柠檬酸钠调控水热合成羟基磷灰石微球

doi:10.3724/SP.J.1077.2014.13271

无机材料学报 ›› 2014, Vol. 29 ›› Issue (3): 284-288.DOI: 10.3724/SP.J.1077.2014.13271 CSTR: 32189.14.SP.J.1077.2014.13271

柠檬酸钠调控水热合成羟基磷灰石微球

马艺娟^1,2, 郝丽静^1,2, 杜绍龙², 赵娜如^1,2

(华南理工大学 1. 国家人体组织功能重建工程技术研究中心; 2. 材料科学与工程学院, 广州510641)

收稿日期:2013-05-16 修回日期:2013-07-02 出版日期:2014-03-20 网络出版日期:2014-02-18
作者简介:马艺娟(1988–), 女, 硕士研究生. E-mail: yijuanma@126.com
基金资助:
国家 973 科技计划项目(2012CB619100, 2011CB606204);国家自然科学基金重点项目(51230002);111计划(B13030);省部产学研项目(2009B090300454) National Basic Research Program of China (973 Program) (2012 CB619100, 2011 CB606204);National Natural Science Foundation of China (51230002);Project 111 (B13030);Special Project on the Integration of Industry, Education and Research of Guangdong Province (2009B090300454)

Synthesis of Hydroxyapatite Microspheres by Hydro-thermal Method under the Control of Sodium Citrate

MA Yi-Juan^{1, 2}, HAO Li-Jing^{1, 2}, DU Shao-Long², ZHAO Na-Ru^{1, 2}

(1. The National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Gungzhou 510641, China; 2. College of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China)

Received:2013-05-16 Revised:2013-07-02 Published:2014-03-20 Online:2014-02-18
About author:MA Yi-Juan. E-mail: yijuanma@126.com

摘要/Abstract

摘要：

本研究采用四水硝酸钙(Ca(NO₃)₂·4H₂O)和磷酸氢二铵((NH₄)₂HPO₄)分别作为钙源和磷源, 以丙酰胺为pH调节剂调控溶液的过饱和度, 以柠檬酸钠为钙源缓释剂调控羟基磷灰石(Hydroxyapatite, HA)的形貌, 经水热法处理成功制备出高结晶度、形貌均一和分散性良好的HA微球。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)和扫描电镜(SEM)对反应产物进行了表征, 研究了初始pH值、柠檬酸钠加入量和水热反应温度对HA结晶度、组成及形貌的影响。研究结果表明, 当初始pH值为3, 柠檬酸钠与钙源的摩尔比为1︰1.5, 反应温度为180℃时, 有利于HA微球的形成。

关键词: 水热法, 羟基磷灰石, 微球, 柠檬酸钠

Abstract:

Hydroxyapatite (HA) microspheres were prepared by using calcium nitrate tetra hydrate (Ca(NO₃)₂·4H₂O) and diammonium phosphate ((NH₄)₂HPO₄) as the resource of calcium and phosphorus, respectively. During the synthesis, propionamide was used as pH adjusting agent to control the supersaturation of the solution, and trisodium citrate was used as the calcium source relievers to control the morphology of HA. The HA microspheres with high crystallinity, regular morphology and good dispersion were synthesized through hydrothermal method. XRD, FTIR and SEM were used to characterize the product. The effects of starting pH value, the amount of trisodium citrate and reaction temperature on the crystallinity, composition and morphology of HA were investigated. The results show that the optimal condition for uniform HA microspheres was as follows, pH=3, molar ratio of sodium citrate to calcium source at about 1:1.5, and reaction temperature of 180℃.

Key words: hydrothermal method, hydroxyapatite, microspheres, sodium citrate

中图分类号:

TB321

马艺娟, 郝丽静, 杜绍龙, 赵娜如. 柠檬酸钠调控水热合成羟基磷灰石微球[J]. 无机材料学报, 2014, 29(3): 284-288.

MA Yi-Juan, HAO Li-Jing, DU Shao-Long, ZHAO Na-Ru. Synthesis of Hydroxyapatite Microspheres by Hydro-thermal Method under the Control of Sodium Citrate[J]. Journal of Inorganic Materials, 2014, 29(3): 284-288.

图/表 7

图1 不同初始pH值条件下产物的XRD图谱

Fig. 1 XRD patterns of products under varied initial pH values (a) pH=2; (b) pH=3; (c) pH =4; ( d) pH=5 Tick marks below the patterns corresponding to the position of the Bragg reflections of the HA (JCPDS 72-1243)

图2 不同初始pH条件下产物的FTIR图谱

Fig. 2 FTIR patterns of synthesized products by hydrothermal method under varied initial pH values (a) pH=2; (b) pH=3; (c) pH =4; (d) pH=5

图3 不同初始pH条件下产物的SEM照片

Fig. 3 SEM images of synthesized products by hydrothermal method under varied initial pH values (a) pH=2; (b) pH=3; (c) pH =4; (d) pH=5

图4 不同柠檬酸钠与钙源摩尔比产物的XRD图谱

Fig. 4 XRD patterns of the products synthesized with varied molar ratios of sodium citrate to calcium source (a) TSC/Ca=1:0.5; (b) TSC/Ca =1:1; (c) TSC/Ca =1:1.5; (d) TSC/Ca =1:3 Tick marks below the patterns correspond to the position of the Bragg reflections of the Earlandite (JCPDS 28-2003) and the hexagonal HA (JCPDS 72-1243)

图5 不同柠檬酸钠与钙源摩尔比产物的SEM照片

Fig. 5 SEM images of the products synthesized with varied molar ratios of sodium citrate to calcium source (a) TSC/Ca =1:0.5; (b) TSC/Ca =1:1; (c) TSC/Ca =1:1.5; (d) TSC/Ca =1:3

图6 不同水热反应温度下产物的XRD图谱

Fig. 6 XRD patterns of the products synthesized under varied hydrothermal temperatures (a) T=120℃; (b) T =150℃; (c) T =180℃ Tick marks below the patterns correspond to the position of the Bragg reflections of the Earlandite (JCPDS 28-2003) and the hexagonal HA (JCPDS 72-1243)

图7 不同水热反应温度下产物的SEM照片

Fig.7 SEM images of the products synthesized under varied hydrothermal temperatures (a) T=120℃; (b) T=150℃; (c) T=180℃

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柠檬酸钠调控水热合成羟基磷灰石微球

Synthesis of Hydroxyapatite Microspheres by Hydro-thermal Method under the Control of Sodium Citrate

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