3-D printing of chitosan-calcium phosphate inks: rheology, interactions and characterization
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Bone substitute fabrication is of interest to meet the worldwide incidence of bone disorders. Physical chitosan hydrogels with intertwined apatite particles were chosen to meet the bio-physical and mechanical properties required by a potential bone substitute. A set up for 3-D printing by robocasting was found adequate to fabricate scaffolds. Inks consisted of suspensions of calcium phosphate particles in chitosan acidic aqueous solution. The inks are shear-thinning and consist of a suspension of dispersed platelet aggregates of dicalcium phosphate dihydrate in a continuous chitosan phase. The rheological properties of the inks were studied, including their shear-thinning characteristics and yield stress. Scaffolds were printed in basic water/ethanol baths to induce transformation of chitosan-calcium phosphates suspension into physical hydrogel of chitosan mineralized with apatite. Scaffolds consisted of a chitosan polymeric matrix intertwined with poorly crystalline apatite particles. Results indicate that ink rheological properties could be tuned by controlling ink composition: in particular, more printable inks are obtained with higher chitosan concentration (0.19 mol·L−1).
The authors are grateful to the JECS Trust for funding (Contract No. 2015101). This work was also supported by the LABEX iMUST (ANR-10-LABX-0064) of Université de Lyon, within the program “Investissements d’Avenir” (ANR-11-IDEX-0007) operated by the French National Research Agency (ANR). The authors also are grateful to the staff in the Centre of Advanced Structural Ceramics at Imperial College London for the collaboration work. Special thanks to Ezra Feilden and Esther García-Tuñon Blanca for the Robocasting machine training.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- 1.Amini AR, Laurencin CT, Nukavarapu SP. Bone tissue engineering: recent advances and challenges. Crit Rev Biomed Eng. 2012;40(5):363–408. https://doi.org/10.1615/CritRevBiomedEng.v40.i5.10.CrossRefGoogle Scholar
- 2.Vallet-Regi M. Bio-ceramics with clinical applications. John Wiley & Sons, 2014.Google Scholar
- 3.Philippart A, Boccaccini AR, Fleck C, Schubert DW, Roether JA. Toughening and functionalization of bioactive ceramic and glass bone scaffolds by biopolymer coatings and infiltration: a review of the last 5 years. Expert Rev Med Devices. 2015;12(1):93–111. https://doi.org/10.1586/17434440.2015.958075.CrossRefGoogle Scholar
- 5.Peroglio M, Gremillard L, Chevalier J, Chazeau L, Gauthier C, Hamaide T. Toughening of bio-ceramics scaffolds by polymer coating. J Eur Ceram Soc. 2007;27(7):2679–2685. https://doi.org/10.1016/j.jeurceramsoc.2006.10.016.CrossRefGoogle Scholar
- 9.Peroglio M, Gremillard L, Gauthier C, Chazeau L, Verrier S, Alini M, Chevalier J. Mechanical properties and cytocompatibility of poly(ε-caprolactone)-infiltrated biphasic calcium phosphate scaffolds with bimodal pore distribution. Acta Biomater. 2010;6(11):4369–4379. https://doi.org/10.1016/j.actbio.2010.05.022.CrossRefGoogle Scholar
- 14.Ladet SG, Tahiri K, Montembault AS, Domard AJ, Corvol MTM. Multi-membrane chitosan hydrogels as chondrocytic cell bioreactors. Biomaterials. 2011;32(23):5354–5364. https://doi.org/10.1016/j.biomaterials.2011.04.012.CrossRefGoogle Scholar
- 15.Chedly J, Soares S, Montembault A, Von Boxberg Y, Veron-Ravaille M, Mouffle C, Nothias F. Physical chitosan microhydrogels as scaffolds for spinal cord injury restoration and axon regeneration. Biomaterials. 2017;138:91–107. https://doi.org/10.1016/j.biomaterials.2017.05.024.CrossRefGoogle Scholar
- 21.Dash M, Chiellini F, Ottenbrite RM, Chiellini E. Chitosan—A versatile semi-synthetic polymer in biomedical applications. Progress Polym Sci. 2011;36(8):981–1014. https://doi.org/10.1016/j.progpolymsci.2011.02.001.CrossRefGoogle Scholar
- 24.Peniche C, Solís Y, Davidenko N, García R. Chitosan/hydroxyapatite-based composites. Biotecnol Apl. 2010;27(3):202–210.Google Scholar
- 29.Billiet T, Vandenhaute M, Schelfhout J, Van Vlierberghe S, Dubruel P. A review of trends and limitations in hydrogel-rapid prototyping for tissue engineering. Biomaterials. 2012;33(26):6020–6041. https://doi.org/10.1016/j.biomaterials.2012.04.050.CrossRefGoogle Scholar
- 39.Franck AJ. Understanding rheology of structured fluids. Book of TA instruments, 1–17, 2004. http://www.tainstruments.com/pdf/literature/AAN016_V1_U_StructFluids.pdf.
- 40.Feilden E, Garcia-Tunon Blanca E, Giuliani F, Saiz E, Vandeperre L. Robocasting of structural ceramic parts with hydrogel inks. J Eur Ceram Soc. 2016;36(10):2525–2533. https://doi.org/10.1016/j.jeurceramsoc.2016.03.001.CrossRefGoogle Scholar
- 42.Mekmene O, Quillard S, Rouillon T, Bouler JM, Piot M, Gaucheron F. Effects of pH and Ca/P molar ratio on the quantity and crystalline structure of calcium phosphates obtained from aqueous solutions. Dairy Sci & Technol. 2009;89(3–4):301–316. https://doi.org/10.1051/dst/2009019.CrossRefGoogle Scholar