室温挤出3D打印HA/β-TCP/DCPA骨支架的复合浆料研究

硅酸盐通报 ›› 2024, Vol. 43 ›› Issue (9): 3472-3478.

室温挤出3D打印HA/β-TCP/DCPA骨支架的复合浆料研究

韩峥, 汪涛, 刘治伟, 聂云鹏, 王雪婷

南京航空航天大学材料科学与技术学院,南京 211106

收稿日期:2024-03-06 修订日期:2024-05-16 出版日期:2024-09-15 发布日期:2024-09-19
通信作者: 汪涛,博士,教授。E-mail:taowang@nuaa.cn
作者简介:韩峥(1999—),男,硕士研究生。主要从事骨水泥陶瓷方面的研究。E-mail:h920781656@163.com
基金资助:
国际科技合作计划(2018YFE0194100)

Composite Slurry for Room-Temperature Extrusion 3D Printing HA/β-TCP/DCPA Bone Scaffold

HAN Zheng, WANG Tao, LIU Zhiwei, NIE Yunpeng, WANG Xueting

School of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 211106, China

Received:2024-03-06 Revised:2024-05-16 Published:2024-09-15 Online:2024-09-19

摘要/Abstract

摘要： 基于3D打印骨支架的骨组织工程是一种具有应用潜力的骨修复策略。本文将植酸螯合改性的羟基磷灰石(IP6-HA)、β-磷酸三钙(β-TCP)与无水磷酸二氢钙(MCPA)按照不同摩尔比混合的复合粉体作为固相,以不同丙三醇(甘油)含量的水溶液作为液相,通过调整复合粉体中IP6-HA粉末的含量与固化液中甘油的含量,制备了能够应用于室温挤出3D打印骨支架的透钙磷石体系磷酸钙复合浆料。结果表明:复合浆料的水化产物主要为HA、β-TCP和无水磷酸氢钙(DCPA);当固化液中甘油含量为50%(质量分数)时,复合浆料均表现出优异的可打印性能与力学性能,抗压强度最高可达19.8 MPa;残余IP6-HA的存在改变了固化样品表面磷灰石的矿化结构并提升了矿化能力;制备的支架结构完整,孔洞均匀,抗压强度可达5.8 MPa。本研究制备的磷酸钙复合浆料能够通过室温挤出式3D打印技术制备骨支架,在3D打印领域具有良好的应用前景。

关键词: 透钙磷石, 羟基磷灰石, 3D打印, 力学性能, 骨支架

Abstract: Bone tissue engineering based on 3D printing bone scaffolds is a potential bone repair strategy. The composite powders of phytic acid chelating modified hydroxyapatite (IP6-HA), β-tricalcium phosphate (β-TCP) and anhydrous calcium dihydrogen phosphate (MCPA) with different molar ratios were used as solid phase, and the aqueous solution with different propylene glycol (glycerine) content was used as liquid phase. By adjusting IP6-HA powder content in composite powders and glycerine content in the curing solution, the calcium phosphate composite slurries of brushite system that can be applied to the room-temperature extrusion 3D printing bone scaffolds were prepared. The results show that hydration products of the composite slurries are mainly hydroxyapatite (HA), β-TCP and anhydrous calcium hydrogen phosphate (DCPA). When the glycerine content in the curing solution is 50% (mass fraction), the composite slurries exhibit excellent printability and mechanical properties, and the compressive strength can reach up to 19.8 MPa. The presence of residual IP6-HA changes the mineralization structure of apatite on surface of the solidified samples and improves the mineralization ability. The prepared scaffolds have a complete structure and uniform pores, and the compressive strength can reach 5.8 MPa. The composite slurries prepared in this study can be used to prepare bone scaffolds by room-temperature extrusion 3D printing technology, and has a good application prospect in the field of 3D printing bone scaffolds.

Key words: brushite, hydroxyapatite, 3D printing, mechanical property, bone scaffold

中图分类号:

TB321

韩峥, 汪涛, 刘治伟, 聂云鹏, 王雪婷. 室温挤出3D打印HA/β-TCP/DCPA骨支架的复合浆料研究[J]. 硅酸盐通报, 2024, 43(9): 3472-3478.

HAN Zheng, WANG Tao, LIU Zhiwei, NIE Yunpeng, WANG Xueting. Composite Slurry for Room-Temperature Extrusion 3D Printing HA/β-TCP/DCPA Bone Scaffold[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(9): 3472-3478.

