PFDoA KAPLI YÜZEYLERİN AMFİFOBİK ÖZELLİKLERİNİN İNCELENMESİ

Tugba Demir Çalışkan

doi:10.17780/ksujes.1822763

EN TR

INVESTIGATION OF AMPHIPHOBIC PROPERTIES OF PFDoA COATED SURFACES

Abstract

In this study, coatings with highly amphiphobic features developed through the chemical vapor deposition of perfluorododecanoic acid (PFDoA) onto a poly(glycidyl methacrylate) (PGMA) anchoring layer. Silicon wafers were employed as model substrates, while TiO₂–polyurethane (TiO₂–PU) composite films and filter papers served as rough surface models. The PGMA films were thermally annealed at 110°C to ensure strong adhesion to the substrate, followed by a chemical reaction with PFDoA. Contact angle measurements revealed that the water and hexadecane contact angles on PFDoA/PGMA-coated silicon surfaces were 108.2±1.1° and 67.6±1.5°, respectively. On rough substrates, a pronounced enhancement in oleophobic behavior was observed, with the hexadecane contact angle increasing to 81.4° on TiO₂–PU rough surfaces and reaching 95.5° on filter papers. In addition, PFDoA/PGMA-coated filter papers exhibited superhydrophobic characteristics, achieving a water contact angle of 129.4°. Free surface energy (FSE) calculations indicated that the surface energy of PGMA films decreased from 48.6 mN/m to 13.8 mN/m after deposition of an approximately 9.9 nm-thick PFDoA layer. These results demonstrate that the achieved surface energies are lower than that of polytetrafluoroethylene (PTFE,~18 mN/m), which is commonly regarded as a benchmark material for low-surface-energy applications, highlighting PFDoA-based nanocoatings as a potential alternative to PTFE.

Keywords

PFDoA KAPLI YÜZEYLERİN AMFİFOBİK ÖZELLİKLERİNİN İNCELENMESİ

Öz

Bu çalışmada, yüksek amfifobik özellik gösteren kaplamaların geliştirilmesi amacıyla, poliglisidil metakrilat (PGMA) ara yüzeyi üzerine kimyasal buhar biriktirme yöntemiyle perflorododekanoik asit (PFDoA) kaplamaları hazırlanmıştır. Silikon tabakalar model yüzey olarak kullanılırken, TiO2–poliüretan (TiO2–PU) kompozit filmler ve filtre kâğıtları pürüzlü yüzey modelleri olarak kullanılmıştır. PGMA filmleri 110 °C’de tavlanarak substrat yüzeyine güçlü şekilde bağlanmış, ardından PFDoA asidi ile tepkimeye girmiştir. Temas açısı ölçümleri, PFDoA/PGMA kaplı Si yüzeylerinde su ve hekzadekan temas açılarının 108,2 ± 1.1° ve 67,6 ± 1.5° olduğunu göstermiştir. Pürüzlü yüzeylerde oleofobik davranışın belirgin şekilde arttığı, hekzadekan temas açısının TiO2–PU pürüzlü yüzeylerinde 81,4°’ye, filtre kâğıtlarında ise 95,5°’ye ulaştığı belirlenmiştir. PFDoA/PGMA kaplamalı filtre kâğıtları ayrıca süperhidrofobik karakter sergileyerek su temas açısında 129,4° değerine ulaşmıştır. Serbest yüzey enerjisi (SYE) hesaplamaları, PGMA filmlerinde 48,6 mN/m olan yüzey enerjisinin, yaklaşık 9,9 nm kalınlığında PFDoA tabakasıyla kaplandıktan sonra 13,8 mN/m’ye düştüğünü ortaya koymuştur. Elde edilen bu değerler, düşük yüzey enerjili uygulamalarda referans malzeme olarak kabul edilen politetrafloroetilene (PTFE, ~18 mN/m) kıyasla daha düşük yüzey enerjilere ulaşıldığını göstermekte ve PFDoA bazlı nanokaplamaların PTFE’ye potensiyel bir alternatif olduğunu ortaya koymaktadır.

Anahtar Kelimeler

Etik Beyan

Çalışmanın tüm süreçlerinin araştırma ve yayın etiğine uygun olduğunu, etik kurallara ve bilimsel atıf gösterme ilkelerine uyduğumu beyan ederim.

Teşekkür

Makalenin hazırlanma sürecinde değerli görüş ve önerileriyle katkı sağlayan sayın Prof. Dr. Igor LUZINOV’ a teşekkür ederim.

