纳米晶体纤维素增强磷酸钙骨水泥的研究

doi:10.15541/jim20140385

无机材料学报 ›› 2015, Vol. 30 ›› Issue (3): 318-324.DOI: 10.15541/jim20140385 CSTR: 32189.14.10.15541/jim20140385

纳米晶体纤维素增强磷酸钙骨水泥的研究

赵军胜¹, 屈树新¹, 黄萍¹, 刘宗光¹, 王铈汶^{1, 2}, 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. 国家纳米科学中心, 中国科学院纳米生物安全性与生物效应重点实验室, 北京 100190)

收稿日期:2014-07-25 修回日期:2014-09-17 出版日期:2015-03-20 网络出版日期:2015-03-06
作者简介:赵军胜(1987–), 男, 硕士研究生. E-mail: junshengz0901@163.com
基金资助:
973项目(2012CB933602);国家自然科学基金(51372210);教育部博士点基金(20130184110023);四川省高校科研创新团队建设计划项目(14TD0050)

Calcium Phosphate Cement Reinforced by Nanocrystalline Cellulose

ZHAO Jun-Sheng¹, QU Shu-Xin¹, HUANG Ping¹, LIU Zong-Guang¹, WANG Shi-Wen^{1, 2}, WENG Jie¹

(1. Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China; 2. Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Chinese Academy of Sciences, National Center for Nanoscience and Technology, Beijing 100190, China)

Received:2014-07-25 Revised:2014-09-17 Published:2015-03-20 Online:2015-03-06
About author:ZHAO Jun-Sheng. E-mail: junshengz0901@163.com
Supported by:
National Basic Research Program of China (973 Program, 2012CB933602);National Natural Science Foundation of China (51372210);Research Fund for the Doctoral Program of Higher Education of China (20130184110023);Construction Program for Innovative Research Team of University in Sichuan Province (14TD0050)

摘要/Abstract

摘要： 本研究探索具有良好力学性能的纳米晶体纤维素(NCC)对磷酸钙骨水泥(CPC)抗压强度的影响。采用万能力学试验机、Gilmore双针、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)表征含不同NCC的CPC理化性能; 利用扫描电子显微镜(SEM)和荧光显微镜观察CPC断面形貌和荧光标记的NCC在CPC中的分散。抗压强度结果表明: NCC能显著提高CPC的抗压强度, 且2% NCC-CPC的抗压强度最高, 约为27 MPa; CPC的凝固时间随NCC含量的增加而延长, 含量为2%时基本符合临床要求; XRD和XPS结果显示NCC与Ca²⁺形成不稳定的配合物, 促进了CPC中二水磷酸氢钙(DCPD)和CaCO₃的溶解和转化; SEM观察结果显示加入NCC使CPC内部结构更致密, 孔隙和裂纹减少; 荧光显微观察结果表明NCC在CPC中均匀分散。

关键词: 磷酸钙骨水泥, 纳米晶体纤维素, 抗压强度, 分散性

Abstract:

The aim of this study is to investigate the effect of nanocrystalline cellulose (NCC) with favorable mechanical properties on the compressive strength of calcium phosphate cement (CPC). Compressive test, Gilmore needle test, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to analyze the physicochemical properties of CPC influenced by different contents of NCC. Scanning electron microscope (SEM) and fluorescence microscope were used to observe the morphologies of CPC and the dispersity of labeled-NCC in CPC, respectively. NCC significantly increased the compressive strength of CPC up to about 27 MPa when the content of NCC was 2%. Setting times of CPC were prolonged with increased NCC, but still met the clinical requirements when the content of NCC was not more than 2%. XRD and XPS indicated that the combination of NCC with Ca²⁺ could form unstable coordination compound and NCC promoted the dissolution and conversion of dicalcium phosphate dehydrate (DCPD) and CaCO₃. SEM showed that CPC became denser with fewer pores and cracks by addition of NCC. Fluorescence microscope demonstrated the homogeneous dispersion of labeled-NCC in CPC.

