并通过傅里叶变换红外光谱(FTIR)、X射线荧光光谱(XRF)、X射线衍射(XRD)、透射电镜(TEM)对材料进行了表征。结果表明较低温(40℃)时有利于合成纯净的仿生纳米含硅羟基磷灰石, SiO₄^4-取代部分PO₄^3-进入羟基磷灰石的晶格。随着含硅量的增加, 仿生纳米含硅羟基磷灰石的结晶度和晶粒尺寸均降低, 晶胞参数a和c均增大。

关键词: 硅, 羟基磷灰石, 化学沉淀, 仿生

Abstract:

To explore the synthesis condition of the bionic nano-silicon-substituted hydroxyapatite and the impact of the silicon content on its crystallization properties, hydroxyapatite of different silicon content were synthesized from Ca(NO₃)₂, (NH₄)₂HPO₄ and Si(OCH₂CH₃)₄(TEOS) via an aqueous precipitation reaction. Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence spectrum (XRF), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used for hydroxyapatite characterization. The results show that relative low temperature (40℃) is conducive to obtain pure bionic nano-silicon-substituted hydroxyapatite. Under this condition, SiO₄^4- enters the lattice of hydroxyapatite and replaces part of PO₄^3-. The more the content of silicon is, the lower the crystallinity is, the smaller the grain size is and the higher the lattice parameters a and c are.

Key words: silicon, hydroxyapatite, aqueous precipitation reaction, bionoid

中图分类号:

TQ174

翟倩倩, 赵士贵, 王孝海, 李秀芝, 李文杰, 郑亚森. 仿生纳米含硅羟基磷灰石的合成与表征[J]. 无机材料学报, 2013, 28(1): 58-62.

ZHAI Qian-Qian, ZHAO Shi-Gui, WANG Xiao-Hai, LI Xiu-Zhi, LI Wen-Jie, ZHENG Ya-Sen. Synthesis and Characterization of Bionic Nano-silicon-substituted Hydroxyapatite[J]. Journal of Inorganic Materials, 2013, 28(1): 58-62.

图/表 11

Table 1 Quantities of used reactants

Samples	Ca(NO₃)₂ /mol	(NH₄)₂HPO₄ /mol	TEOS /mol	Expected w(Si)/%	Calculated chemical formula of Si-HA
HA	0.025	0.01500	0.00000	0	Ca₁₀(PO₄)₆(OH)₂
2%Si-HA	0.025	0.01470	0.00030	0.335	Ca₁₀(PO₄)_5.88(SiO₄)_0.12(OH)_1.88
7%Si-HA	0.025	0.01395	0.00105	1.181	Ca₁₀(PO₄)_5.58(SiO₄)_0.42(OH)_1.58
12%Si-HA	0.025	0.01320	0.00180	2.037	Ca₁₀(PO₄)_5.28(SiO₄)_0.72(OH)_1.28
17%Si-HA	0.025	0.01245	0.00255	2.903	Ca₁₀(PO₄)_4.98(SiO₄)_1.02(OH)_0.98

图1 化学沉淀法合成Si-HA流程图

Fig. 1 Flow chart of the preparation of Si-HA by the aqueous precipitation route

图2 不同反应温度条件下12%Si-HA的XRD图谱

Fig. 2 XRD patterns of 12% Si-HA prepared at (a) 40℃, (b) 50℃ and (c) 60℃

图3 HA标准XRD图谱(a)与60℃、陈化24 h的12%Si-HA的XRD图谱(b)

Fig. 3 Standard XRD of HA (a) XRD pattern of 12%Si-HA prepared at 60℃ and aging for 24 h (b)

图4 60℃不同陈化时间条件下12%Si-HA的XRD图谱

Fig. 4 XRD patterns of 12%Si-HA prepared at 60℃ and (a) aging for 24 h (a), 48 h (b) and 72 h (c)

图5 HA和Si-HA的FTIR图谱

Fig. 5 FTIR spectra of (a) HA, (b) 2%Si-HA, (c) 7%Si-HA, (d) 12%Si-HA and (e) 17%Si-HA

Table 2 The content of Ca and Si of Si-HA

Samples	Expected w(Si)/%	Found w(Si)/%	Expected w(Ca)/%	Found w(Ca)/%
HA	0	0	39.84	36.70
2%Si-HA	0.335	0.22	39.90	36.52
7%Si-HA	1.181	0.83	40.18	36.07
12%Si-HA	2.037	1.75	40.42	36.16
17%Si-HA	2.903	2.30	40.67	34.24

图6 不同含硅量的Si-HA的XRD衍射图谱

Fig. 6 XRD patterns of (a) HA, (b) 2%Si-HA, (c) 7%Si-HA, (d) 12%Si-HA and (e) 17%Si-HA

Table 3 Grain size of c-axis and average grain size of Si-HA

Samples	Grain size/nm
Samples	c-axis	Average
HA	27	26.6
2%Si-HA	30.5	23.7
7%Si-HA	21.6	21.1
12%Si-HA	20.1	16.1
17%Si-HA	18.9	13

Table 4 Lattice parameters of HA and Si-HA

Samples	a/nm	c/nm
HA	0.941572	0.686471
2%Si-HA	0.942215	0.690142
7%Si-HA	0.943736	0.686588
12%Si-HA	0.947851	0.686749
17%Si-HA	0.948608	0.687302

图7 Si-HA的TEM照片

Fig.7 TEM images of (a)2%Si-HA and (b)7%Si-HA

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