Polycaprolactone and Poly(Lactic Acid) Filled with Low Content of Oxidized Carbon Nanotubes-Hydroxyapatite (o-CNT-HAp) Hybrid Filler: Effect of Proportion between o-CNT/HAp and Type of Polymer on the Properties and Interaction
Multiwall carbon nanotubes are known as multifunctional materials due to their nanometric nature and specific physical and chemical properties. Their oxidation induces structural chemical modification leading to better interaction with polymers. In this context, it was studied the effect of low content (0.05 wt.%) of hybrid filler constituted of oxidized carbon nanotubes (o-CNT)/hydroxyapatite (HAp) at different proportions added to the sustainable polyesters-polycaprolactone (PCL) and poly(lactic acid) (PLA). Properties and polymer-filler interaction were assessed. By spin-spin relaxation times, T1 showed no expressive variation for PCL and composites while spin-lattice relaxation times revealed that T2 changed for PLA-o-CNT-HAp(2:1). Thermogravimetry showed that there was no significant alteration in thermal stability of PCL and composites but PLA-o-CNT-HAp(2:1) revealed a slight increase in thermal stability. Only PLA-o-CNT-HAp(2:1) exhibited increase of crystalline melting temperature and decrease of degree of crystallinity whereas no change was achieved for PCL composites. Owing to the low content of fillers, the rheological measurement was driven by polymer matrices. The results suggested that the chemical structure of polymer matrix and the arrangement of the hybrid fillers jointly or to some extent influenced the chemical interaction and properties of the composites.
References
[1]
Walden, R., Jayadevan, S., Aliyana, A.K., Aazem, I., Perova, T., Hinder, S., et al. (2026) Effects of Pin-to-Plate Plasma on the TENG Properties of Electrospun PCL-Ag/PA6,6 Core-Sheath Yarns. Materials Science and Engineering: B, 327, Article ID: 119258. https://doi.org/10.1016/j.mseb.2026.119258
[2]
Mahovi？ Polja？ek, S., Toma？egovi？, T. and Priselac, D. (2026) Toward Sustainable Printed Packaging: Surface Properties and Ink Adhesion Behavior of PLA/PCL/Nanosilica Biopolymer Blends. Polymers, 18, Article No. 422. https://doi.org/10.3390/polym18030422
[3]
do Espirito Santo, G., Merlo, J.L., Botta, P., Rennó, A.C.M. and Rivero, G. (2025) Electrospun Polycaprolactone Scaffolds with Marine-Derived Biosilica Nanoparticles (Dragmacidon reticulatum) for Bone Tissue Engineering Applications. ACS Omega, 10, 56171-56182. https://doi.org/10.1021/acsomega.5c07836
[4]
Hosseini, M., Najmoddin, N. and Zamanlouie, S. (2026) 3D Printed Biomimetic Nanocomposite Scaffold with Potential Osteo-Neurogenic Differentiation of Mesenchymal Stem Cells for Bone Repair. Chemical Engineering Journal Advances, 26, Article ID: 101100. https://doi.org/10.1016/j.ceja.2026.101100
[5]
Anitasari, S., Tandirogang, N., Irawiraman, H., Budi, H.S., Shen, Y., Alus, L.N., et al. (2026) Optimizing Graphene-Enhanced Polycaprolactone Scaffolds for Bone Tissue Engineering. Journal of Oral Biology and Craniofacial Research, 16, Article ID: 101418. https://doi.org/10.1016/j.jobcr.2026.101418
[6]