Kaynakça

Abdollahi, H., Najafi, V. & Amiri, F. (2021). Determination of monomer reactivity ratios and thermal properties of poly(GMA-co-MMA) copolymers. Polym. Bull. 78, 493–511 (2021). https://doi.org/10.1007/s00289-020-03123-5
Adarraga, O., Agustín-Sáenz, C., Bustero, I., & Brusciotti, F. (2023). Superhydrophobic and oleophobic microtextured aluminum surface with long durability under corrosive environment. Scientific Reports, 13(1), 1737. https://doi.org/10.1038/s41598-023-28587-z
Ajeya, K. V., Dhanabalan, K., Thong, P. T., Kim, S.-C., Park, S.-C., Son, W.-K., & Jung, H.-Y. (2024). Short-side-chain perfluorosulfonic acid incorporated with functionalized silane-based hybrid membrane for the application of energy devices. International Journal of Hydrogen Energy, 55, 432-440. https://doi.org/10.1016/j.ijhydene.2023.11.229
Askin, S., Kizil, S., & Bulbul Sonmez, H. (2021). Creating of highly hydrophobic sorbent with fluoroalkyl silane cross-linker for efficient oil-water separation. Reactive and Functional Polymers, 167, 105002. https://doi.org/10.1016/j.reactfunctpolym.2021.105002
Aslanidou, D., & Karapanagiotis, I. (2018). Superhydrophobic, superoleophobic and antimicrobial coatings for the protection of silk textiles. Coatings, 8(3). https://doi.org/10.3390/coatings8030101.
Bao, Q., Nishimura, N., Kamata, H., Furue, K., Ono, Y., Hosomi, M., & Terada, A. (2017). Antibacterial and anti-biofilm efficacy of fluoropolymer coating by a 2,3,5,6-tetrafluoro-pphenylenedimethanol structure. Colloids and Surfaces B: Biointerfaces, 151, 363-371. https://doi.org/10.1016/j.colsurfb.2016.12.020
Bliznyuk, V., Galabura, Y., Burtovyy, R., Karagani, P., Lavrik, N., & Luzinov, I. (2014). Electrical conductivity of insulating polymer nanoscale layers: environmental effects. Physical Chemistry Chemical Physics, 16(5), 1977-1986. https://doi.org/10.1039/C3CP54020K
Borodinov, N., Soliani, A. P., Galabura, Y., Zdyrko, B., Tysinger, C., Novak, S., Du, Q., Huang, Y., Singh, V., Han, Z., Hu, J., Kimerling, L., Agarwal, A. M., Richardson, K., & Luzinov, I. (2016). Gradient polymer nanofoams for encrypted recording of chemical events. ACS Nano, 10(12), 10716-10725. https://doi.org/10.1021/acsnano.6b06044

