journal article·2025-12-08Open access

The Impact of Post-Printing Hydration in NaCl Solution on the Properties of Binder Jet 3D-Printed Calcium Sulfate and Its Converted Hydroxyapatite

Faungchat Thammarakcharoen, Autcharaporn Srion, Waraporn Suvannapruk, Wiroj Limtrakarn, Jintamai Suwanprateeb

Journal of Functional Biomaterials· Volume 16· Issue 12

Abstract

Binder jet 3D printing of calcium sulfate-based materials combined with phase transformation offers a versatile route for fabricating customized bone grafts; however, controlling the transformation process remains a key challenge. This study investigates the effect of post-printing hydration in sodium chloride (NaCl) solutions on the phase transformation, dimension, and compressive properties of binder jet-printed calcium sulfate (3DPCaS) toward hydroxyapatite (3DPHA) formation. The as-printed 3DPCaS primarily consisted of bassanite with minor gypsum, which progressively transformed into gypsum upon immersion in NaCl solutions of varying concentrations (1–5 M) and durations (2–30 min). Increased immersion time and moderate NaCl concentrations (2–4 M) promoted gypsum formation without inducing dimensional instability. Subsequent transformation in phosphate solution produced 3DPHA with high hydroxyapatite (HA) purity, reaching 100% conversion. Microstructural analysis revealed recrystallized, plate-like gypsum crystals that served as favorable templates for HA nucleation. The resulting 3DPHA exhibited enhanced specific modulus (up to 274.9 MPa.m3/kg) and specific strength (up to 7.5 MPa.m3/kg). The optimal condition, immersion in 4 M NaCl solution for 30 min, achieved a balance between complete HA transformation, mechanical enhancement, and dimensional stability. Controlled ionic hydration thus represents a simple, low-cost, and effective strategy for improving properties of 3DPHA bone grafts.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Bone Tissue Engineering Materials · Calcium Carbonate Crystallization and Inhibition · 3D Printing in Biomedical Research

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Biofunctional Materials and Devices Research Group, National Metal and Materials Technology Center (MTEC), National Science and Technology Development Agency (NSTDA), Khlong Nueng, Khlong Luang, Pathum Thani 12120, Thailand

Department of Mechanical Engineering, Faculty of Engineering, Thammasat University, Khlong Nueng, Khlong Luang, Pathum Thani 12120, Thailand

Thammasat University Center of Excellence in Computational Mechanics and Medical Engineering, Thammasat University, Khlong Nueng, Khlong Luang, Pathum Thani 12120, Thailand

Funding

Platform Technology, the National Metal Materials Technology Center

References (47)

