Effect of sintering temperature and polyvinyl alcohol composition as binder on the formation of porous hydroxyapatite as bone graft using sponge replication method: A review

Main Article Content

Baharudin Priwintoko
Rifky Ismail
Deni Fajar Fitriyana
Yusuf Subagyo
Athanasius Priharyoto Bayuseno


Hydroxyapatite (HA) is one of the inorganic components that has a role as a bone regeneration material. The potential for utilizing waste is one of the opportunities in HA commodities. Several waste materials that can be used as raw materials for HA include egg shells, beef bones, fish bones, limestone, and marine biota shells. Nowadays, the use of HA is not only limited to regeneration materials but also as a bone tissue scaffold. Porous HA is a form of HA that is in great demand today because it can be a good scaffold and regeneration material. One method that can be used to fabricate porous HA is the sponge replicated method. In its fabrication, the sponge replicated method is influenced by sintering temperature and binder composition. Polyvinyl alcohol (PVA) is a widely used binder because it can be evaporated without leaving traces and is biocompatible. This paper will examine the effect of sintering temperature and composition of PVA as a binder in pore HA fabrication. In particular, this paper compares the fabrication process with the characteristics of the resulting porous HA against commercial products and ISO 13379:2015 standards. According to the preliminary study, pore HA that conforms to the standard will have a good impact on the healing process of bone defects. The novelty of this research is to explore in depth related to the fabrication of HA pores using the sponge replicated method with sintering temperature parameters and the composition of PVA as a binder so that it is expected to be a literature for future researchers.


Download data is not yet available.

Article Details



[1] A. Atala, R. Lanza, and R. Nerem, Principles of Regenerative Medicine. Elsevier, 2019.
[2] Y. Zhang and L. Rehmmann, “Extraction of high-value compounds from marine biomass via ionic liquid-based techniques,” in Innovative and Emerging Technologies in the Bio-marine Food Sector, Elsevier, 2022, pp. 417–439.
[3] T. U. Habibah and H. G. Salisbury, Hydroxyapatite Dental Material. Treasure Island (FL): StatPearls Publishing, 2019.
[4] M. Sari, Aminatun, T. Suciati, Y. W. Sari, and Y. Yusuf, “Porous Carbonated Hydroxyapatite-Based Paraffin Wax Nanocomposite Scaffold for Bone Tissue Engineering: A Physicochemical Properties and Cell Viability Assay Analysis,” Coatings, vol. 11, no. 10, p. 1189, Sep. 2021, doi: 10.3390/coatings11101189.
[5] W. Wang and K. W. K. Yeung, “Bone grafts and biomaterials substitutes for bone defect repair: A review,” Bioactive Materials, vol. 2, no. 4, pp. 224–247, Dec. 2017, doi: 10.1016/j.bioactmat.2017.05.007.
[6] S. Bhat, U. T. Uthappa, T. Altalhi, H.-Y. Jung, and M. D. Kurkuri, “Functionalized Porous Hydroxyapatite Scaffolds for Tissue Engineering Applications: A Focused Review,” ACS Biomaterials Science & Engineering, vol. 8, no. 10, pp. 4039–4076, Oct. 2022, doi: 10.1021/acsbiomaterials.1c00438.
[7] Z. Wu, Z. Zhou, and Y. Hong, “Isotropic freeze casting of through-porous hydroxyapatite ceramics,” Journal of Advanced Ceramics, vol. 8, no. 2, pp. 256–264, Jun. 2019, doi: 10.1007/s40145-018-0312-2.
[8] K. Zhou et al., “Hierarchically Porous Hydroxyapatite Hybrid Scaffold Incorporated with Reduced Graphene Oxide for Rapid Bone Ingrowth and Repair,” ACS Nano, vol. 13, no. 8, pp. 9595–9606, Aug. 2019, doi: 10.1021/acsnano.9b04723.
[9] A. Fadli, P. Widiyanti, D. Noviana, A. Prabowo, and H. Ismawati, “Preparation of Hydroxyapatite Scaffold using Luffa Cylindrica Sponge as Template,” Jurnal Rekayasa Kimia & Lingkungan, vol. 15, no. 2, pp. 62–70, 2020, doi: 10.23955/rkl.v15i2.15957.
