掺铜羟基磷灰石微球的制备及表征

doi:10.3724/SP.J.1077.2014.13532

无机材料学报 ›› 2014, Vol. 29 ›› Issue (7): 769-775.DOI: 10.3724/SP.J.1077.2014.13532 CSTR: 32189.14.SP.J.1077.2014.13532

掺铜羟基磷灰石微球的制备及表征

肖东琴^1,2, 王东微^1,2, 任俊臣¹, 段可^1,2, 姚宁¹, 鲁雄¹, 郑晓彤¹, 翁杰¹

(1. 西南交通大学材料科学与工程学院, 材料先进技术教育部重点实验室, 成都610031; 2. 江苏省介入医疗器械研究重点实验室, 淮阴工学院, 淮阴 223003)

收稿日期:2013-10-10 修回日期:2013-11-20 出版日期:2014-07-20 网络出版日期:2014-06-20
作者简介:肖东琴(1986–), 女, 博士研究生. E-mail: xdqdxs@163.com
基金资助:
国家重点基础研究发展计划(973计划, 2012CB933600);国家自然科学基金(51172188,81071456);四川省科技支撑计划(2010FZ0048);中央高校基本科研业务费(SWJTU11ZT11);教育部博士点基金(20100184120011);2013年西南交通大学博士创新基金

Synthesis and Characterization of Copper-substituted Hydroxyapatite Micrspheres

XIAO Dong-Qin^1,2, WANG Dong-Wei^1,2, REN Jun-Chen¹, DUAN Ke^1,2, YAO Ning¹, LU Xiong¹, ZHENG Xiao-Tong¹, WENG Jie¹

(1. Key Laboratory of Advanced Technologies of Materials, Ministry of Education, School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China; 2. Jiangsu Provincial Key Laboratory for Interventional Medical Devices, Huaiyin Institute of Technology, Huaiyin 223003, China)

Received:2013-10-10 Revised:2013-11-20 Published:2014-07-20 Online:2014-06-20
About author:XIAO Dong-Qin. E-mail: xdqdxs@163.com
Supported by:
National Basic Research Program of China 973 Program(2012CB933600);National Natural Science Foundation of China(51172188, 81071456);Science and Technology Pillar Project of Sichuan(2010FZ0048);Fundamental Research Funds for Central Universities(SWJTU11ZT11);Specialized Research Fund for the Doctoral Program of Higher Education(20100184120011);2013 Doctoral Innovation Foundation of Southwest Jiaotong University

摘要/Abstract

摘要：

铜作为人体含量第二的必需微量元素, 不仅在人体新陈代谢过程中起着重要作用, 同时还具有抗菌性。因此, 合成掺铜羟基磷灰石(Cu-HA)可望获得具有优良生物学性能兼具抗菌性能的生物陶瓷。本研究以硝酸钙、硝酸铜和磷酸氢二钠为原料, 采用水热合成法制备掺铜HA。采用扫描电镜、透射电镜、X射线衍射、红外和原子吸收光谱对样品进行表征。结果表明: 溶液体系中加入Cu²⁺后, Cu取代部分Ca进入HA晶格, 使其形貌由带状转变为花瓣状微球; 但Cu的掺入, 并不影响HA晶体结构; 当溶液中Cu/(Cu+Ca) 摩尔比高于0.05时, HA产物的热稳定性下降。

关键词: 羟基磷灰石, 铜掺杂, 微球, 水热合成法

Abstract:

As the second essential trace element in human body, copper plays vital roles in metabolism and antimicrobial. Therefore, synthesis of copper-substituted hydroxyapatite (Cu-HA) is expected to create bioceramics with improved biological and antimicrobial properties. In this study, Cu-HA was prepared by hydrothermal reactions using Ca(NO₃)₂∙4H₂O, Cu(NO₃)₂∙3H₂O and Na₂HPO₄∙12H₂O. Products were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscope and atomic absorption spectrometry. Results show that copper is incorporated into the HA crystals. Correspondingly, the products retain HA structure but their morphologies transform from ribbons to flower-like microspheres. Moreover, when Cu/(Cu+Ca) (molar ratio) of the reaction solution is greater than 0.05, the thermal stability of the HA product is decreased.

