Influence of Graft Copolymerization Initiators on the Morphology and Wettability of VA/CG-g-EGD Membranes

Öz

The development of hybrid polymeric membranes with tunable surface properties is crucial for advanced separation and controlled release technologies. In this study, poly(vinyl alcohol)/(κ-carrageenan-graft-ethylene glycol dimethacrylate) (VA/CG-g-EGD) membranes were prepared by blending poly(vinyl alcohol) (VA) with κ-carrageenan-graft-ethylene glycol dimethacrylate (CG-g-EGD) copolymers synthesized using different initiators: cerium ammonium nitrate (CAN), ammonium persulfate (APS), and benzoyl peroxide (BPO). The aim was to examine how the initiator type influences grafting efficiency and, consequently, the morphology and surface characteristics of the membranes. AFM and contact angle analyses revealed that the initiator type significantly affected surface roughness and wettability. Among the initiators, BPO produced the most uniform surface, whereas CAN yielded a rougher morphology with lower grafting efficiency. Compared to pristine VA membranes, the VA/CG-g-EGD membranes exhibited smoother, more stable surfaces with a tunable hydrophilic–hydrophobic balance, confirming the successful grafting. These findings demonstrate that controlling grafting parameters effectively enhances membrane surface performance. The improved surface integrity and morphological stability make VA/CG-g-EGD membranes promising candidates for pervaporation-based separations and drug-delivery applications requiring selective permeability and mechanical durability.

Anahtar Kelimeler

• Atomic force microscopy
• contact angle
• poly(vinyl alcohol)
• initiator

Destekleyen Kurum

Kırklareli Üniversitesi

Proje Numarası

DPT-2010K121120, KLUBAP-204, and KLUBAP-264.

Teşekkür

The authors express their gratitude to the Kırklareli University Advanced Technologies Application and Research Center (ITUAM) for granting access to the facilities utilized in this work. Appreciation is also extended to the Kırklareli University Scientific Research Projects Coordination Unit for their financial support under project numbers DPT-2010K121120, KLUBAP-204, and KLUBAP-264.

Aşı Kopolimerizasyon Başlatıcılarının VA/CG-g-EGD Membranlarının Morfolojisi ve Islatılabilirliği Üzerindeki Etkisi

Öz

Ayarlanabilir yüzey özelliklerine sahip hibrit polimerik membranların geliştirilmesi, ileri düzey ayırma ve kontrollü salım teknolojileri açısından büyük önem taşımaktadır. Bu çalışmada, farklı başlatıcılar olan seryum amonyum nitrat (CAN), amonyum persülfat (APS) ve benzoil peroksit (BPO) kullanılarak κ-karragenan (CG) üzerine sentezlenen κ-karragenan-aşı-etilen glikol dimetakrilat (CG-g-EGD) kopolimerleri, poli(vinil alkol) (VA) ile karıştırılarak poli(vinil alkol)/(κ-karragenan-greft-etilen glikol dimetakrilat (VA/CG-g-EGD) membranları hazırlanmıştır. Çalışmanın amacı, başlatıcı tipinin aşı verimliliğini ve buna bağlı olarak elde edilen membranların morfolojik ve yüzey özelliklerini nasıl etkilediğini incelemektir. AFM ve temas açısı analizleri, başlatıcı türünün yüzey pürüzlülüğü ve ıslanabilirlik üzerinde önemli bir etkiye sahip olduğunu göstermiştir. Başlatıcılar arasında, BPO en homojen yüzey yapısını oluştururken, CAN daha düşük aşı verimliliğine sahip daha pürüzlü bir morfoloji üretmiştir. Saf VA membranlara kıyasla, sentezlenen VA/CG-g-EGD membranları daha düzgün, daha kararlı yüzeyler ve ayarlanabilir hidrofilik–hidrofobik denge sergileyerek başarılı aşı polimerizasyonunu doğrulamıştır. Elde edilen sonuçlar, aşı polimerizasyon parametrelerinin kontrolünün membran yüzey performansını etkili biçimde geliştirdiğini göstermektedir. Gelişmiş yüzey bütünlüğü ve morfolojik kararlılık, VA/CG-g-EGD membranlarını pervaporasyon temelli ayırma ve seçici geçirgenlik ile mekanik dayanım gerektiren ilaç salım uygulamaları için umut vadeden adaylar haline getirmektedir.

Anahtar Kelimeler

• Atomik kuvvet mikroskobu
• temas açısı
• poli(vinil alkol)
• başlatıcı

Destekleyen Kurum

Kırklareli Üniversitesi

Proje Numarası

DPT-2010K121120, KLUBAP-204, and KLUBAP-264.

Teşekkür

Yazarlar, bu çalışmada kullanılan tesislere erişim imkânı sağlayan Kırklareli Üniversitesi İleri Teknolojiler Uygulama ve Araştırma Merkezi'ne (İTÜAM) teşekkürlerini sunarlar. Ayrıca, DPT-2010K121120, KLUBAP-204 ve KLUBAP-264 proje numaraları kapsamındaki mali destekleri için Kırklareli Üniversitesi Bilimsel Araştırma Projeleri Koordinasyon Birimi'ne de teşekkürlerini sunarlar.