Cengiz, U., Ünzal, Ö., & Belen, S. N. (2023). Fabrication of self-cleaning perfluoroacrylate blend films by spray coating method. Journal of Advanced Research in Natural and Applied Sciences, 9(1), 158-166. https://doi.org/10.28979/jarnas.1168028
Demir Çalışkan, T. (2025). Perfloropolieter (PFPE) temelli polyesterlerin nylon filmlerinde su ve yağ iticiliğini arttırmadaki etkisi. Harran Üniversitesi Mühendislik Dergisi, 10(3), 213-227. https://doi.org/10.46578/humder.1717177
Demir Caliskan, T. D. (2025). Impact of fluorinated segment chemistry on film wettability: comparative study of short-chain perfluoroalkyl and perfluoropolyether structures. Polymer Engineering & Science, 65(8), 4052-4060. https://doi.org/10.1002/pen.27269
Demir Caliskan, T., Hukum, K. O., Caykara, T., & Luzinov, I. (2022). Toward the replacement of long-chain perfluoroalkyl compounds: perfluoropolyether-based low surface energy grafted nanocoatings. ACS Applied Polymer Materials, 4(2), 980-986. https://doi.org/10.1021/acsapm.1c01438
Demir, T., Wei, L., Nitta, N., Yushin, G., Brown, P. J., & Luzinov, I. (2017). Toward a long-chain perfluoroalkyl replacement: water and oil repellency of polyethylene terephthalate (PET) films modified with perfluoropolyether-based polyesters. ACS Applied Materials & Interfaces, 9(28), 24318-24330. https://doi.org/10.1021/acsami.7b05799
Divandari, M., Arcifa, A., Ayer, M. A., Letondor, C., & Spencer, N. D. (2021). Applying an oleophobic/hydrophobic fluorinated polymer monolayer coating from aqueous solutions. Langmuir, 37(14), 4387-4394. https://doi.org/10.1021/acs.langmuir.1c00479
Ebajo, V. D., Jr., Huang, J.-Y., Lin, S.-W., Liu, Y.-T., Valinton, J. A. A., Yang, H.-C., & Chen, C.-H. (2025). Reversible restoration of superhydrophobicity in fluoroalkylsilyl-grafted graphene via C-F-containing solvents for anticorrosion and self-cleaning coatings. ACS Applied Nano Materials, 8(35), 17287-17296. https://doi.org/10.1021/acsanm.5c03497
Erbil, H. Y. (2020). Industrial applications of superhydrophobic coatings: Challenges and prospects. Hacettepe Journal of Biology and Chemistry, 48(5), 447-457. https://doi.org/10.15671/hjbc.810490
Eshaghi, A. (2020). Fabrication of transparent Silica-Silica nanotube/PFTS nano-composite thin films with superhydrophobic, oleophobic, self-cleaning and anti-icing properties. Optical and Quantum Electronics, 52(12), 516. https://doi.org/10.1007/s11082-020-02656-3
Galabura, Y., Soliani, A. P., Giammarco, J., Zdyrko, B., & Luzinov, I. (2014). Temperature controlled shape change of grafted nanofoams. Soft Matter, 10(15), 2567-2573. https://doi.org/10.1039/C4SM00055B
Han, D. K., Jeong, S. Y., Kim, Y. H., & Min, B. G. (1993). Surface structure and inert surface characteristics of perfluorodecanoic acid-grafted polyurethane. Journal of Applied Polymer Science, 47(5), 761-769. https://doi.org/10.1002/app.1993.070470502
Hare, E. F., Shafrin, E. G., & Zisman, W. A. (1954). Properties of films of adsorbed fluorinated acids. The Journal of Physical Chemistry, 58(3), 236-239. https://doi.org/10.1021/j150513a011
Huang, J., Sha, G., Cui, M., Quan, M., Wang, Y., Lu, Y., Zhu, J., & Chen, J. (2024). A highly reactive soybean oil-based superhydrophobic polyurethane film with long-lasting antifouling and abrasion resistance. Nanoscale Advances, 6(22), 5663-5670. https://doi.org/10.1039/D4NA00674G
Huang, L., Song, J., Lu, Y., Chen, F., Liu, X., Jin, Z., Zhao, D., Carmalt, C. J., & Parkin, I. P. (2017). Superoleophobic surfaces on stainless steel substrates obtained by chemical bath deposition. Micro & Nano Letters, 12(2), 76-81. https://doi.org/10.1049/mnl.2016.0576
Hüküm Özkan, K. (2025). Korozyona dirençli amfifobik yüzey tasarımı: silika-perflorosilan tabanlı kaplamalar. Gazi Üniversitesi Fen Fakültesi Dergisi, 6(1), 161-170. https://doi.org/10.63716/guffd.1677675
Hukum Ozkan, K., Demir Caliskan, T., Caykara, T., & Demirel, G. (2024). Toward water and oil repellent coating: synthesis of fluorinated methacrylate-glycidyl methacrylate copolymers. ACS Omega, 9(32), 34650-34660. https://doi.org/10.1021/acsomega.4c03275
Khanjani, P., King, A. W. T., Partl, G. J., Johansson, L.-S., Kostiainen, M. A., & Ras, R. H. A. (2018). Superhydrophobic paper from nanostructured fluorinated cellulose esters. ACS Applied Materials & Interfaces, 10(13), 11280-11288. https://doi.org/10.1021/acsami.7b19310