Show source-provided references
1. Sustainable Pathways for the Synthesis of Calcium Sulfate Hemihydrate10.1002/anie.202415161 ↗
2. Effects of Magnesia and Potassium Sulfate on Gypsum-Bonded Alumina Dental Investment for High-Fusing Casting10.4012/dmj.17.301 ↗
3. Straub, J., Sewing, A., Walter, N., Wong, R.M.Y., Alt, V., Heiss, C., and Rupp, M. (2025). Calcium Sulfate Bone Substitutes in Clinical Use: History, Material Properties, Application, and Outlook for the Future. J. Biomed. Mater. Res. B Appl. Biomater., 113.10.1002/jbm.b.35555 ↗
4. Bone Regeneration: Properties and Clinical Applications of Bi-Phasic Calcium Sulfate10.1016/j.cden.2019.12.006 ↗
5. In-situ X-ray Tomographic Monitoring of Gypsum Plaster Setting10.1016/j.cemconres.2015.12.011 ↗
6. 4D In Situ Monitoring of the Setting of Alpha Plaster Using Synchrotron X-ray Tomography with High Spatial and Temporal Resolution10.1016/j.conbuildmat.2021.124632 ↗
7. Zafar, M.J., Zhu, D., and Zhang, Z. (2019). 3D Printing of Bioceramics for Bone Tissue Engineering. Materials, 12.10.3390/ma12203361 ↗
8. 3D Printing of Calcium Phosphate Ceramics for Bone Tissue Engineering and Drug Delivery10.1007/s10439-016-1678-3 ↗
9. Castro-Sastre, M.Á., Fernández-Abia, A.I., Piep, J., Rodríguez-González, P., and Barreiro, J. (2020). Towards Functional Parts by Binder Jetting Calcium-Sulphate with Thermal Treatment Post-Processing. Materials, 13.10.3390/ma13173818 ↗
10. Mechanical anisotropy and fracture mode of binder jetting 3D printed calcium sulfate moldings10.1016/j.apmt.2021.101160 ↗
11. Process capability analysis of binder jetting 3D printing process for fabrication of calcium sulphate-based porous bone scaffolds10.1080/14484846.2020.1842295 ↗
12. Unraveling the influence of solvent composition on Drop-on-Demand binder jet 3D printed tablets containing calcium sulfate hemihydrate10.1016/j.ijpharm.2023.123652 ↗
13. Asadi-Eydivand, M., Solati-Hashjin, M., Shafiei, S.S., Mohammadi, S., Hafezi, M., and Abu Osman, N.A. (2016). Structure, Properties, and In Vitro Behavior of Heat-Treated Calcium Sulfate Scaffolds Fabricated by 3D Printing. PLoS ONE, 11.10.1371/journal.pone.0151216 ↗
14. Couți, N., Porfire, A., Iovanov, R., Crișan, A.G., Iurian, S., Casian, T., and Tomuță, I. (2024). Polyvinyl Alcohol, a Versatile Excipient for Pharmaceutical 3D Printing. Polymers, 16.10.3390/polym16040517 ↗
15. Model Approach for Binder Selection in Binder Jetting10.1021/acs.iecr.1c02856 ↗
16. Use of Aqueous Polyvinyl Alcohol in Binder Jetting of Inconel 71810.1007/s00170-024-14649-7 ↗
17. Calcium Sulphate Hemihydrate Hydration Leading to Gypsum Crystallization10.1016/j.pcrysgrow.2007.01.002 ↗
18. Low Temperature Preparation of Calcium Phosphate Structure via Phosphorization of 3DP Calcium Sulfate Hemihydrate Based Material10.1007/s10856-009-3883-1 ↗
19. In Vitro Resorbability and Granular Characteristics of 3D-Printed Hydroxyapatite Granules versus Allograft, Xenograft, and Alloplast for Alveolar Cleft Surgery Applications10.1177/09544119211034370 ↗
20. Meesuk, L., Suwanprateeb, J., Thammarakcharoen, F., Tantrawatpan, C., Kheolamai, P., Palang, I., Tantikanlayaporn, D., and Manochantr, S. (2022). Osteogenic Differentiation and Proliferation Potentials of Human Bone Marrow and Umbilical Cord-Derived Mesenchymal Stem Cells on 3D-Printed Hydroxyapatite Scaffolds. Sci. Rep., 12.10.1038/s41598-022-24160-2 ↗
21. Thammarakcharoen, F., Srion, A., Suvannapruk, W., Chokevivat, W., Limtrakarn, W., and Suwanprateeb, J. (2024). Process Development for Fabricating 3D-Printed Polycaprolactone-Infiltrated Hydroxyapatite Bone Graft Granules: Effects of Infiltrated Solution Concentration and Agitating Liquid. Biomedicines, 12.10.3390/biomedicines12092161 ↗
22. Clinical Evaluation of 3D-Printed Nanoporous Hydroxyapatite Bone Graft for Alveolar Ridge Preservation: A Randomized Controlled Trial10.1016/j.jds.2021.05.003 ↗
