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

Abstract

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

CLC Number:

TB321

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.

References

[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.