[10] X. Wang, G. Wang, A. Marchetti, L. Wu, L. Wu, and Y. Guan, “Preparation of porous hydroxyapatite and its application in Pb ions effective removal,” AIP Advances, vol. 9, no. 2, p. 025123, Feb. 2019, doi: 10.1063/1.5086705.
[11] S.-M. Huang, S.-M. Liu, C.-L. Ko, and W.-C. Chen, “Advances of Hydroxyapatite Hybrid Organic Composite Used as Drug or Protein Carriers for Biomedical Applications: A Review,” Polymers, vol. 14, no. 5, p. 976, Feb. 2022, doi: 10.3390/polym14050976.
[12] A. Prasad, M. R. Sankar, and V. Katiyar, “State of Art on Solvent Casting Particulate Leaching Method for Orthopedic ScaffoldsFabrication,” Materials Today: Proceedings, vol. 4, no. 2, pp. 898–907, 2017, doi: 10.1016/j.matpr.2017.01.101.
[13] M. Friuli, P. Nitti, M. Madaghiele, and C. Demitri, “A possible method to avoid skin effect in polymeric scaffold produced through thermally induced phase separation,” Results in Engineering, vol. 12, p. 100282, Dec. 2021, doi: 10.1016/j.rineng.2021.100282.
[14] J. Xue, T. Wu, Y. Dai, and Y. Xia, “Electrospinning and Electrospun Nanofibers: Methods, Materials, and Applications,” Chemical Reviews, vol. 119, no. 8, pp. 5298–5415, Apr. 2019, doi: 10.1021/acs.chemrev.8b00593.
[15] F. Baino and S. Yamaguchi, “The use of simulated body fluid (SBF) for assessing materials bioactivity in the context of tissue engineering: Review and challenges,” Biomimetics, vol. 5, no. 4, pp. 1–19, 2020, doi: 10.3390/biomimetics5040057.
[16] T. Nonoyama, “Bioceramics x soft material as a simple model to mimic functions in bones,” Journal of the Ceramic Society of Japan, vol. 130, no. 10, pp. 817–824, 2022, doi: 10.2109/jcersj2.22089.
[17] Sutygina, Betke, and Scheffler, “Open-Cell Aluminum Foams by the Sponge Replication Technique,” Materials, vol. 12, no. 23, p. 3840, Nov. 2019, doi: 10.3390/ma12233840.
[18] C. Wang, H. Chen, X. Zhu, Z. Xiao, K. Zhang, and X. Zhang, “An improved polymeric sponge replication method for biomedical porous titanium scaffolds,” Materials Science and Engineering: C, vol. 70, pp. 1192–1199, Jan. 2017, doi: 10.1016/j.msec.2016.03.037.
[19] A. Fadli, A. Lubis, F. Huda, and K. Komalasari, “Hydroxyapatite Scaffolds Fabrication using Gambas Sponge ( Luffa cylindrica ) as Novel Template,” in Proceeding of the First International Conference on Technology, Innovation and Society, Jul. 2016, pp. 53–56, doi: 10.21063/ICTIS.2016.1009.
[20] M. Yazdimamaghani, M. Razavi, D. Vashaee, K. Moharamzadeh, and A. R. Boccaccini, “Porous Magnesium-Based Scaffolds for Tissue Engineering,” Materials Science and Engineering: C, vol. 71, no. February, pp. 1253–1266, 2017, doi: 10.1016/j.msec.2016.11.027.
[21] J. T. Y. Lee and K. L. Chow, “SEM sample preparation for cells on 3D scaffolds by freeze‐drying and HMDS,” Scanning, vol. 34, no. 1, pp. 12–25, Feb. 2012, doi: 10.1002/sca.20271.
[22] C. Zhang, H. Li, Z. Guo, B. Xue, and C. Zhou, “Fabrication of Hydroxyapatite Nanofiber via Electrospinning as a Carrier for Protein,” Journal of Nanoscience and Nanotechnology, vol. 17, no. 2, pp. 1018–1024, Feb. 2017, doi: 10.1166/jnn.2017.12620.
[23] J. Liu et al., “Polycaprolactone/Gelatin/Hydroxyapatite Electrospun Nanomembrane Materials Incorporated with Different Proportions of Attapulgite Synergistically Promote Bone Formation,” International Journal of Nanomedicine, vol. Volume 17, pp. 4087–4103, Sep. 2022, doi: 10.2147/IJN.S372247.
