机械活化增强多孔磷酸钙骨水泥支架的研究

doi:10.15541/jim20140618

无机材料学报 ›› 2015, Vol. 30 ›› Issue (4): 432-438.DOI: 10.15541/jim20140618

机械活化增强多孔磷酸钙骨水泥支架的研究

黄萍, 李鹏, 赵军胜, 屈树新, 冯波, 翁杰

(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)

收稿日期:2014-11-27 修回日期:2015-01-08 出版日期:2015-04-29 网络出版日期:2015-03-26
作者简介:黄萍(1989–), 女, 硕士研究生. E-mail: huangping135515@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)

Mechanical Activation Reinforced Porous Calcium Phosphate Cement

HUANG Ping, LI Peng, ZHAO Jun-Sheng, QU Shu-Xin, FENG Bo, WENG Jie

(Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China)

Received:2014-11-27 Revised:2015-01-08 Published:2015-04-29 Online:2015-03-26
About author:HUANG Ping. E-mail: huangping135515@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：

本研究采用球磨对磷酸钙骨水泥(CPC)起始粉末进行机械活化处理, 以期改善CPC力学性能, 并探讨了其影响机理。采用激光粒度仪、比表面积测量仪和X射线衍射仪(XRD)表征球磨后的CPC粉末(Ball milling CPC, BCPC)。利用发泡法制备多孔BCPC支架, 采用万能力学试验机、XRD和扫描电子显微镜(SEM)表征多孔BCPC支架。结果显示, 球磨后的BCPC粉末平均粒径减小, 比表面积增大, 表观密度、堆积密度及紧密密度减小。BCPC支架孔隙率为(77.98 ± 0.58)%, 抗压强度为(4.11 ± 0.46) MPa, 相比CPC支架的(64.23 ± 2.32)%和(1.99 ± 0.43) MPa有显著提高。SEM结果显示BCPC支架具有数微米和数百微米的两种孔隙结构。XRD结果表明机械活化作用降低了DCPD、α-TCP、CaCO₃和HA的晶粒尺寸和结晶度, 促使DCPD向DCPA转化, 促进了各相磷酸钙盐的水化和HA的沉积, 提高了BCPC支架的力学性能, 为增强CaP基多孔材料的力学性能和扩展其临床应用提供了新途径。

null

关键词: 磷酸钙骨水泥, 球磨, 机械活化, 多孔支架, 抗压强度

Abstract:

Calcium phosphate cement (CPC) powder was activated by ball milling to improve the mechanical properties of porous CPC scaffolds. The mechanical activation mechanism was investigated by specific surface analyses, X-ray diffraction (XRD) and scanning electron microscopy (SEM). After ball milling, the average particle sizes of BCPC powder decreased while the specific surface area, apparent density, bulk density, and compact density increased when compared with non-activated CPC powder. The porosity and compressive strength of porous CPC scaffolds prepared from ball-milled powders (BCPC-S) were (77.98 ± 0.58)% and (4.11 ± 0.46) MPa, both significantly higher than those non-activated CPC powders (CPC-S), whose porosity and compressive strength were (64.23 ± 2.32)% and (1.99 ± 0.43) MPa, respectively. SEM revealed that there were two types of pores in the BCPC-S: one ranged a few microns in size and the other ranged several hundred microns. XRD indicated that grain sizes and crystallinities of dicalcium phosphate dehydrate (DCPD), α-tricalcium phosphate (α-TCP), calcium carbonate (CaCO₃) and hydroxyapatite (HA) in BCPC powder decreased, due to the mechanical activation compared to those of the non-activated CPC powders. In addition, the mechanical activation resulted in the conversion of DCPD to dicalcium phosphate anhydrous (DCPA), which promoted the hydration of CPC and the precipitation of HA, and improved the compressive strength of BCPC-S finally. This study provided a potential approach to improve the mechanical properties of porous CaP based scaffold to meet the clinic requirement.

