Halloysit Nanotüp Takviyeli Poliüretan Nanolifli Membran: Yapısal, Termal, Mekanik ve Transport Özellikleri Üzerindeki Etkileri

Öz

Poliüretan (PU) nanolifli membranlar, yüksek yüzey alanları, esneklikleri ve ayarlanabilir yüzey özellikleri nedeniyle filtrasyon, koruyucu tekstiller ve biyomedikal uygulamalar için umut verici malzemeler olarak önemli ilgi görmüştür. Ancak saf PU nanolifler çoğu zaman sınırlı mekanik dayanım ve bariyer performansı göstermektedir. Bu çalışmada, yapısal, termal, mekanik ve taşınım özellikleri üzerindeki HNT katkısının (1-5 a.% ) etkisini araştırmak amacıyla halloysit nanotüp (HNT) takviyeli PU nanolifli membranlar elektro-üflemeli çekim yöntemiyle üretilmiştir. SEM analizi, lif çapının saf PU’da 758±266 nm iken, %1 ve %3 HNT içeriğinde sırasıyla 656±147 nm ve 636±136 nm’ye düştüğünü göstermiştir. Çekme dayanımı, saf PU için 1.53±0.20 N mm⁻² iken, PU/HNT (%1) kompozit nanolifli yapıda anlamlı biçimde artarak 6.68 ± 0.21 N mm⁻²’ye ulaşmıştır. HNT ilavesi ayrıca yüzey ıslanabilirliğini artırmış, temas açısını saf PU’da 133°’den PU/HNT (%3) membranda 108°’ye düşürmüştür. Buna ek olarak, hava geçirgenliği saf PU’da 4.67 L m⁻² s⁻¹ iken, PU/HNT (%3) membranda 7.03 L m⁻² s⁻¹’ye yükselmiş ve buna su buharı taşınım özelliklerinde iyileşme eşlik etmiştir.

Anahtar Kelimeler

• Poliüretan
• Halloysit
• Nanolifli membran
• Transport özellikleri
• Elektro-üflemeli çekim

HALLOYSITE NANOTUBE REINFORCED POLYURETHANE NANOFIBROUS MEMBRANE: EFFECTS ON STRUCTURAL, THERMAL, MECHANICAL AND TRANSPORT PROPERTIES

Öz

Polyurethane (PU) nanofibrous membranes have attracted significant attention due to their high surface area, flexibility, and tunable surface properties, making them promising materials for filtration, protective textiles, and biomedical applications. However, neat PU nanofibers often suffer from limited mechanical strength and barrier performance. In this study, halloysite nanotube (HNT)-reinforced PU nanofibrous membranes were fabricated by electro-blown spinning to investigate the influence of HNT incorporation (1-5 wt%) on structural, thermal, mechanical, and transport properties. SEM analysis showed that fiber diameter decreased from 758 ± 266 nm in neat PU to 656 ± 147 nm and 636 ± 136 nm at 1 wt% and 3 wt% HNT. Tensile strength significantly improved from 1.53 ± 0.20 N mm⁻² for neat PU to 6.68 ± 0.21 N mm⁻² for the PU/HNT (1%) composite nanofibrous mat. The incorporation of HNT also enhanced surface wettability, reducing the contact angle from 133° for neat PU to 108° for the PU/HNT (3%) membrane. In addition, air permeability increased from 4.67 L m⁻² s⁻¹ for neat PU to 7.03 L m⁻² s⁻¹ for the PU/HNT (3%) membrane, accompanied by improved water vapor transport properties.

Anahtar Kelimeler

• Polyurethane
• Halloysite
• Nanofibrous membrane
• Transport properties
• Electro-blown spinning

Kaynakça

1. Abdullayev, E., Lvov, Y. (2016). Halloysite for Controllable Loading and Release. Developments in Clay Science, 7, 554-605. https://doi.org/10.1016/b978-0-08-100293-3.00022-4
2. Cavallaro, G., Donato, D. I., Lazzara, G., Milioto, S. (2011). Films of Halloysite Nanotubes Sandwiched between Two Layers of Biopolymer: From the Morphology to the Dielectric, Thermal, Transparency, and Wettability Properties. Journal of Physical Chemistry C, 115(42), 20491-20498. https://doi.org/10.1021/jp207261r
3. Corcione, C. E., Frigione, M. (2012). Characterization of Nanocomposites by Thermal Analysis. Materials, 5(12), 2960. https://doi.org/10.3390/ma5122960
4. Daraie, M., Bagheri, D., Malmir, M., Heravi, M. M. (2021). Investigation of halloysite nanotubes and Schiff base combination with deposited copper iodide nanoparticles as a novel heterogeneous catalytic system. Scientific Reports 2021 11:1, 11(1), 23658. https://doi.org/10.1038/s41598-021-02991-9
5. Gaaz, T. S., Sulong, A. B., Kadhum, A. A. H., Al-Amiery, A. A., Nassir, M. H., Jaaz, A. H. (2017). The Impact of Halloysite on the Thermo-Mechanical Properties of Polymer Composites. Molecules, 22(5), 838. https://doi.org/10.3390/molecules22050838
6. Ghasemi-Mobarakeh, L., Semnani, D., Morshed, M. (2007). A novel method for porosity measurement of various surface layers of nanofibers mat using image analysis for tissue engineering applications, Journal of Applied Polymer Science, 106(4), 2536-2542. https://doi.org/10.1002/app.26949
7. Godlewska, J., Smorawska, J., Głowińska, E. (2024). Chemical Structure and Thermal Properties versus Accelerated Aging of Bio-Based Poly(ether-urethanes) with Modified Hard Segments. Molecules, 29(15), 3585. https://doi.org/10.3390/molecules29153585
8. Gorji, M., Jeddi, A. A. A., Gharehaghaji, A. A. (2012). Fabrication and characterization of polyurethane electrospun nanofiber membranes for protective clothing applications. Journal of Applied Polymer Science, 125(5), 4135-4141. https://doi.org/10.1002/app.36611