[24] S. N. Aulia, R. H. Mulyani, and D. H. Prajitno, “Electrodeposition of Composite Hydroxyapatite-Chitosan from Local Materials on Stainless Steel 304,” Jurnal Kartika Kimia, vol. 2, no. 2, Nov. 2019, doi: 10.26874/jkk.v2i2.37.
[25] N. Kanasan, S. Adzila, N. AzimahMustaffa, and P. Gurubaran, “The Effect of Sodium Alginate on the Properties of Hydroxyapatite,” Procedia Engineering, vol. 184, pp. 442–448, 2017, doi: 10.1016/j.proeng.2017.04.115.
[26] A. S. Neto and J. M. F. Ferreira, “Biphasic calcium phosphate scaffolds derived from hydrothermally synthesized powders,” Lekar a Technika, vol. 48, no. 3, pp. 77–83, 2018.
[27] K. Okuda, R. Shigemasa, K. Hirota, and T. Mizutani, “In Situ Crystallization of Hydroxyapatite on Carboxymethyl Cellulose as a Biomimetic Approach to Biomass-Derived Composite Materials,” ACS Omega, vol. 7, no. 14, pp. 12127–12137, Apr. 2022, doi: 10.1021/acsomega.2c00423.
[28] S. Sözügeçer and N. P. Bayramgil, “Preparation and characterization of polyacrylic acid-hydroxyapatite nanocomposite by microwave-assisted synthesis method,” Heliyon, vol. 7, no. 6, p. e07226, Jun. 2021, doi: 10.1016/j.heliyon.2021.e07226.
[29] M. R. Mohd Roslan et al., “The State of Starch/Hydroxyapatite Composite Scaffold in Bone Tissue Engineering with Consideration for Dielectric Measurement as an Alternative Characterization Technique,” Materials, vol. 14, no. 8, p. 1960, Apr. 2021, doi: 10.3390/ma14081960.
[30] M. B. Jalageri and G. C. Mohan Kumar, “Hydroxyapatite Reinforced Polyvinyl Alcohol/Polyvinyl Pyrrolidone Based Hydrogel for Cartilage Replacement,” Gels, vol. 8, no. 9, p. 555, Sep. 2022, doi: 10.3390/gels8090555.
[31] J. Brady, T. Dürig, P. I. Lee, and J.-X. Li, “Polymer Properties and Characterization,” in Developing Solid Oral Dosage Forms, Elsevier, 2017, pp. 181–223.
[32] I. Novella, B. Rupaedah, D. R. Eddy, Suryana, F. S. Irwansyah, and A. R. Noviyanti, “The Influence of Polyvinyl Alcohol Porogen Addition on the Nanostructural Characteristics of Hydroxyapatite,” Materials, vol. 16, no. 18, p. 6313, Sep. 2023, doi: 10.3390/ma16186313.
[33] P. Ghelich, M. Kazemzadeh-Narbat, A. Hassani Najafabadi, M. Samandari, A. Memić, and A. Tamayol, “(Bio)manufactured Solutions for Treatment of Bone Defects with an Emphasis on US‐FDA Regulatory Science Perspective,” Advanced NanoBiomed Research, vol. 2, no. 4, p. 2100073, Apr. 2022, doi: 10.1002/anbr.202100073.
[34] T. Ghassemi, A. Shahroodi, M. H. Ebrahimzadeh, A. Mousavian, J. Movaffagh, and A. Moradi, “Current concepts in scaffolding for bone tissue engineering,” Archives of Bone and Joint Surgery, vol. 6, no. 2, pp. 90–99, 2018, doi: 10.22038/abjs.2018.26340.1713.
[35] M. Filippi, G. Born, M. Chaaban, and A. Scherberich, “Natural Polymeric Scaffolds in Bone Regeneration,” Frontiers in Bioengineering and Biotechnology, vol. 8, May 2020, doi: 10.3389/fbioe.2020.00474.
[36] M. Shariful Islam, M. Abdulla-Al-Mamun, A. Khan, and M. Todo, “Excellency of Hydroxyapatite Composite Scaffolds for Bone Tissue Engineering,” in Biomaterials, IntechOpen, 2020.
