Advanced Ceramics Progress

Advanced Ceramics Progress

Evaluating in Vitro Calcium Phosphate Formation on the Surfaces of Synthesized Silanated Polymethylmethacrylate Microspheres

Document Type : Original Research Article

Authors
Fatemeh Mohammadi 1
Saeed Hesaraki 2
Rahim Naghizadeh 3
Nader Nezafati 4
Mojtaba Beygzadeh 5
1 MSc Student, School of Materials and Metallurgical Engineering Iran University of Science and Technology, Tehran, Iran.
2 Professor, Department of Nanotechnology and Advanced Materials, Materials and Energy Research Center, Karaj, Iran.
3 Associate Professor, School of Materials and Metallurgical Engineering Iran University of Science and Technology, Tehran, Iran.
4 Associate Professor, Department of Nanotechnology and Advanced Materials, Materials and Energy Research Center, Karaj, Iran.
5 Assistant Professor, Department of Energy, Materials and Energy Research Center, Karaj, Iran.
10.30501/acp.2025.538730.1182
Abstract
Poly(methyl methacrylate) (PMMA) bone cement is widely used in orthopedic applications such as kyphoplasty and prosthesis fixation due to its favorable mechanical properties. However, its inherent bioinertness limits direct bonding with bone tissue. This study presents a novel approach to enhance the bioactivity of PMMA through surface chemical modification of the powder phase. PMMA microspheres were synthesized using the solvent evaporation emulsification method, which involved optimizing the surfactant type and concentration, as well as process parameters, to achieve morphological stability. Surface hydrolysis with sulfuric acid was conducted to introduce carboxylic functional groups. Subsequently, chemical functionalization was performed using varying concentrations of silane coupling agents, GPTMS and TEOS. FTIR spectroscopy and SEM analyses confirmed successful surface modification while preserving microsphere morphology. Bioactivity was evaluated by immersing the samples in simulated body fluid (SBF) for 1, 7, and 14 days. A gradual formation of a hydroxyapatite layer was observed on the modified surfaces, as evidenced by SEM imaging, FTIR spectra, and XRD patterns. The results demonstrate that surface silanization considerably improves the bioactivity of PMMA microspheres. This surface modification strategy shows strong potential for developing PMMA-based implant materials with enhanced osseointegration capability.
Keywords
Polymethyl Methacrylate
Y-Glycidoxypropyltrimethoxysilane
Tetraethylorthosilcate
Simulated Body Fluid
Bioactivity
Subjects
1.      Aquino, L. R. C., SILVA, C. C. d., Sombra, A. S., & MACÊDO, A. A. M. (2016). Bone cement: a review. https://repositorio.ufma.br/jspui/handle/123456789/913
2.      Clarke, B. (2008). Normal bone anatomy and physiology. Clinical journal of the American Society of Nephrology, 3(Supplement_3), S131-S139. http://doi.org/10.2215/CJN.04151206
3.      Gabrielli, L., Russo, L., Poveda, A., Jones, J. R., Nicotra, F., Jiménez‐Barbero, J., & Cipolla, L. (2013). Epoxide opening versus silica condensation during sol–gel hybrid biomaterial synthesis. Chemistry–A European Journal, 19(24), 7856-7864. http://doi.org/10.1002/chem.201204326
4.      Ghorbani, F., Zamanian, A., Behnamghader, A., & Daliri Joupari, M. (2018). A novel pathway for in situ synthesis of modified gelatin microspheres by silane coupling agents as a bioactive platform. Journal of Applied Polymer Science, 135(41), 46739. https://doi.org/10.1002/app.46739