9. Greiner, A., Wendorff, J. H., Heitz, W., Greiner, A., Wendorff, J. H. (2007). Electrospinning: A Fascinating Method for the Preparation of Ultrathin Fibers. Angewandte Chemie International Edition, 46(30), 5670-5703. https://doi.org/10.1002/anie.200604646
10. Hebbar, R. S., Isloor, A. M., Ananda, K., Ismail, A. F. (2016). Fabrication of polydopamine functionalized halloysite nanotube/polyetherimide membranes for heavy metal removal. Journal of materials chemistry A, 4(3), 764-774. https://doi.org/10.1039/c5ta09281g
11. Jo, S. B., Erdenebileg, U., Dashnyam, K., Jin, G. Z., Cha, J. R., El-Fiqi, A., Knowles, J. C., Patel, K. D., Lee, H. H., Lee, J. H., Kim, H. W. (2020). Nano-graphene oxide/polyurethane nanofibers: mechanically flexible and myogenic stimulating matrix for skeletal tissue engineering. Journal of Tissue Engineering, 11. https://doi.org/10.1177/2041731419900424
12. Józó, M., Várdai, R., Hegyesi, N., Móczó, J., Pukánszky, B. (2021). Poly-ε-caprolactone/halloysite nanotube composites for resorbable scaffolds: Effect of processing technology on homogeneity and electrospinning. Polymers, 13(21), 3772. https://doi.org/10.3390/polym13213772
13. Kausar, A. (2018). Review on polymer/halloysite nanotube nanocomposite. Polymer-Plastics Technology and Engineering, 57(6), 548-564. https://doi.org/10.1080/03602559.2017.1329436
14. Koh, A., Carpenter, A. W., Slomberg, D. L., Schoenfisch, M. H. (2013). Nitric Oxide-Releasing Silica Nanoparticle-Doped Polyurethane Electrospun Fibers. ACS Applied Materials and Interfaces, 5(16), 7956-7964. https://doi.org/10.1021/am402044s
15. Lee, Y. H., Kang, B. K., Kim, H. Do, Yoo, H. J., Kim, J. S., Huh, J. H., Jung, Y. J., Lee, D. J. (2009). Effect of hot pressing/melt mixing on the properties of thermoplastic polyurethane. Macromolecular Research, 17(8), 616-622. https://doi.org/10.1007/BF03218918
16. Liang, W., Xu, Y., Li, X., Wang, X. X., Zhang, H. Di, Yu, M., Ramakrishna, S., Long, Y. Z. (2019). Transparent Polyurethane Nanofiber Air Filter for High-Efficiency PM2.5 Capture. Nanoscale Research Letters, 14(1), 361. https://doi.org/10.1186/S11671-019-3199-0
17. Mrówka, M., Szymiczek, M., Machoczek, T., Pawlyta, M. (2021). Influence of the Halloysite Nanotube (HNT) Addition on Selected Mechanical and Biological Properties of Thermoplastic Polyurethane. Materials, 14(13), 3625. https://doi.org/10.3390/ma14133625
18. Muralidhara, B., Babu, S. P. K., Suresha, B., Yogesha, K. K., Vasundhara, M. G., Kalavathi, G. K., Goudar, D. M., Kurahatti, R. V., Bhat, S. K. (2025). Enhanced mechanical, thermal, and wear performance of halloysite nanotube infused carbon fiber epoxy composites. Scientific Reports, 15(1), 30019. https://doi.org/10.1038/s41598-025-15142-1
19. Ouyang, C.F., Gong, B., Gao, Q. (2014). Nanocomposite Reinforcement Effects in Millable Polyurethane Elastomer with Low Content of Halloysite Nanotubes. Proceedings of the 2015 International Conference on Material Science and Applications, 3, 531-536. https://doi.org/10.2991/icmsa-15.2015.96
20. Ouyang, Z., Li, J., Wang, J., Li, Q., Ni, T., Zhang, X., Wang, H., Li, Q., Su, Z., Wei, G. (2013). Fabrication, characterization and sensor application of electrospun polyurethane nanofibers filled with carbon nanotubes and silver nanoparticles. Journal of Materials Chemistry B, 1(18), 2415-2424. https://doi.org/10.1039/c3tb20316f
21. Pasbakhsh, P., Ismail, H., Fauzi, M. A., Bakar, A. A. (2010). EPDM/modified halloysite nanocomposites. Applied Clay Science, 48(3), 405-413. https://doi.org/10.1016/j.clay.2010.01.015
22. Petrovic, Z. S., Petrovic, P., Javni, I., Waddon, A., Bánhegyi, G. (2000). Structure and Properties of Polyurethane-Silica Nanocomposites. J Appl Polym Sci, 76, 133-151. https://doi.org/10.1002/(sici)1097-4628(20000411)76:2<133::aid-app3>3.0.co;2-k