[37] M. Bahraminasab, “Challenges on optimization of 3D-printed bone scaffolds,” BioMedical Engineering Online, vol. 19, no. 1, pp. 1–33, 2020, doi: 10.1186/s12938-020-00810-2.
[38] C. O’Connor, I. Woods, A. Hibbitts, A. Dervan, and F. J. O’Brien, “The Manufacture and Characterization of Biomimetic, Biomaterial‐Based Scaffolds for Studying Physicochemical Interactions of Neural Cells in 3D Environments,” Current Protocols, vol. 3, no. 2, Feb. 2023, doi: 10.1002/cpz1.688.
[39] H. Siddiqui, K. Pickering, and M. Mucalo, “A Review on the Use of Hydroxyapatite-Carbonaceous Structure Composites in Bone Replacement Materials for Strengthening Purposes,” Materials, vol. 11, no. 10, p. 1813, Sep. 2018, doi: 10.3390/ma11101813.
[40] Y. Chen, N. Wang, O. Ola, Y. Xia, and Y. Zhu, “Porous ceramics: Light in weight but heavy in energy and environment technologies,” Materials Science and Engineering: R: Reports, vol. 143, p. 100589, Jan. 2021, doi: 10.1016/j.mser.2020.100589.
[41] A. Scarano, F. Lorusso, P. Santos de Oliveira, S. Kunjalukkal Padmanabhan, and A. Licciulli, “Hydroxyapatite Block Produced by Sponge Replica Method: Mechanical, Clinical and Histologic Observations,” Materials, vol. 12, no. 19, p. 3079, Sep. 2019, doi: 10.3390/ma12193079.
[42] T. G. Chatzimitakos and C. D. Stalikas, “Sponges and Sponge-Like Materials in Sample Preparation: A Journey from Past to Present and into the Future,” Molecules, vol. 25, no. 16, p. 3673, Aug. 2020, doi: 10.3390/molecules25163673.
[43] J. S. Meschke, “Validation of a Sponge Processing Method for Characterizing Microbes in the Bullitt Center,” 2015.
[44] E. Al-Qadhi, G. Li, and Y. Ni, “Influence of a Two-Stage Sintering Process on Characteristics of Porous Ceramics Produced with Sewage Sludge and Coal Ash as Low-Cost Raw Materials,” Advances in Materials Science and Engineering, vol. 2019, pp. 1–12, Nov. 2019, doi: 10.1155/2019/3710692.
[45] L. K. Singh, A. Bhadauria, S. Jana, and T. Laha, “Effect of Sintering Temperature and Heating Rate on Crystallite Size, Densification Behaviour and Mechanical Properties of Al-MWCNT Nanocomposite Consolidated via Spark Plasma Sintering,” Acta Metallurgica Sinica (English Letters), vol. 31, no. 10, pp. 1019–1030, Oct. 2018, doi: 10.1007/s40195-018-0795-4.
[46] Y. Shi et al., “Polymer materials for additive manufacturing—powder materials,” in Materials for Additive Manufacturing, Elsevier, 2021, pp. 9–189.
[47] M. A. Mazo, I. Padilla, A. Tamayo, J. I. Robla, A. López-Delgado, and J. Rubio, “Evaluation of thermal shock resistance of silicon oxycarbide materials for high-temperature receiver applications,” Solar Energy, vol. 173, pp. 256–267, Oct. 2018, doi: 10.1016/j.solener.2018.07.080.
[48] N. J. Lóh, L. Simão, J. Jiusti, A. De Noni Jr., and O. R. K. Montedo, “Effect of temperature and holding time on the densification of alumina obtained by two-step sintering,” Ceramics International, vol. 43, no. 11, pp. 8269–8275, Aug. 2017, doi: 10.1016/j.ceramint.2017.03.159.
[49] V. Momeni et al., “Research Progress on Low-Pressure Powder Injection Molding,” Materials, vol. 16, no. 1, p. 379, Dec. 2022, doi: 10.3390/ma16010379.
[50] H. Miyanaji, K. M. Rahman, M. Da, and C. B. Williams, “Effect of fine powder particles on quality of binder jetting parts,” Additive Manufacturing, vol. 36, p. 101587, Dec. 2020, doi: 10.1016/j.addma.2020.101587.