23. Customized 3D-Printed Nanohydroxyapatite Bone Block Grafts for Implant Sites: A Case Series10.2186/jpr.JPR_D_22_00037 ↗
24. Jiamton, C., Apivatgaroon, A., Aunaramwat, S., Chawalitrujiwong, B., Chuaychoosakoon, C., Suwannaphisit, S., Jirawison, C., Iamsumang, C., Kongmalai, P., and Sukvanich, P. (2023). Efficacy and Safety of Antibiotic-Impregnated Microporous Nanohydroxyapatite Beads for Chronic Osteomyelitis Treatment: A Multicenter, Open-Label, Prospective Cohort Study. Antibiotics, 12.10.3390/antibiotics12061049 ↗
25. Development of Polycaprolactone-Infiltrated Anti-Tuberculosis Drug-Loaded 3D-Printed Hydroxyapatite for Localized and Sustained Drug Release in Bone and Joint Tuberculosis Treatment10.12982/CMJS.2022.009 ↗
26. Suwanprateeb, J., Thammarakcharoen, F., Phanphiriya, P., Chokevivat, W., Suvannapruk, W., and Chernchujit, B. (2014). Preparation and Characterization of Antibiotic-Impregnated Microporous Nano-Hydroxyapatite for Osteomyelitis Treatment. Biomed. Eng. Appl. Basis Commun., 26.10.4015/S1016237214500410 ↗
27. Effects of Impurities on CaSO4 Crystallization in the Ca(H2PO4)2–H2SO4–H3PO4–H2O System10.1021/acsomega.9b01114 ↗
28. Sim, S., Lee, H., Jeon, D., Song, H., Yum, W.S., Kim, D., Suh, J.-I., and Oh, J.E. (2018). Gypsum-Dependent Effect of NaCl on Strength Enhancement of CaO-Activated Slag Binders. Appl. Sci., 8.10.3390/app8122515 ↗
29. Effect of Pre-Introduced Sodium Chloride on Cement Hydration Process10.1680/jadcr.19.00159 ↗
30. Solubility of Gypsum in Aqueous NaCl + K2SO4 Solution Using Calcium Ion Selective Electrode: Investigation of Ionic Interactions10.1016/j.fluid.2015.10.011 ↗
31. Influence of Impurities on Hydration, Hardening and Morphology of Flue Gas Desulphurization Gypsum Plaster10.1016/j.proeng.2011.12.466 ↗
32. Structural Insights into the Dehydration and Rehydration of Gypsum10.1021/acs.cgd.4c01414 ↗
33. The Hydrophobic Modification of Gypsum Binder by Peat Products: Physico-Chemical and Technological Basis10.19189/MAP.2017.OMB.300 ↗
34. Competition between Crystallization-Induced Expansion and Creep Compaction during Gypsum Formation, and Implications for Serpentinization10.1029/2017JB015369 ↗
35. Linear setting expansion of three different types of dental stones available in Iraqi market: A comparative study10.32828/mdj.v3i1.620 ↗
36. Environmental aspects of saline water disposal
37. Gypsum Nucleation into Sodium Chloride Solutions10.1002/aic.690470415 ↗
38. Effect of pH on the Solubility of CaSO4·2H2O in Aqueous NaCl Solutions and Physicochemical Solution Properties at 35 °C10.1021/je800465f ↗
39. Solubility and Physical Properties of α-Calcium Sulfate Hemihydrate in NaCl and Glycerol Aqueous Solutions at 303.15–343.15 K10.1021/acs.jced.1c00214 ↗
40. Effect of Incorporation of Disinfectant Solutions on Setting Time, Linear Dimensional Stability, and Detail Reproduction in Dental Stone Casts10.1111/j.1532-849X.2009.00466.x ↗
41. Apatite Formation from Amorphous Calcium Phosphate and Mixed Amorphous Calcium Phosphate/Amorphous Calcium Carbonate10.1002/chem.201601280 ↗
42. Phase Evolution during the Low-Temperature Formation of Stoichiometric Hydroxyapatite–Gypsum Composites10.1016/j.ceramint.2010.09.046 ↗
43. Communication: Modeling of Concentration-Dependent Water Diffusivity in Ionic Solutions: Role of Intermolecular Charge Transfer10.1063/1.4938083 ↗
44. Hydrothermal Synthesis of Hydroxyapatite Crystals with and without Seed Crystals and Surfactant10.1007/s42452-024-05754-z ↗
45. Effect of Microporosity on Scaffolds for Bone Tissue Engineering10.1093/rb/rby001 ↗
46. Beta-TCP Scaffolds with Rationally Designed Macro-Micro Hierarchical Structure Improved Angio/Osteogenesis Capability for Bone Regeneration10.1007/s10856-023-06733-3 ↗
47. Chan, S.S.L., Black, J.R., Franks, G.V., and Heath, D.E. (2025). Hierarchically Porous 3D-Printed Ceramic Scaffolds for Bone Tissue Engineering. Biomater. Adv., 169.10.1016/j.bioadv.2024.214149 ↗