23. Pourmohammadi-Mahunaki, M., Haddadi-Asl, V., Roghani-Mamaqani, H., Koosha, M., Yazdi, M. (2020). Halloysite-reinforced thermoplastic polyurethane nanocomposites: Physico-mechanical, rheological, and thermal investigations. Polymer Composites, 41(8), 3260-3270. https://doi.org/10.1002/pc.25617
24. Pourmohammadi-Mahunaki, M., Haddadi-Asl, V., Roghani-Mamaqani, H., Koosha, M., Yazdi, M. (2021). Preparation of polyurethane composites reinforced with halloysite and carbon nanotubes. Polymer Composites, 42(1), 450-461. https://doi.org/10.1002/PC.25838
25. Que, Y. H., Shi, Y., Liu, L. Z., Wang, Y. X., Wang, C. C., Zhang, H. C., Han, X. Y. (2021). The Crystallisation, Microphase Separation and Mechanical Properties of the Mixture of Ether-Based TPU with Different Ester-Based TPUs. Polymers, 13(20), 3475. https://doi.org/10.3390/polym13203475
26. Rajeev, M., Helms, C. C. (2023). A Study of the Relationship between Polymer Solution Entanglement and Electrospun PCL Fiber Mechanics. Polymers, 15(23), 4555. https://doi.org/10.3390/polym15234555
27. Reneker, D. H., Yarin, A. L. (2008). Electrospinning jets and polymer nanofibers. Polymer, 49(10), 2387-2425. https://doi.org/10.1016/j.polymer.2008.02.002
28. Saha, K., Butola, B. S., Joshi, M. (2014). Drug-loaded polyurethane/clay nanocomposite nanofibers for topical drug-delivery application. Journal of Applied Polymer Science, 131(10), 40230. https://doi.org/10.1002/app.40230
29. Shi, H., Liu, H., Luan, S., Shi, D., Yan, S., Liu, C., Li, R. K. Y., Yin, J. (2016). Effect of polyethylene glycol on the antibacterial properties of polyurethane/carbon nanotube electrospun nanofibers. RSC Advances, 6(23), 19238-19244. https://doi.org/10.1039/c6ra00363j
30. Shokraei, N., Asadpour, S., Shokraei, S., Nasrollahzadeh Sabet, M., Faridi-Majidi, R., Ghanbari, H. (2019). Development of electrically conductive hybrid nanofibers based on CNT-polyurethane nanocomposite for cardiac tissue engineering. Microscopy Research and Technique, 82(8), 1316-1325. https://doi.org/10.1002/jemt.23282
31. Unnithan, A. R., Barakat, N. A. M., Tirupathi Pichiah, P. B., Gnanasekaran, G., Nirmala, R., Cha, Y. S., Jung, C. H., El-Newehy, M., Kim, H. Y. (2012). Wound-dressing materials with antibacterial activity from electrospun polyurethane-dextran nanofiber mats containing ciprofloxacin HCl. Carbohydrate Polymers, 90(4), 1786-1793. https://doi.org/10.1016/j.carbpol.2012.07.071
32. Wang, B., Wang, J., Lou, Y., Ding, S., Jin, X., Liu, F., Xu, Z., Ma, J., Sun, Z., Li, X. (2022). Halloysite nanotubes strengthened electrospinning composite nanofiber membrane for on-skin flexible pressure sensor with high sensitivity, good breathability, and round-the-clock antibacterial activity. Applied Clay Science, 228. https://doi.org/10.1016/j.clay.2022.106650
33. Yuan, P., Tan, D., Annabi-Bergaya, F. (2015). Properties and applications of halloysite nanotubes: recent research advances and future prospects. Applied Clay Science, 112-113, 75-93. https://doi.org/10.1016/j.clay.2015.05.001
34. Zahidah, K. A., Kakooei, S., Ismail, M. C., Bothi Raja, P. (2017). Halloysite nanotubes as nanocontainer for smart coating application: A review. Progress in Organic Coatings, 111, 175-185. https://doi.org/10.1016/j.porgcoat.2017.05.018
35. Zia, F., Zia, K. M., Nazli, Z. i. H., Tabasum, S., Khosa, M. K., Zuber, M. (2020). Preparation of hydroxyethyl cellulose/halloysite nanotubes graft polylactic acid-based polyurethane bionanocomposites. International Journal of Biological Macromolecules, 153(5), 591-599. https://doi.org/10.1016/j.ijbiomac.2020.03.038