Key words: calcium phosphate cement, ball milling, mechanical activation, porous scaffold, compression strength

中图分类号:

黄萍, 李鹏, 赵军胜, 屈树新, 冯波, 翁杰. 机械活化增强多孔磷酸钙骨水泥支架的研究[J]. 无机材料学报, 2015, 30(4): 432-438.

HUANG Ping, LI Peng, ZHAO Jun-Sheng, QU Shu-Xin, FENG Bo, WENG Jie. Mechanical Activation Reinforced Porous Calcium Phosphate Cement[J]. Journal of Inorganic Materials, 2015, 30(4): 432-438.

图/表 9

表1 BCPC-S、CPC-S和Control-S的最优参数组合

Table 1 The optimal parameter combinations of orthogonal test for CPC-S, BCPC-S and Control-S

Samples	(L/P ratio)/ (mL·g^-1)	C_H2O2/%	pH	T/℃
BCPC-S	1.0	25	8.0	60
CPC-S	0.4	25	8.0	60
Control-S	1.0	0	8.0	60

图1 原料粒径随球磨时间的变化

Fig. 1 Variation of particle size with ball billing time

表 2 BCPC-P和CPC-P的表观密度d、堆积密度dB、紧密密度dC和比表面积SSA (n=6)

Table. 2 Apparent densities, bulk densities, compact densities and specific surface areas of BCPC-P and CPC-P(n=6)

Samples	d/(g·cm^-3)	d_B/(g·cm^-3)	d_C/(g·cm^-3)	SSA/(m²·g^-1)
BCPC	2.430 ± 0.138^a	0.498 ± 0.098^b	1.937 ± 0.106^c	15.100
CPC	2.871 ± 0.112^a	0.891 ± 0.127^b	2.135 ± 0.114^c	8.616

图2 BCPC-P和CPC-P的XRD图谱(a)和不同处理条件下DCPD的XRD图谱(b)

Fig. 2 XRD patterns of BCPC-P and CPC-P (a) and XRD patterns of DCPD with different treatments (b) DCPD: Drying at 37℃; DCPD-80℃: Drying at 80℃; DCPD + ethanol - 80℃: Drying at 80℃ after adding 50 mL ethanol; Ball milling DCPD-80℃: Drying at 80℃ after ball milling

表3 BCPC-P和CPC-P中不同磷酸钙的晶粒尺寸

Table 3 Grain sizes of different calcium phosphates of BCPC-P and CPC-P

Grain size/nm	DCPD	α-TCP	CaCO₃	HA
BCPC-P	59.42	29.48	33.16	42.59
CPC-P	74.26	51.65	51.85	47.15

图3 BCPC-S、CPC-S和Control-S的抗压强度(a)和典型应力应变曲线(b)

Fig. 3 Compression strengths of the CPC-S, BCPC-S and Control-S (a), and typical stress-strain curves (b)

图4 BCPC-S、CPC-S和Control-S水化后的XRD图谱(a)和BCPC-S、CPC-S和Control-S中α-TCP和HA的相对含量(b)

Fig. 4 XRD patterns of CPC-S, BCPC-S and Control-S after hydration for 24 h (a) and relative quantity of α-TCP and HA in BCPC-S, CPC-S and Control-S (b)

图5 BCPC-S、CPC-S和Control-S总孔隙率Ptotal和大孔率Pmacro

Fig. 5 Ptotal and Pmacro of BCPC-S and CPC-S *p<0.05, **p<0.01

图6 BCPC-S(a1, a2)、CPC-S(b1, b2)与Control-S(c1, c2)的自然断面的SEM照片

Fig. 6 SEM images of cross-section of BCPC-S (a1, a2), CPC-S (b1, b2) and Control-S (c1, c2)

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机械活化增强多孔磷酸钙骨水泥支架的研究

Mechanical Activation Reinforced Porous Calcium Phosphate Cement

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