不同碳纳米管/羟基磷灰石复合粉末的添加对磷酸钙骨水泥性能和结构的影响

doi:10.3724/SP.J.1077.2013.12226

摘要/Abstract

摘要：

采用物理共混法(PB)、化学共沉积法(CC)和仿生浸泡法(BI)合成了多壁碳纳米管/羟基磷灰石复合粉(MWNTs/HA), 并将其作为磷酸钙骨水泥(CPC)的固相粉末之一, 分别制备了相应的CPC样品。由于MWNTs对液相中水分子的吸附、毛细管作用以及表面存在较多的亲水基团, 使得含有MWNTs的CPC样品的亲水性得以提高, 且初凝时间和终凝时间都有所缩短, 但仍满足临床应用的要求。由于CPC中的MWNTs/HA复合粉末的合成方式不同, 使之对CPC的抗压性能、CPC中HA的结晶性、微观形貌影响均较大, 但并不影响CPC的晶相组成。其中PB法所合成的MWNTs/HA复合粉末能促进CPC中纳米级HA晶体的转化和生长, 使针状HA含量的表现为最高, 且抗压力学性能为最好, 其抗压强度和弹性模量分别较空白CPC提高了48.23%和41.87%。

关键词: 磷酸钙骨水泥, 碳纳米管, 羟基磷灰石, 物理共混, 化学共沉积, 仿生浸泡

Abstract:

The multi-walled carbon nanotubes (MWNTs)/ hydroxyapatite (HA) composites were synthesized by three different methods, namely physical blending (PB), chemical coprecipitation (CC) and bionic immersion (BI), and used as one of solid phase powders for the preparation of calcium phosphate cement (CPC). For the addition of MWNTs/HA composites, CPC had an increasing hydrophilicity and a decreasing initial and final setting time. However, the initial setting time and final of CPC made of MWNTs/HA powders still met the clinical requirements for the biomedical applications. The addition of MWNTs/HA composites synthesized by different methods had great effect on the compressive properties of CPC and HA crystallinity in CPC, but had no effect on the phase composition of CPC. Compared with blank CPC, CPC-CC and CPC-BI, CPC-PB had the best compressive mechanical properties and the highest HA conversion and content. Compared with blank CPC, the compressive strength and elastic modulus of CPC synthesized by PB method increased 48.23% and 41.87%, respectively.

Key words: calcium phosphate cement, carbon nanotubes, hydroxyapatite, physical blending, chemical coprecipit-

中图分类号:

TB321

邱添, 黄静静, 张苗, 王先福, 李辰, 卢晓英, 翁杰. 不同碳纳米管/羟基磷灰石复合粉末的添加对磷酸钙骨水泥性能和结构的影响[J]. 无机材料学报, 2013, 28(1): 91-96.

QIU Tian, HUANG Jing-Jing, ZHANG Miao, WANG Xian-Fu, LI Chen, LU Xiao-Ying, WENG Jie. Effects of Adding Carbon Nanotubes/Hydroxyapatite Composites on the Properties and Structure of Calcium Phosphate Cement[J]. Journal of Inorganic Materials, 2013, 28(1): 91-96.

图/表 9

Table 1 Constituents and liquid-solid ratio of CPC

Cements	Constituents				Liquid- solid ratio /(mL·g^-1)
Cements	8.5wt%	58wt%	25wt%	8.5wt%	Liquid- solid ratio /(mL·g^-1)
CPC-Blank	HA	β-TCP	DCPA	CaCO₃	0.35
CPC-PB CPC-CC CPC-BI	MWNTs/HA	β-TCP	DCPA	CaCO₃	0.47

图1 不同CPC样品的初凝时间和终凝时间

Fig. 1 Initial and final setting time of different CPC samples

图2 不同CPC样品的接触角和表面能图3为CPC的压缩应力-应变曲线。由图可知, 空白CPC和CPC-PB呈现脆性断裂, CPC-CC和CPC-BI呈现一定程度的韧性断裂; 在断裂前, CPC-PB曲线的斜率最大, 说明其弹性模量最大, 其平均值为(294.1±33.1) MPa(图4)。三种含有MWNTs的CPC的抗压强度和弹性模量有相同的变化趋势, 其中CPC-PB的抗压强度最大, 其平均值为(4.2±0.5) MPa, 对比空白CPC, 其弹性模量和抗压强度分别提高了41.87%和48.23%。基于此种情况, 本实验对三种CPC中的MWNTs/HA的复合粉作了FT-IR检测, 结果见图5。由图可知, 在PB法制备的MWNTs/HA的复合粉中, 952 cm-1处出现Si-O-P基团的吸收峰, Si-O-P基团的存在可以证明KH-792能够与HA发生化学键合作用而结合, 由于KH-792溶于95%乙醇溶液后发生水解生成Si-OH, 与HA的PO43-作用, 形成了稳定的Si-O-P键; 并且通过内标法发现位于1800 cm-1处-NH2吸收峰的吸收强度减弱, 以及吸收峰的位置发生红移现象, 说明部分-NH2与MWNTs上的-COOH联结, 将HA与MWNTs连接在一起, 起到桥梁剂的效果。因此, 通过KH-792可使得MWNTs在HA间均匀分散, 与HA形成良好的结合, 从而使得CPC-PB的力学性能有了一定提高。

Fig. 2 Contact angle and surface energy of different CPC samples

图3 不同CPC样品的应力-应变曲线

Fig. 3 Stress-strain curves of different CPC samples

图4 不同CPC样品的抗压强度和弹性模量

Fig. 4 Compressive strength and elastic modulus of different CPC samples

图5 不同方法制备的MWNTs/HA复合粉的红外图谱

Fig. 5 FTIR spectra of MWNTs/HA powder synthesized by different methods

图6 不同CPC样品的断面SEM照片

Fig. 6 SEM photographs of the fracture surface of different CPC samples(arrows: holes among the particles of CPC)

Table 2 Crystal size and content of HA in CPC samples

CPC	CPC-Blank	CPC-PB	CPC-CC	CPC-BI
Crystal size/nm	50.6	63.3	69.2	42.2
Content/wt%	33.97	37.52	31.84	33.57

图7 不同CPC样品的XRD图谱

Fig. 7 XRD patterns of different CPC samples

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