参考文献

[1] MIRTCHI A A, LEMAITRE J, TERAO N. Calcium phosphate cements: study of the β-tricalcium phosphate: monocalcium phosphate system[J]. Biomaterials, 1989, 10(7): 475-480.
[2] MIRTCHI A A, LEMAÎTRE J, MUNTING E. Calcium phosphate cements: effect of fluorides on the setting and hardening of beta-tricalcium phosphate-dicalcium phosphate-calcite cements[J]. Biomaterials, 1991, 12(5): 505-510.
[3] ZHOU H, LUCHINI T J F, AGARWAL A K, et al. Development of monetite-nanosilica bone cement: a preliminary study[J]. Journal of Biomedical Materials Research Part B, Applied Biomaterials, 2014, 102(8): 1620-1626.
[4] KIM S Y, JEON S H. Setting properties, mechanical strength and in vivo evaluation of calcium phosphate-based bone cements[J]. Journal of Industrial and Engineering Chemistry, 2012, 18(1): 128-136.
[5] WANG C, HUANG W, ZHOU Y, et al. 3D printing of bone tissue engineering scaffolds[J]. Bioactive Materials, 2020, 5(1): 82-91.
[6] SHU Y, ZHOU Y, MA P W, et al. Degradation in vitro and in vivo of β-TCP/MCPM-based premixed calcium phosphate cement[J]. Journal of the Mechanical Behavior of Biomedical Materials, 2019, 90: 86-95.
[7] 祁燕, 汪涛, 杨心, 等. 螯合型羟基磷灰石骨水泥的制备[J]. 硅酸盐通报, 2016, 35(2): 496-499.
QI Y, WANG T, YANG X, et al. Fabrication of chelating hydroxyapatite cement[J]. Bulletin of the Chinese Ceramic Society, 2016, 35(2): 496-499 (in Chinese).
[8] NIE Y P, WANG T, WU M, et al. Characterization of a high strength hydroxyapatite cement with dual chelate-setting using phytic acid and citric acid[J]. International Journal of Applied Ceramic Technology, 2022, 19(3): 1498-1510.
[9] PENG J H, QU J D, ZHANG J X, et al. Adsorption characteristics of water-reducing agents on gypsum surface and its effect on the rheology of gypsum plaster[J]. Cement and Concrete Research, 2005, 35(3): 527-531.
[10] 刘琳, 孔祥东, 李玉成, 等. 预处理对丝素蛋白膜调控羟基磷灰石晶体生长的影响[J]. 高等学校化学学报, 2009, 30(10): 1987-1991.
LIU L, KONG X D, LI Y C, et al. Effect of pretreated silk fibroin films on the regulation of hydroxyapatite crystal growth[J]. Chemical Journal of Chinese Universities, 2009, 30(10): 1987-1991 (in Chinese).
[11] SAMAVEDI S, WHITTINGTON A R, GOLDSTEIN A S. Calcium phosphate ceramics in bone tissue engineering: a review of properties and their influence on cell behavior[J]. Acta Biomaterialia, 2013, 9(9): 8037-8045.
[12] TAMIMI F, SHEIKH Z, BARRALET J. Dicalcium phosphate cements: brushite and monetite[J]. Acta Biomaterialia, 2012, 8(2): 474-487.
[13] MIRTCHI A A, LEMAÎTRE J, MUNTING E. Calcium phosphate cements: action of setting regulators on the properties of the beta-tricalcium phosphate-monocalcium phosphate cements[J]. Biomaterials, 1989, 10(9): 634-638.
[14] HUAN Z G, CHANG J. Novel bioactive composite bone cements based on the β-tricalcium phosphate-monocalcium phosphate monohydrate composite cement system[J]. Acta Biomaterialia, 2009, 5(4): 1253-1264.
[15] ZHOU Z X, BUCHANAN F, MITCHELL C, et al. Printability of calcium phosphate: calcium sulfate powders for the application of tissue engineered bone scaffolds using the 3D printing technique[J]. Materials Science & Engineering C, Materials for Biological Applications, 2014, 38: 1-10.
[16] MARTÍNEZ-VÁZQUEZ F J, CABAÑAS M V, PARIS J L, et al. Fabrication of novel Si-doped hydroxyapatite/gelatine scaffolds by rapid prototyping for drug delivery and bone regeneration[J]. Acta Biomaterialia, 2015, 15: 200-209.
[17] SAHMANI S, KHANDAN A, ESMAEILI S, et al. Calcium phosphate-PLA scaffolds fabricated by fused deposition modeling technique for bone tissue applications: fabrication, characterization and simulation[J]. Ceramics International, 2020, 46(2): 2447-2456.