Kashanizadeh, P., Rad, I., hatamie, S. and Esmaeili, E. (2026) Biofunctional Electrospun PCL Scaffolds Incorporating Halloysite Nanoclay-Silver Nanohybrids for Antibacterial and Osteoinductive Bone Regeneration. Polymer Bulletin, 83, Article No. 157. https://doi.org/10.1007/s00289-025-06246-9
[7]
Pandey, R.P., Ouda, M., Almarzooqi, S.A., Almazrouei, R.M. and Hasan, S.W. (2026) Constructing Eco-Friendly, PLA/Silylpropyl Quaternary Ammonium Graphene Oxide Composite Membrane via Chemical Grafting for Improved Oil/Water Separation and Antibacterial Performance. Cleaner Engineering and Technology, 31, Article ID: 101186. https://doi.org/10.1016/j.clet.2026.101186
[8]
Yang, S., Li, J., Zhang, H., Guo, X., Dahanayake, R., Wang, Y., et al. (2026) Exceptional Mechanical Reinforcement of Polylactic Acid via 2D Conformal Coating of Graphene Oxide. ACS Applied Materials & Interfaces, 18, 8908-8919. https://doi.org/10.1021/acsami.5c24140
[9]
Sarosi, I., Paltinean, G.A., Moldovan, A., Cuc, S., Carpa, R., Sarosi, C., et al. (2026) Antimicrobial PLA-Based Composite Gels with Improved Functional Properties for Food Packaging. Gels, 12, Article No. 194. https://doi.org/10.3390/gels12030194
[10]
Dave, P.N., Macwan, P.M. and Kamaliya, B. (2024) Reinforcing Effect of Oxidized Multiwalled Carbon Nanotubes on Swelling and Mechanical Properties of Gum Ghatti-cl-poly(NIPAm-co-AA) Hydrogels. Mechanics of Soft Materials, 6, Article No. 2. https://doi.org/10.1007/s42558-024-00057-0
[11]
Lavagna, L., Bartoli, M., Suarez-Riera, D., Cagliero, D., Musso, S. and Pavese, M. (2022) Oxidation of Carbon Nanotubes for Improving the Mechanical and Electrical Properties of Oil-Well Cement-Based Composites. ACS Applied Nano Materials, 5, 6671-6678. https://doi.org/10.1021/acsanm.2c00706
[12]
Kim, Y.J., Shin, T.S., Choi, H.D., Kwon, J.H., Chung, Y. and Yoon, H.G. (2005) Electrical Conductivity of Chemically Modified Multiwalled Carbon Nanotube/Epoxy Composites. Carbon, 43, 23-30. https://doi.org/10.1016/j.carbon.2004.08.015
[13]
Zhou, X., Hu, A. and Zhou, J. (2026) Silver Nanoparticle-Decorated PCL Scaffolds: In-Vitro Antimicrobial Activity and Effects on Osteogenic Cell Responses. Journal of Nanostructure in Chemistry, 16, 1-19.
[14]
Faramarzi Jolfaei, A. and Haddadi-Asl, V. (2026) Enhanced PCL Bimodal Foams Utilizing Phospho-Calcified Graphene Oxide to Promote Osteogenic Differentiation of HMSCs. Colloid and Interface Science Communications, 72, Article ID: 100883. https://doi.org/10.1016/j.colcom.2026.100883
[15]
Fallah, R., Zahedi, P., Shams, S., Nazari, A., Naderi, F., Khosroabadi, K., et al. (2026) Poly(？-Caprolactone)/Poly(ethylene Oxide)/Hydroxyapatite Nanofibrous Composite Scaffolds Used for Bone Tissue Regeneration, Potentially: Effect of Chamomile Extract. Materials & Design, 265, Article ID: 115827. https://doi.org/10.1016/j.matdes.2026.115827
[16]
Jiang, H., Fu, H., Wei, Q. and Wang, Y. (2026) A Hierarchical Bilayer Sponge Dressing Based on QCMCS@GO/PLA for Synergistic Wound Healing via Hemostasis and Anti-Adhesion. International Journal of Biological Macromolecules, 344, Article ID: 150565. https://doi.org/10.1016/j.ijbiomac.2026.150565
[17]