5.      Gül, C., Albayrak, S., Durmuş, H., & Çömez, N. (2021). Characterization of SiO2 sol-gel coated Ti6Al4V alloy obtained by using TEOS and GPTMS. Science of Sintering, 53(4), 461-473. https://doi.org/10.2298/SOS2104461G
6.      Heinrich, H. T., Bremer, P. J., Daughney, C. J., & McQuillan, A. J. (2007). Acid− Base Titrations of Functional Groups on the Surface of the Thermophilic Bacterium Anoxybacillus flavithermus: Comparing a Chemical Equilibrium Model with ATR-IR Spectroscopic Data. Langmuir, 23(5), 2731-2740. https://doi.org/10.1021/la062401j
7.      Hosseini, S., Ibrahim, F., Djordjevic, I., & Koole, L. H. (2014). Recent advances in surface functionalization techniques on polymethacrylate materials for optical biosensor applications. Analyst,139(12),2933-2943. http://doi.org/10.1039/C3AN01789C
8.      Kokubo, T., & Takadama, H. (2006). How useful is SBF in predicting in vivo bone bioactivity? Biomaterials, 27(15), 2907-2915. https://doi.org/10.1016/j.biomaterials.2006.01.017
9.      Loi, F., Córdova, L. A., Pajarinen, J., Lin, T.-h., Yao, Z., & Goodman, S. B. (2016). Inflammation, fracture and bone repair. Bone, 86, 119-130.https://doi.org/10.1016/j.bone.2016.02.020
10.    Mashhadian, A., Afjoul, H., & Shamloo, A. (2022). An integrative method to increase the reliability of conventional double emulsion method. Analytica Chimica Acta, 1197, 339523. http://doi.org/10.1016/j.aca.2022.339523
11.    Pahlevanzadeh, F., Bakhsheshi-Rad, H., & Hamzah, E. (2018). In-vitro biocompatibility, bioactivity, and mechanical strength of PMMA-PCL polymer containing fluorapatite and graphene oxide bone cements. Journal of the mechanical behavior of biomedical materials,82,257-267. http://doi.org/10.1016/j.jmbbm.2018.03.016
12.    Pletincx, S., Marcoen, K., Trotochaud, L., Fockaert, L.-L., Mol, J. M., Head, A. R.,  Hauffman, T. (2017). Unravelling the chemical influence of water on the PMMA/aluminum oxide hybrid interface in situ. Scientific reports, 7(1), 13341. https://doi.org/10.1038/s41598-017-13549-z
13.    Singh, B., Singh, P., Sutherland, A. J., & Pal, K. (2017). Control of shape and size of poly (lactic acid) microspheres based on surfactant and polymer concentration. Materials Letters, 195, 48-51.https://doi.org/10.1016/j.matlet.2017.02.068
14.    Sivakumar, M., & Rao, K. P. (2000). Synthesis and characterization of poly (methyl methacrylate) functional microspheres. Reactive and functional polymers, 46(1), 29-37. https://doi.org/10.1016/S1381-5148(00)00033-X
15.    Teimouri, R., Abnous, K., Taghdisi, S. M., Ramezani, M., & Alibolandi, M. (2023). Surface modifications of scaffolds for bone regeneration. Journal of Materials Research and Technology,24,7938-7973. https://doi.org/10.1016/j.jmrt.2023.05.076
16.    Wang, F., Zhang, Y., Li, X., Wang, B., Feng, X., Xu, H.,Sui, X. (2020). Cellulose nanocrystals-composited poly (methyl methacrylate) encapsulated n-eicosane via a Pickering emulsion-templating approach for energy storage. Carbohydrate Polymers, 234, 115934. http://doi.org/10.1016/j.carbpol.2020.115934
17.    Zhao, Z.-B., Tai, L., Zhang, D.-M., & Jiang, Y. (2017). Facile fabrication of siloxane@ poly (methylacrylic acid) core-shell microparticles with different functional groups. Journal of Nanoparticle Research, 19, 1-9. https://doi.org/10.1007/s11051-017-3777-y

  • Receive Date 02 August 2025
  • Revise Date 11 September 2025
  • Accept Date 16 November 2025