Key words: calcium phosphate cement, nanocrystalline cellulose, compressive strength, dispersity

中图分类号:

赵军胜, 屈树新, 黄萍, 刘宗光, 王铈汶, 翁杰. 纳米晶体纤维素增强磷酸钙骨水泥的研究[J]. 无机材料学报, 2015, 30(3): 318-324.

ZHAO Jun-Sheng, QU Shu-Xin, HUANG Ping, LIU Zong-Guang, WANG Shi-Wen, WENG Jie. Calcium Phosphate Cement Reinforced by Nanocrystalline Cellulose[J]. Journal of Inorganic Materials, 2015, 30(3): 318-324.

图/表 10

图1 CPC、2% NCC-CPC和4% NCC-CPC水化24 h后的抗压强度(a)和典型的应力—应变曲线(b)

Fig. 1 Compressive strength of CPC, 2 %NCC-CPC and 4 %NCC-CPC after setting for 24 h (n=6, *p<0.05, **p<0.01) (a) and the typical stress-strain curves (b)

图 2 CPC、2% NCC-CPC和4% NCC-CPC的初凝和终凝时间

Fig. 2 Initial and final setting times of CPC, 2% NCC-CPC and 4% NCC-CPC (n=3, *p<0.05, **p<0.01)

图 3 CPC、2% NCC-CPC和4% NCC-CPC水化24 h后的XRD图谱(a)和各组CPC样品中DCPD和CaCO3主极大衍射峰强度(Ix)与空白CPC中DCPD和CaCO3主极大衍射峰强度(I0)的比值(b)

Fig. 3 XRD patterns of CPC, 2% NCC-CPC and 4% NCC-CPC (a) and the ratio of the primary diffraction maximum of DCPD and CaCO3 of each CPC sample (Ix) to that of CPC (I0) (b)

表1 CPC和2% NCC-CPC中C1s、O1s和Ca2p的结合能

Table 1 The binding energy of C1s, O1s and Ca2p core levels from CPC and 2% NCC-CPC

Elements and functional groups		Binding energy/eV
Elements and functional groups		CPC	2% NCC-CPC
C1s	C-C、C-H C-O/C=O C-C/C-O-C	284.8 286.5/288.8 -	284.8 - 286.1/288.3
O1s	P=O P-OH/H₂O C-OH/C-O-C	531.2 532.5 -	531.4 - 532.8
Ca2p	Ca2p_3/2 Ca2p_1/2	351.0 347.3	351.1 347.6

图4 NCC的化学结构图(其中DP为聚合度[8])

Fig. 4 Chemical structure of NCC DP represents the degree of polymerization

图5 CPC和2% NCC-CPC水化24 h后的XPS图谱

Fig. 5 XPS spectra of CPC and 2% NCC-CPC after setting for 24 h (a) Survey; (b) C1s; (c) O1s; (d) Ca2p

图6 CPC、2% NCC-CPC和4% NCC-CPC水化24 h后自然断面的SEM照片

Fig. 6 SEM images of the cross-sections of CPC (a1, a2), 2% NCC-CPC (b1, b2) and 4% NCC-CPC (c1, c2) after setting for 24 h

图7 NCC与Ca2+配位结合促进CPC水化的示意图

Fig. 7 Schematic diagram of NCC promoting the setting of CPC by coordination with Ca2+

图8 NCC的TEM照片

Fig. 8 TEM image of NCC

图9 7-氨基-4-甲基香豆素(AMC)标记的NCC在CPC中均匀分布的荧光显微照片

Fig. 9 Fluorescence micrographs of NCC labeled by 7-amino-4-methyl coumarin (AMC) that evenly distributed in CPC (a) 2% NCC-CPC; (b) 2% NCC-AMC-CPC; (c) 4% NCC-AMC-CPC

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纳米晶体纤维素增强磷酸钙骨水泥的研究

Calcium Phosphate Cement Reinforced by Nanocrystalline Cellulose

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