Kaynakça

1. Amiri, S., Vatanpour, V., & He, T. (2023). Antifouling thin-film nanocomposite NF membrane with polyvinyl alcohol-sodium alginate-graphene oxide nanocomposite hydrogel coated layer for As(III) removal. Chemosphere, 322, 138159. https://doi.org/10.1016/j.chemosphere.2023.138159
2. Baysak, F. K., & Geyik, G. (2024). Hidrofilik Aşı Kopolimer Membranların Şişme Davranışının Kinetik İncelenmesi. Kirklareli University Journal of Engineering and Science, 10(2), 191-206. https://doi.org/10.34186/klujes.1562185
3. Cebeci, B., & Geyik, G. (2025). Graft copolymerization and characterization of 2-hydroxyethyl methacrylate (HEMA) onto sodium alginate using different initiators. International Journal of Biological Macromolecules, 328, 147699. https://doi.org/10.1016/j.ijbiomac.2025.147699
4. Chavez-Baldovino, E., Malca-Reyes, C. A., Masso, R., Feng, P., & Díaz-Vázquez, L. M. (2025). Development and Characterization of κ-Carrageenan and Boron Nitride Nanoparticle Membranes for Improved Ionic Conductivity in Fuel Cells. Fuels, 6(1), 15. https://doi.org/10.3390/fuels6010015
5. Çaykara, T., Demirci, S., Eroğlu, M. S., & Güven, O. (2006). Surface properties of binary blend films of poly( N ‐vinyl‐2‐pyrrolidone) and poly(vinyl alcohol) with sodium alginate. Journal of Polymer Science Part B: Polymer Physics, 44(2), 426-430. https://doi.org/10.1002/polb.20712
6. Danish, M. (2022). Contact angle studies of hydrophobic and hydrophilic surfaces. Içinde In Handbook of Magnetic Hybrid Nanoalloys and Their Nanocomposites (Pp. 1-22). Cham: Springer International Publishing. Handbook of Magnetic Hybrid Nanoalloys and their Nanocomposites (ss. 1-22). Springer, Cham. Geliş tarihi gönderen https://doi.org/10.1007/978-3-030-34007-0_24-1
7. Fathiraja, P., Gopalrajan, S., Karunanithi, M., Nagarajan, M., Obaiah, M. C., Durairaj, S., & Neethirajan, N. (2022). Response surface methodology model to optimize concentration of agar, alginate and carrageenan for the improved properties of biopolymer film. Polymer Bulletin, 79(8), 6211-6237. https://doi.org/10.1007/s00289-021-03797-5
8. Geyik, G. (2025a). Etilen Glikol Dimetakrilatın, Sodyum Aljinat, Kitosan ve Polivinil Alkol Üzerine Farklı Başlatıcılar Kullanılarak Aşılanması ve Karakterizasyonu. Afyon Kocatepe University Journal of Sciences and Engineering, 25(1), 59-69. https://doi.org/10.35414/akufemubid.1479986