Keerthi, A.S., Manju, M.S., Thomas, L.V. and Sujith, A. (2026) Design of Thermoplastic and Few-Layer Graphene Modified Epoxy Coatings with Semi-Interpenetrating Polymer Networks for Hydrogen-Bond Mediated Self-healing and Mechanical Performance Enhancement. Journal of Applied Polymer Science, 143, e70617. https://doi.org/10.1002/app.70617
[18]
Litha, T.T., Nair, P.P. and Sajith Babu, C. (2026) A Novel Dual Nano-Filler Reinforcement System (Graphene Oxide-Hydroxyapatite/cellulose Nano-Whiskers) of PLA/PCL Bio-Nanocomposites for Enhanced Biomechanical Properties. The European Physical Journal Special Topics. https://doi.org/10.1140/epjs/s11734-026-02236-8
[19]
Pekdemir, M.E., K？k, M., Qader, I.N. and Aydo？du, Y. (2022) Preparation and Physicochemical Properties of MWCNT Doped Polyvinyl Chloride/Poly(ε-Caprolactone) Blend. Journal of Polymer Research, 29, Article No. 109. https://doi.org/10.1007/s10965-022-02947-1
[20]
Qader, I.N., K？k, M., Mohammed, K.S., Coskun, M., ？ner, E.？. and Aydo？du, Y. (2025) Development of a PLA/PHA-TiO2 Polymer Blend with Improved Physicochemical and Thermal Properties. Journal of Polymers and the Environment, 33, 2502-2514. https://doi.org/10.1007/s10924-025-03547-y
[21]
Demir, P. (2023) Thermal Degradation Kinetics, Mechanism, Thermodynamics, Shape Memory Properties and Artificial Neural Network Application Study of Polycaprolactone (PCL)/Polyvinyl Chloride (PVC) Blends. Polymer Bulletin, 80, 9685-9708. https://doi.org/10.1007/s00289-022-04522-6
[22]
Abdelrazek, E.M., Hezma, A.M., El-Khodary, A., Elzayat, A.M. and Rajeh, A. (2023) Modifying of Structural, Optical, Thermal, and Mechanical Properties of PCL/PMMA Biomaterial Blend Doped with MWCNTs as an Application in Materials Science. Journal of Inorganic and Organometallic Polymers and Materials, 33, 4117-4126. https://doi.org/10.1007/s10904-023-02625-9
[23]
Mantecón-Oria, M., Tapia, O., Lafarga, M., Berciano, M.T., Munuera, J.M., Villar-Rodil, S., et al. (2022) Influence of the Properties of Different Graphene-Based Nanomaterials Dispersed in Polycaprolactone Membranes on Astrocytic Differentiation. Scientific Reports, 12, Article No. 13408. https://doi.org/10.1038/s41598-022-17697-9
[24]
Pereira, K.A.B., Cestari, S.P., Cucinelli Neto, R.P., Macedo, K.R.M. and Mendes, L.C. (2019) Oxidized-Sulfonated Multi-Walled Carbon Nanotube/Hydroxyapatite Hybrid Particles: Synthesis and Characterization. Journal of Solid State Chemistry, 279, Article ID: 120924. https://doi.org/10.1016/j.jssc.2019.120924
[25]
Contreras, M.M., Nascimento, C.R., Cucinelli Neto, R.P., Teixeira, S., Berry, N., Costa, M.F., et al. (2018) TD-NMR Analysis of Structural Evolution in PVDF Induced by Stress Relaxation. Polymer Testing, 68, 153-159. https://doi.org/10.1016/j.polymertesting.2018.03.051
[26]
Ramos, V.S., Merat, P.P., Iulianelli, G., Silva, E.M., Bello, T.M.H. and Tavares, M.I.B. (2023) Extraction of Stem Oils from Cinnamomum Cassia and NMR Characterization to Produce Nutraceuticals. Food Science and Technology, 43, e14523. https://doi.org/10.5327/fst.14523
[27]
Fernández-Tena, A., Pérez-Camargo, R.A., Coulembier, O., Sangroniz, L., Aranburu, N., Guerrica-Echevarria, G., et al. (2023) Effect of Molecular Weight on the Crystallization and Melt Memory of Poly(ε-Caprolactone) (PCL). Macromolecules, 56, 4602-4620. https://doi.org/10.1021/acs.macromol.3c00234