[51] T. Dürig and K. Karan, Binders in Pharmaceutical Granulation. 2021.
[52] S. P. Forster, E. Dippold, and T. Chiang, “Twin-Screw Melt Granulation for Oral Solid Pharmaceutical Products,” Pharmaceutics, vol. 13, no. 5, p. 665, May 2021, doi: 10.3390/pharmaceutics13050665.
[53] O. O. Kunle, “Starch Source and Its Impact on Pharmaceutical Applications,” in Chemical Properties of Starch, IntechOpen, 2020.
[54] A. Cholewinski, P. Si, M. Uceda, M. Pope, and B. Zhao, “Polymer Binders: Characterization and Development toward Aqueous Electrode Fabrication for Sustainability,” Polymers, vol. 13, no. 4, p. 631, Feb. 2021, doi: 10.3390/polym13040631.
[55] G. Paltanea et al., “A Review of Biomimetic and Biodegradable Magnetic Scaffolds for Bone Tissue Engineering and Oncology,” International Journal of Molecular Sciences, vol. 24, no. 5, p. 4312, Feb. 2023, doi: 10.3390/ijms24054312.
[56] J. A. Lett, S. M, R. K, and B. M, “Physical characterization of porous hydroxyapatite scaffolds,” Rheumatology and Orthopedic Medicine, vol. 3, no. 3, 2018, doi: 10.15761/ROM.1000153.
[57] R. Ismail et al., “The Effect of Hydrothermal Holding Time on The Characterization of Hydroxyapatite Synthesized from Green Mussel Shells,” Journal of Advanced Research in Fluid Mechanics and Thermal Sciences, vol. 80, no. 1, pp. 84–93, 2021, doi: 10.37934/ARFMTS.80.1.8493.
[58] F. Afriani, A. Indriawati, W. B. Kurniawan, Y. Widyaningrum, R. A. Rafsanjani, and Y. Tiandho, “Synthesis of porous hydroxyapatite scaffolds from waste cockle shells by polyurethane sponge replication method,” Gravity : Jurnal Ilmiah Penelitian dan Pembelajaran Fisika, vol. 6, no. 1, Feb. 2020, doi: 10.30870/gravity.v6i1.6741.
[59] R. Ferracini, I. Martínez Herreros, A. Russo, T. Casalini, F. Rossi, and G. Perale, “Scaffolds as Structural Tools for Bone-Targeted Drug Delivery,” Pharmaceutics, vol. 10, no. 3, p. 122, Aug. 2018, doi: 10.3390/pharmaceutics10030122.
[60] J. Serrano-Bello et al., “In vivo Regeneration of Mineralized Bone Tissue in Anisotropic Biomimetic Sponges,” Frontiers in Bioengineering and Biotechnology, vol. 8, Jul. 2020, doi: 10.3389/fbioe.2020.00587.
[61] J. A. Lett et al., “Exploration of gum ghatti-modified porous scaffolds for bone tissue engineering applications,” New Journal of Chemistry, vol. 44, no. 6, pp. 2389–2401, 2020, doi: 10.1039/C9NJ05575D.
[62] S. M. Imani, S. M. Rabiee, A. M. Goudarzi, and M. Dardel, “A novel modification for polymer sponge method to fabricate the highly porous composite bone scaffolds with large aspect ratio suitable for repairing critical-sized bone defects,” Vacuum, vol. 176, p. 109316, Jun. 2020, doi: 10.1016/j.vacuum.2020.109316.
[63] U. Batra and S. Kapoor, “Ionic Substituted Hydroxyapatite Scaffolds Prepared by Sponge Replication Technique for Bone Regeneration,” Nanoscience and Nanotechnology, vol. 6, no. 1A, pp. 18–24, 2016, doi: 10.5923/c.nn.201601.03.
[64] T. S. Vo, T. T. B. C. Vo, T. S. Nguyen, and N. D. Pham, “Incorporation of hydroxyapatite in crosslinked gelatin/chitosan/poly(vinyl alcohol) hybrids utilizing as reinforced composite sponges, and their water absorption ability,” Progress in Natural Science: Materials International, vol. 31, no. 5, pp. 664–671, Oct. 2021, doi: 10.1016/j.pnsc.2021.09.003.