Key words: hydroxyapatite, copper substitution, microspheres, hydrothermal synthesis

中图分类号:

TQ174

肖东琴, 王东微, 任俊臣, 段可, 姚宁, 鲁雄, 郑晓彤, 翁杰. 掺铜羟基磷灰石微球的制备及表征[J]. 无机材料学报, 2014, 29(7): 769-775.

XIAO Dong-Qin, WANG Dong-Wei, REN Jun-Chen, DUAN Ke, YAO Ning, LU Xiong, ZHENG Xiao-Tong, WENG Jie. Synthesis and Characterization of Copper-substituted Hydroxyapatite Micrspheres[J]. Journal of Inorganic Materials, 2014, 29(7): 769-775.

图/表 10

表1 水热制备掺铜羟基磷灰石所用溶液组成

Table 1 Solutions used for hydrothermal preparation of Cu-HA

Solution	Ca(NO₃)₂ /mmol	Cu(NO₃)₂ /mmol	=n(Cu)/ n(Cu+Ca)
S0	3	0	0
S1	2.97	0.03	0.01
S2	2.91	0.09	0.03
S3	2.85	0.15	0.05
S4	2.7	0.3	0.1
S5	2.4	0.6	0.2

图1 150℃保温3 h条件下不同溶液中合成Cu-HA的SEM照片

Fig. 1 SEM images of Cu-HA prepared by reaction at 150℃ for 3 h in different solutions (a) S0; (b) S1; (c) S2; (d) S3; (e) S4; (f) S5

图2 150℃保温3 h条件下合成Cu-HA (S3)的TEM照片

Fig. 2 TEM images of Cu-HA (S3) prepared by reaction at 150℃ for 3 h

图3 150℃保温3 h条件下不同溶液中合成Cu-HA的XRD图谱

Fig. 3 XRD patterns of Cu-HA prepared by reaction at 150℃ for 3 h in different solutionse

图4 150℃保温3 h条件下合成Cu-HA (S2、S3、S4和S5)经900℃处理1 h后XRD图谱

Fig. 4 XRD patterns of Cu-HA (S2, S3, S4 and S5) prepared by reaction at 150℃ for 3 h and subsequently calcinated at 900℃ for 1 h

图5 150℃保温3 h条件下合成Cu-HA (S0、S1、S2和S3)的FTIR图谱

Fig. 5 FTIR spectra of Cu-HA (S0, S1, S2 and S3) prepared by reaction at 150℃ for 3 h

表2 样品Cu-HA (S1、S2和S3)的掺铜率

Table 2 Cu-substitution ratio of Cu-HA

Sample	χ_t (Theoretical)	χ_a (Actual)	R /%
S1	0.01	0.0076	76
S2	0.03	0.0144	48
S3	0.05	0.0155	31

图6 不同水热温度下保温3 h合成Cu-HA(S3)的SEM照片

Fig. 6 SEM images of Cu-HA (S3) prepared by reaction at 120℃(a, b), 150℃(c, d) and 200℃(e, f) for 3 h

图7 不同水热温度下保温3 h合成Cu-HA(S3)的XRD图谱

Fig. 7 XRD patterns of Cu-HA (S3) prepared by reaction at different temperatures for 3 h

图8 150℃条件下反应0.5 h (a), 1 h (b), 2 h (c)和3 h (d)所得Cu-HA(S3)的SEM照片和XRD图谱

Fig. 8 SEM images and XRD patterns of Cu-HA (S3) prepared by reaction at 150℃ for 0.5 h (a), 1 h (b), 2 h (c) and 3 h (d)

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掺铜羟基磷灰石微球的制备及表征

Synthesis and Characterization of Copper-substituted Hydroxyapatite Micrspheres

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