[28]
Akdevelio？lu, Y., Alanalp, M.B., Randall, J., Gehrung, M., Durmus, A., Jahani, D., et al. (2026) Joncryl Chain Extender Reactivity with Polylactide: Effect of PLA Molecular Weight and the Resultant Rheological and Crystallization Behaviors. Journal of Polymers and the Environment, 34, Article No. 21. https://doi.org/10.1007/s10924-025-03753-8
[29]
Adeniyi, M., Parvin, M., Akter, K., Arbab, A.S., Quirino, R.L. and Khan, M. (2026) Synthesis and Processing of PCL (Polycaprolactone) and IRDye Nanoparticles and Their Biodistribution. BioMedical Engineering OnLine, 25, Article No. 49. https://doi.org/10.1186/s12938-026-01544-3
[30]
Justino Netto, J.M., Sousa, D., Amaral, P. and Leite, M. (2026) Feedstock Characterization and Process Calibration for Fused Pellet Fabrication of PLA/Limestone Composites. Progress in Additive Manufacturing, 11, 4061-4075. https://doi.org/10.1007/s40964-026-01567-1
[31]
Ramírez-Pedroza, J.P., del Pilar Ramos-Godínez, M., Ali, A., Tomás-Velázquez, S.A., Hernández-Martínez, E. and Luna-Arias, J.P. (2026) Hydroxyapatite Nanoparticles Synthesis with PAMAM-Like Dendrimers Grown in Situ on Their Surface for Potential Therapeutic Use. Journal of Nanoparticle Research, 28, Article No. 99. https://doi.org/10.1007/s11051-026-06626-w
[32]
Targońska, S., Kardach, M., Andrzejewski, J., Wiatrak, B., Nowotarska, P., G？barowski, T., et al. (2026) Effect of Carbon Fibers Coated with Nanosized Hydroxyapatite on the Strength and Biocompatibility of Polymer Composites. Journal of Applied Polymer Science, 143, e58139. https://doi.org/10.1002/app.58139
[33]
Cao, L., Zhang, J., Chen, S., Osaka, A. and Chen, W. (2026) Fabrication, Characterization, Tailored Structure, and in Vitro Biocompatibility of Hydroxyapatite Hollow Microspheres. International Journal of Applied Ceramic Technology, 23, e70143. https://doi.org/10.1111/ijac.70143
[34]
Puliyasseri, R., Haribabu, J., Arulraj, A., Moraga, D., Nishanth, T. and Sastikumar, D. (2026) Boron-Doped Graphene Oxide Nanoparticles Synthesized by Nanosecond Pulsed Laser Ablation of Graphene in Ethanol: Structural, Optical, and Bioimaging Studies. Optics & Laser Technology, 194, Article ID: 114371. https://doi.org/10.1016/j.optlastec.2025.114371
[35]
Saipanya, S., Sriwichai, S., Themsirimongkon, S., Sudrungruang, S., Jakmunee, J. and Waenkaew, P. (2026) Electrodeposition of Platinum on Electropolymerized Poly(3-Aminobenzylamine)-Graphene Oxide as a Catalyst for Alcohol Oxidation in Alkaline Solution. International Journal of Hydrogen Energy, 206, Article ID: 153444. https://doi.org/10.1016/j.ijhydene.2026.153444
[36]
Doostmohammadi, N., Yousefpour, M., Nourbakhsh, M.S. and Bahraminasab, M. (2025) Fabrication and Characterization of 3D Printed PCL/ZrO2/FA Scaffolds for Bone Tissue Engineering. Materials Chemistry and Physics, 338, Article ID: 130659. https://doi.org/10.1016/j.matchemphys.2025.130659
[37]