[65] F. Habib, S. Alam, M. Irfan, and S. Nosheen, “Development and Characterization of Porous Hydroxyapatite Scaffold by Using Polymeric Sponge Method,” International Journal of Sciences: Basic and Applied Research, vol. 38, no. 2, pp. 1–7, 2018.
[66] X. Liu, Y. Zheng, Y. Ma, T. Huo, and C. Pei, “Self-assembled sponge-like hydroxyapatite induced by modified articular cartilage membrane template,” Ceramics International, vol. 44, no. 14, pp. 16400–16406, Oct. 2018, doi: 10.1016/j.ceramint.2018.06.050.
[67] S. A. Siddiqi et al., “Fabrication of biocompatible nano-carbonated hydroxyapatite/polymer spongy scaffolds,” Digest Journal of Nanomaterials and Biostructures, vol. 13, no. 2, pp. 439–450, 2018.
[68] D. Pristiono and D. I. Rudyardjo, “The synthesis and characterization of porous hydroxyapatite using gelatin coating for bone scaffold application,” in AIP Conference Proceedings, 2020, p. 050007, doi: 10.1063/5.0034658.
[69] P. Liu, D. Zhang, Y. Dai, J. Lin, Y. Li, and C. Wen, “Microstructure, mechanical properties, degradation behavior, and biocompatibility of porous Fe-Mn alloys fabricated by sponge impregnation and sintering techniques,” Acta Biomaterialia, vol. 114, pp. 485–496, Sep. 2020, doi: 10.1016/j.actbio.2020.07.048.
[70] J. Liu, J. Ruan, L. Chang, H. Yang, and W. Ruan, “Porous Nb-Ti-Ta alloy scaffolds for bone tissue engineering : Fabrication , mechanical properties and in vitro / vivo biocompatibility,” Materials Science & Engineering C, vol. 78, pp. 503–512, 2017, doi: 10.1016/j.msec.2017.04.088.
[71] J. Liu, J. Ruan, L. Chang, H. Yang, and W. Ruan, “Porous Nb-Ti-Ta alloy scaffolds for bone tissue engineering: Fabrication, mechanical properties and in vitro/vivo biocompatibility,” Materials Science and Engineering: C, vol. 78, pp. 503–512, Sep. 2017, doi: 10.1016/j.msec.2017.04.088.
[72] A. A. Mehatlaf, S. B. H. Farid, and A. A. Atiyah, “Fabrication and Investigation of Bioceramic Scaffolds by a Polymer Sponge Replication Technique,” IOP Conference Series: Materials Science and Engineering, vol. 1076, no. 1, p. 012080, Feb. 2021, doi: 10.1088/1757-899X/1076/1/012080.
[73] S. Eka Prawira, J. Triyono, and T. Triyono, “Pengaruh Temperatur Kalsinasi Terhadap Sifat Mekanik Material Scaffold Hidroksiapatit Dari Tulang Kambing,” Mekanika: Majalah Ilmiah Mekanika, vol. 18, no. 1, pp. 22–27, 2019, doi: 10.20961/mekanika.v18i1.35042.
[74] C. L. A. Leung, R. Tosi, E. Muzangaza, S. Nonni, P. J. Withers, and P. D. Lee, “Effect of preheating on the thermal, microstructural and mechanical properties of selective electron beam melted Ti-6Al-4V components,” Materials & Design, vol. 174, p. 107792, Jul. 2019, doi: 10.1016/j.matdes.2019.107792.
[75] N. Madadi Shishavan, R. Eslami-Farsani, H. Ebrahimnezhad-Khaljiri, and H. Aghamohammadi, “The effects of pre-heating and sintering temperature on the sol-gel synthesis of mullite nanoparticles,” Materials Research Express, vol. 6, no. 10, p. 105045, Aug. 2019, doi: 10.1088/2053-1591/ab3929.
[76] N. A. Salleh, S. Kheawhom, N. Ashrina A Hamid, W. Rahiman, and A. A. Mohamad, “Electrode polymer binders for supercapacitor applications: A review,” Journal of Materials Research and Technology, vol. 23, pp. 3470–3491, Mar. 2023, doi: 10.1016/j.jmrt.2023.02.013.

Most read articles by the same author(s)