DLP打印β-磷酸三钙/纳米黏土复合支架的制备与表征

doi:10.15541/jim20210745

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1116-1122.DOI: 10.15541/jim20210745

所属专题：【生物材料】骨骼与齿类组织修复

DLP打印β-磷酸三钙/纳米黏土复合支架的制备与表征

张航¹(), 韩坤原², 董兰兰¹, 李祥¹()

1.上海交通大学机械与动力工程学院, 机械系统与振动国家重点实验室, 上海 200240
2.上海理工大学健康科学与工程学院, 上海 200093

收稿日期:2021-12-07 修回日期:2022-01-25 出版日期:2022-10-20 网络出版日期:2022-06-16
通讯作者: 李祥, 副研究员. E-mail: xiangliwj@sjtu.edu.cn
作者简介:张航(1994-), 男, 博士研究生. E-mail: hangzhang@sjtu.edu.cn
基金资助:
国家自然科学基金(51475293);上海交通大学医工交叉基金(YG2021ZD06)

Preparation and Characterization of β-tricalcium Phosphate/Nano Clay Composite Scaffolds via Digital Light Processing Printing

ZHANG Hang¹(), HAN Kunyuan², DONG Lanlan¹, LI Xiang¹()

1. State Key Laboratory of Mechanical System and Vibration, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
2. School of Heal Science and Engineering, Shanghai University of Technology, Shanghai 200093, China

Received:2021-12-07 Revised:2022-01-25 Published:2022-10-20 Online:2022-06-16
Contact: LI Xiang, associate professor. E-mail: xiangliwj@sjtu.edu.cn
About author:ZHANG Hang (1994-), male, PhD candidate. E-mail: hangzhang@sjtu.edu.cn
Supported by:
National Natural Science Foundation of China(51475293);Cross-Institute Research Fund of Shanghai Jiao Tong University(YG2021ZD06)

摘要/Abstract

摘要：

β-磷酸三钙(β-TCP)具有生物降解性和生物相容性, 但其固有的脆性限制了其在承重种植体中的应用。为进一步提高β-TCP的力学性能和生物相容性, 本研究以纳米黏土(Nano clay, NC)为添加剂, 采用数字光处理(Digital light processing, DLP)技术制备了β-TCP/NC(TNC)复合支架, 支架TNC10多孔结构孔径为200~300 μm。当加入NC含量为10%(质量分数)时, 支架(TNC10)各结构特征的烧结收缩最小。加入NC不会改变TCP的物相成分, 且支架表面均匀分布Si、Mg元素。加入NC可以提高TCP支架的压缩强度, NC(粒径<500 nm)融合在TCP颗粒的间隙中, 对比纯TCP支架, TNC10支架的压缩强度提高了10%。另外, TNC10 组较纯TCP的比表面积增加2倍以上。TNC降解速率更快, 可以持续释放Ca、Mg、Si、Li等离子, 并且TNC降解液保持弱碱性的环境。研究结果表明: 加入NC对β-TCP支架的力学强度、降解性能均具有一定的促进作用。利用DLP方法打印的具有良好的理化性能的多孔生物陶瓷支架在骨修复领域有巨大应用前景。

关键词: β-磷酸三钙, DLP打印, 多孔支架, 纳米黏土

Abstract:

β-tricalcium phosphate (β-TCP) has biodegradability and biocompatibility, but its inherent brittleness limits its application in load-bearing implants. In order to further improve the mechanical property and biocompatibility of β-TCP, β-TCP/NC (TNC) composite scaffold with nano clay (NC) as additive and the porous structure of the scaffold has a pore size of 200-300 μm was prepared by digital light processing (DLP) technique. When the content of NC is 10% (in mass), the sintering shrinkage of each structural feature of the support (TNC10) is the smallest. Addition of NC does not change the phase composition of TCP, and Si and Mg elements are evenly distributed on the surface of the scaffold. Addition of NC can improve the compression strength of TCP scaffolds. NC (particle size < 500 nm) is fused in the gap of TCP particles. Compared with pure TCP scaffolds, the compression strength of TNC10 is increased by 10%. In addition, the specific surface area of TNC10 group was more than 2 times higher than that of pure TCP. TNC degradation rate is faster while Ca²⁺, Mg²⁺, Si⁴⁺, and Li²⁺ can be continuously released, which maintains a weakly alkaline environment. The results demonstrate that the addition of NC has a certain promotion effect on the mechanical strength, degradation performance β-TCP scaffolds. Porous bioceramic scaffolds with good physical, chemical property by DLP method have great application prospects in the field of bone repair.

Key words: β-tricalcium phosphate, DLP printing, porous scaffold, nano clay

中图分类号:

TQ174

张航, 韩坤原, 董兰兰, 李祥. DLP打印β-磷酸三钙/纳米黏土复合支架的制备与表征[J]. 无机材料学报, 2022, 37(10): 1116-1122.

ZHANG Hang, HAN Kunyuan, DONG Lanlan, LI Xiang. Preparation and Characterization of β-tricalcium Phosphate/Nano Clay Composite Scaffolds via Digital Light Processing Printing[J]. Journal of Inorganic Materials, 2022, 37(10): 1116-1122.

图/表 9

表1 制备多孔生物陶瓷的主要原料与试剂

Table 1 Main raw materials and reagents for preparation of porous bioceramics

Materials and reagent	Chemical agent	Dosage/% (in mass)
Ceramic powder	β-TCP	50-60
Resin monomer	PEG200DA	20-40
Crosslinking agent	3,3-Dimethylacrylic acid	2-4
Dispersant	DCA-1228	0.3-1.0
Photoinitiator	TPO	0.5
Nano clay	Laponite	0-10

图1 DLP陶瓷打印设备原理图

Fig. 1 Schematic diagram of DLP ceramic printing equipment

图2 支架表面形貌

Fig. 2 Surface morphologies of scaffold (a, d, g, j) Microscope photos of scaffolds; (b, e, h, k) Microscope photos of scaffolds; (c, f, i, l) SEM images of scaffolds

图3 多孔支架收缩率

Fig. 3 Shrinkage of porous scaffold (a) Definition of pore and bar for porous scaffolds; (b) Sintering shrinkage of scaffolds

图4 多空支架成分分析

Fig. 4 Component analysis of porous scaffolds (a) XRD patterns of porous scaffolds; (b) EDS analysis of the surface of scaffolds

图5 支架力学性能分析

Fig. 5 Mechanical property analysis of porous scaffolds (a) Porosity and specific surface area of the scaffolds; (b) Compression strength of the scaffolds; (c) Schematic diagram of NC enhanced TCP

图6 支架降解后的失重和pH变化情况

Fig. 6 Weight loss and pH change after scaffold degradation (a) Weight loss of scaffold after soaking in SBF for different time; (b) pH change of SBF after soaking the scaffolds

图7 支架经SBF浸泡后释放的离子浓度变化

Fig. 7 Changes of ion concentration released from scaffolds soaked in SBF (a) Ca2+; (b) Mg2+; (c) Li+; (d) Si4+

图8 四组支架经SBF浸泡降解后表面形貌变化

Fig. 8 Surface morphologies of scaffold after degradation in SBF (a, b) TCP; (c, d) TNC2; (e, f) TNC5; (g, h) TNC10

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DLP打印β-磷酸三钙/纳米黏土复合支架的制备与表征

Preparation and Characterization of β-tricalcium Phosphate/Nano Clay Composite Scaffolds via Digital Light Processing Printing

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