Tamburini, G., Bertagnoli, S., Tarricone, G., Piva, S., Sassella, A., Lorenzi, R., et al. (2023) Early Stages of X-Ray Induced Molecular Unit Modifications in Poly(lactic acid). Polymer Degradation and Stability, 216, Article ID: 110485. https://doi.org/10.1016/j.polymdegradstab.2023.110485
[38]
Nurbaiti,, Herliansyah, M.K., Tontowi, A.E., Widiastuti, M.G., Hoten, H.V. and Perkasa, D.P. (2025) Characterization of Three-Dimensional Printed Hydroxyapatite/collagen Composite Slurry. Materials Chemistry and Physics, 329, Article ID: 130047. https://doi.org/10.1016/j.matchemphys.2024.130047
[39]
Gómez, S., Rendtorff, N.M., Aglietti, E.F., Sakka, Y. and Suárez, G. (2016) Surface Modification of Multiwall Carbon Nanotubes by Sulfonitric Treatment. Applied Surface Science, 379, 264-269. https://doi.org/10.1016/j.apsusc.2016.04.065
[40]
Irani, M., Nasirtabrizi, M.H., Ezzatzadeh, E. and Sadeghianmaryan, A. (2025) In-Vitro Study of Co-Electrospun PCL/Gelatin/Chitosan Scaffolds Enhanced with Carbon Nanotube for Cartilage Regeneration. Polymer Bulletin, 82, 6981-6999. https://doi.org/10.1007/s00289-025-05808-1
[41]
Catauro, M., Bollino, F., Cristina Mozzati, M., Ferrara, C. and Mustarelli, P. (2013) Structure and Magnetic Properties of SiO2/PCL Novel Sol-Gel Organic-Inorganic Hybrid Materials. Journal of Solid State Chemistry, 203, 92-99. https://doi.org/10.1016/j.jssc.2013.04.014
[42]
？elik, R.H., ？im？ek, S., Gel, E. and Acuner, S.E. (2025) Molecular Dynamics Insights into the Interactions of Biocompatible Synthetic Polymer Composites with Carbon-Based Nanoparticle Derivatives: A Comparative Study of PLGA and PCL Interactions with GO/rGO. Journal of Computer-Aided Molecular Design, 40, Article No. 19. https://doi.org/10.1007/s10822-025-00726-w
[43]
Mohammed, K.S., Coskun, M., Babakr, K.A., K？k, M. and Qader, I.N. (2025) Blending of Polycaprolactone with Polyvinyl Chloride Polymers Using Silica Gel as a Functional Reinforcement. Journal of Materials Science: Materials in Electronics, 36, Article No. 2020. https://doi.org/10.1007/s10854-025-16102-1
[44]
Mahovi？ Polja？ek, S., Priselac, D., Toma？egovi？, T., Elesini, U.S., Leskov？ek, M. and Leskovac, M. (2022) Effect of the Addition of Nano-Silica and Poly(ε-Caprolactone) on the Mechanical and Thermal Properties of Poly(lactic acid) Blends and Possible Application in Embossing Process. Polymers, 14, Article No. 4861. https://doi.org/10.3390/polym14224861
[45]
Taha, E.O., Shoaib, E., Ahmed, M.A., El-Ghazawy, R.A. and Naguib, H.M. (2026) Smart Biodegradable PLA Nanocomposites Reinforced with ZnO and GO for Thermomechanical and Shape Memory Applications. Discover Materials, 6, Article No. 131. https://doi.org/10.1007/s43939-026-00623-5
[46]
Oliver-Cuenca, V., Salaris, V., Mu？oz-Gimena, P.F., Agüero, á., Peltzer, M.A., Montero, V.A., et al. (2024) Bio-Based and Biodegradable Polymeric Materials for a Circular Economy. Polymers, 16, Article No. 3015. https://doi.org/10.3390/polym16213015
[47]
Lomakin, S., Koverzanova, E., Usachev, S., Shilkina, N., Khvatov, A., Erina, N., et al. (2026) Specific Impact of the Layered Nanomodifiers—Graphene Nanoplates, and Na+ Montmorillonite on Thermal Degradation of Polylactic Acid: Mechanism and Kinetics. Polymers, 18, Article No. 347. https://doi.org/10.3390/polym18030347