9. Geyik, G. (2025b). Synthesis, Characterization, and Swelling Performance of Chitosan-Graft-Poly(ethylene glycol dimethacrylate). ChemistrySelect, 10(37), e03204. https://doi.org/10.1002/slct.202503204
10. Geyik, G., & Işıklan, N. (2020a). PH /temperature‐responsive poly(dimethylaminoethyl methacrylate) grafted κ‐carrageenan copolymer: Synthesis and physicochemical properties. Journal of Applied Polymer Science, 137(48), 49596. https://doi.org/10.1002/app.49596
11. Geyik, G., & Işıklan, N. (2020b). Synthesis, characterization and swelling performance of a temperature/pH-sensitive κ-carrageenan graft copolymer. International Journal of Biological Macromolecules, 152, 359-370. https://doi.org/10.1016/j.ijbiomac.2020.02.129
12. Geyik, G., & Işıklan, N. (2023). Chemical modification of κ-carrageenan with poly(2-hydroxypropylmethacrylamide) through microwave induced graft copolymerization: Characterization and swelling features. International Journal of Biological Macromolecules, 235, 123888. https://doi.org/10.1016/j.ijbiomac.2023.123888
13. Guo, J., Dong, S., Ye, M., Wu, X., Lv, X., Xu, H., & Li, M. (2022). Effects of Hydroxypropyl Methylcellulose on Physicochemical Properties and Microstructure of κ-Carrageenan Film. Foods, 11(19), 3023. https://doi.org/10.3390/foods11193023
14. Ismail, M. F., Islam, M. A., Khorshidi, B., Tehrani-Bagha, A., & Sadrzadeh, M. (2022). Surface characterization of thin-film composite membranes using contact angle technique: Review of quantification strategies and applications. Advances in Colloid and Interface Science, 299, 102524. https://doi.org/10.1016/j.cis.2021.102524
15. Işıklan, N., & Kurşun, F. (2013). Synthesis and characterization of graft copolymer of sodium alginate and poly(itaconic acid) by the redox system. Polymer Bulletin, 70(3), 1065-1084. https://doi.org/10.1007/s00289-012-0876-x
16. Işıklan, N., Kurşun, F., & İnal, M. (2010). Graft copolymerization of itaconic acid onto sodium alginate using benzoyl peroxide. Carbohydrate Polymers, 79(3), 665-672. https://doi.org/10.1016/j.carbpol.2009.09.021
17. Kashyap, S., Pratihar, S. K., & Behera, S. K. (2016). Strong and ductile graphene oxide reinforced PVA nanocomposites. Journal of Alloys and Compounds, 684, 254-260. https://doi.org/10.1016/j.jallcom.2016.05.162
18. Khulbe, K. C., Feng, C. Y., & Matsuura, T. (Ed.). (2008). Atomic Force Microscopy. Içinde Synthetic Polymeric Membranes: Characterization by Atomic Force Microscopy (ss. 19-45). Berlin, Heidelberg: Springer. https://doi.org/10.1007/978-3-540-73994-4_3
19. Khulbe, Kailash Chandra, & Matsuura, T. (2021). Membrane Characterization. Içinde Kailash Chandra Khulbe & T. Matsuura (Ed.), Nanotechnology in Membrane Processes (ss. 89-133). Cham: Springer International Publishing. https://doi.org/10.1007/978-3-030-64183-2_3
20. Krainer, S., & Hirn, U. (2021). Contact angle measurement on porous substrates: Effect of liquid absorption and drop size. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 619, 126503. https://doi.org/10.1016/j.colsurfa.2021.126503
21. Liu, Q., Zhu, X., Chen, B., & Zhu, X. (2024). Applications of AFM in Membrane Characterization and Fouling Analysis. ACS ES&T Engineering, 4(8), 1805-1838. https://doi.org/10.1021/acsestengg.4c00111
22. Lusiana, R. A., Nuryanto, R., Dayanti, D., Muna, N., Safitri, T., & Sasongko, N. A. (2025). Role of Polyvinyl Alcohol in Enhancing Chitosan Membranes for Desalination: An Experimental and Theoretical Study. ChemistrySelect, 10(22), e01611. https://doi.org/10.1002/slct.202501611
23. Megias-Alguacil, D., Tervoort, E., Cattin, C., & Gauckler, L. J. (2011). Contact angle and adsorption behavior of carboxylic acids on α-Al2O3 surfaces. Journal of Colloid and Interface Science, 353(2), 512-518. https://doi.org/10.1016/j.jcis.2010.09.087
24. Rana, D., & Matsuura, T. (2010). Surface Modifications for Antifouling Membranes. Chemical Reviews, 110(4), 2448-2471. https://doi.org/10.1021/cr800208y
25. Suganthi, S., Vignesh, S., Al-Ansari, M. M., Al-Humaid, L. A., Oh, T. H., & Raj, V. (2024). Development of PVA/sodium alginate incorporated with histidine capped silver nanoparticles for food packaging application. Polymers for Advanced Technologies, 35(5), e6413. https://doi.org/10.1002/pat.6413
26. Sukhlaaied, W., & Riyajan, S.-A. (2013). Synthesis and properties of carrageenan grafted copolymer with poly(vinyl alcohol). Carbohydrate Polymers, 98(1), 677-685. https://doi.org/10.1016/j.carbpol.2013.06.047
27. Tripathy, T., & Singh, R. P. (2000). High performance flocculating agent based on partially hydrolysed sodium alginate–g–polyacrylamide. European Polymer Journal, 36(7), 1471-1476. https://doi.org/10.1016/S0014-3057(99)00201-3
28. Wei, M., Zhang, Y., Wang, Y., Liu, X., Li, X., & Zheng, X. (2024). Employing Atomic Force Microscopy (AFM) for Microscale Investigation of Interfaces and Interactions in Membrane Fouling Processes: New Perspectives and Prospects. Membranes, 14(2), 35. https://doi.org/10.3390/membranes14020035
29. Yoshida, W., & Cohen, Y. (2003). Topological AFM characterization of graft polymerized silica membranes. Journal of Membrane Science, 215(1), 249-264. https://doi.org/10.1016/S0376-7388(03)00019-X
30. Zhuikova, Y. V., Zhuikov, V. A., Zubareva, A. A., Akhmedova, S. A., Sviridova, I. K., Sergeeva, N. S., & Varlamov, V. P. (2020). Physicochemical and biological characteristics of chitosan/κ-carrageenan thin layer-by-layer films for surface modification of nitinol. Micron, 138, 102922. https://doi.org/10.1016/j.micron.2020.102922