海藻酸钠调控羟基磷灰石纳米棒的低温快速合成

doi:10.15541/jim20140286

摘要/Abstract

摘要：

以海藻酸钠为晶体生长调节剂, 在水热条件下制备了形貌均匀、高长径比的羟基磷灰石(Hydroxyapatite, HA)单晶纳米棒。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、场发射扫描电镜(FE-SEM)、透射电镜(TEM)以及同步热分析(TG/DSC)等测试方法对合成产物进行了表征, 探索了反应温度和时间对产物的结晶度、组成以及形貌的影响, 并提出了HA纳米棒的合理生长机理。研究表明, 80℃水热条件, 反应24 h, 对于均匀、低有机吸附量的HA单晶纳米棒合成较有利。对纳米棒的不同生长阶段的微结构分析表明: 晶体生长经历了成核、表面调控、继续生长和取向搭接四个阶段。

关键词: 羟基磷灰石, 海藻酸钠, 纳米棒, 水热法

Abstract:

Hydroxyapatite (HA) nanorods with uniform morphology and high aspect ratio were prepared by hydrothermal method using alginate (SA) as controlling agent. The samples were characterized by XRD, FTIR, SEM, TEM and TG/DSC to detect the effects of temperature and time on the crystallinity, composition and morphology of the final products. Meanwhile, the growth mechanism of HA nanorods was explored. Experiments showed that uniform HA nanorods with low organic composition could be well synthesized via hydrothermal method at 80°C after 24 h. Investigations on the microstructures of nanorods revealed that their growth could be divided into four stages: initial nucleation, surface regulation, continuous growth and oriented attachment.

Key words: hydroxyapatite, sodium alginate, nanorods, hydrothermal method

中图分类号:

TQ174

马丽, 朱建华, 黄磊. 海藻酸钠调控羟基磷灰石纳米棒的低温快速合成[J]. 无机材料学报, 2015, 30(3): 311-317.

MA Li, ZHU Jian-Hua, HUANG Lei. Rapid Synthesis of Hydroxyapatite Nanorods at Low Temperature Controlled by Sodium Alginate[J]. Journal of Inorganic Materials, 2015, 30(3): 311-317.

图/表 10

图1 不同水热温度条件下产物的SEM照片

Fig. 1 SEM images of synthesized products by hydrothermal method at 60℃ (a), 80℃ (b), 100℃ (c) and 120℃ (d) for 24 h

表1 不同合成温度下产物直径及长度

Table 1 Diameter and length of HA products prepared at various temperatures

Products	60℃	80℃	100℃	120℃
Diameter/nm	—	40-120	50-250	50-250
Length/μm	—	4-6	2-4	1-3

图2 不同水热温度条件下产物的XRD图谱

Fig. 2 XRD patterns of synthesized products by hydrothermal method at 60℃ (a), 80℃ (b), 100℃ (c) and 120℃ (d) for 24 h Tick marks below the patterns corresponding to the position of the Bragg reflections of the HA (JCPDS 09-0432)

图3 不同水热温度条件下产物的FTIR图谱

Fig. 3 FTIR spectra of synthesized products by hydrothermal method at 60℃ (a), 80℃ (b), 100℃ (c) and 120℃ (d) for 24 h

图4 80℃水热温度下反应24 h产物的TEM和HRTEM照片及选区电子衍射图

Fig. 4 TEM image (a) and HRTEM image (b) of synthesized products by hydrothermal method at 80℃ for 24 h

图5 纯SA和合成产物的TG/DSC图谱

Fig. 5 TG/DSC patterns of pure SA and synthesized product by hydrothermal method for 24 h at 80℃:(a) Pure SA; (b) Synthesized product

图6 80℃水热下不同时期产物的SEM(a, d)、TEM(b, e)和HRTEM(c, f)照片及快速傅里叶转换图片

Fig. 6 SEM (a), TEM (b) and HRTEM (c) images of initial precipitation after 8 h with inset showing the Fast Fourier Transform image (FFT) in (c), and (d-e) SEM (d), TEM (e) and HRTEM (f) images of products after 16 h with inset showing the magnified area in (e)

图7 80℃水热不同时期产物的XRD图谱

Fig. 7 XRD patterns of synthesized products by hydrothermal method at 80℃ for 8 h (a), 16 h (b) and 24 h (c)

图8 80℃水热不同时期产物的FTIR图谱

Fig. 8 FTIR spectra of synthesized products by hydrothermal method at 80℃ for 8 h (a), 16 h (b) and 24 h(c)

图9 HA纳米棒的形成机理的示意图

Fig. 9 Formation mechanism of HA nanorods

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