Koschitzki, F., Özcan, O., Wanka, R., Krisam, M., & Rosenhahn, A. (2024). Marine fouling release performance of amphiphilic carboxybetaine perfluoropolyether methacrylate polymer coatings. Advanced Materials Interfaces, 11(33), 2400370. https://doi.org/10.1002/admi.202400370
Krishnan, S., Weinman, C. J., & Ober, C. K. (2008). Advances in polymers for anti-biofouling surfaces. Journal of Materials Chemistry, 18(29), 3405-3413. https://doi.org/10.1039/B801491D
Liang, H., Zhang, Z., Liu, Y., Ye, M., Hu, C., & Huang, Y. (2023). Self-healable and transparent PDMS-g-poly(fluorinated acrylate) coating with ultra-low ice adhesion strength for anti-icing applications. Chemical Communications, 59(22), 3293-3296. https://doi.org/10.1039/D2CC05834K
Liu, Y., Gao, S., Liu, J., & Zhang, Q. (2023). Biomimetic slippery liquid-infused porous surfaces fabricated by porous fluorinated polyurethane films for anti-icing property. Progress in Organic Coatings, 179, 107524. https://doi.org/10.1016/j.porgcoat.2023.107524
Liu, Y., Klep, V., Zdyrko, B., & Luzinov, I. (2005). Synthesis of high-density grafted polymer layers with thickness and grafting density gradients. Langmuir, 21(25), 11806-11813. https://doi.org/10.1021/la051695q
Lu, S., Zhao, Y., & Hellerman, E. A. P. (2024). UV-durable self-cleaning coatings for autonomous driving. Scientific Reports, 14(1), 8066. https://doi.org/10.1038/s41598-024-58549-y
Mei, G., Lei, S., Li, Q., Xu, J., & Huo, M. (2024). Preparation of fluorinated polyesters by reversible addition–fragmentation chain transfer step-growth polymerization. Polymer Chemistry, 15(12), 1234-1243. https://doi.org/10.1039/D4PY00156G
Mohseni, M., Lahiri, S. K., Nadaraja, A. V., Sundararaj, U., & Golovin, K. (2023). Durable and comfortable superoleophobic fabrics utilizing ultra-short-chain fluorinated surface chemistry. Chemical Engineering Journal, 471, 144726. https://doi.org/10.1016/j.cej.2023.144726
Nan, A., Radu, T., Filip, X., Kacsó, I., Hădade, N. D., Nekvapil, F., & Miclăuş, M. (2023). Efficient chemical synthesis of new thermoplastic fluorinated aromatic polyester. Polymer, 283, 126261. https://doi.org/https://doi.org/10.1016/j.polymer.2023.126261
Qiu, X., Li, J., Wang, J., Yang, X., Li, Y., & Qi, D. (2022). A robust superhydrophobic and oleophobic coating with short chain perfluoroalkyl group and flower-shaped SiO2 nanoparticles. Surface and Coatings Technology, 447, 128810. https://doi.org/10.1016/j.surfcoat.2022.128810
Owens, D. K. ve Wendt, R. C. (1969). Estimation of the surface free energy of polymers. Journal of Applied Polymer Science, 13 (8), 1741-1747. https://doi.org/10.1002/app.1969.070130815
Ramaratnam, K., Tsyalkovsky, V., Klep, V., & Luzinov, I. (2007). Ultrahydrophobic textile surface via decorating fibers with monolayer of reactive nanoparticles and non-fluorinated polymer. Chemical Communications (43), 4510-4512. https://doi.org/10.1039/B709429A
Rodič, P., Može, M., Golobič, I., & Milošev, I. (2024). Functionalization of the aluminium surface by CuCl2 chemical etching and perfluoro silane grafting: Enhanced corrosion protection and improved anti-icing behaviour. Metals, 14(10). https://doi.org/10.3390/met14101118
Sepúlveda, M., Kamnev, K., Pytlicek, Z., Prasek, J., & Mozalev, A. (2021). Superhydrophobic– oleophobic visible–transparent antireflective nanostructured anodic HFO2 multifunctional coatings for potential solar panel applications. ACS Applied Nano Materials, 4(2), 1754-1765. https://doi.org/10.1021/acsanm.0c03202
Sullivan, D. E. (1981). Surface tension and contact angle of a liquid–solid interface. J. Chem. Phys. 74, 2604– 2615, https://doi.org/10.1063/1.441333
Taibi, J., Rouif, S., Ameduri, B., Sonnier, R., & Otazaghine, B. (2023). Radiation induced graft polymerization of fluorinated monomers onto flax fabrics for the control of hydrophobic and oleophobic properties. Polymer, 281, 126132. https://doi.org/10.1016/j.polymer.2023.126132
Tripathi, S., Maidul Haque, S., Divakar Rao, K., De, R., Shripathi, T., Deshpande, U., Ganesan, V., Sahoo, N. K. (2016). Investigation of optical and microstructural properties of RF magnetron sputtered PTFE films for hydrophobic applications. Appl. Surf. Sci., 289–298. https://doi.org/10.1016/j.apsusc.2016.05.121
Tsyalkovsky, V., Klep, V., Ramaratnam, K., Lupitskyy, R., Minko, S., & Luzinov, I. (2008). Fluorescent reactive core–shell composite nanoparticles with a high surface concentration of epoxy functionalities. Chemistry of Materials, 20(1), 317-325. https://doi.org/10.1021/cm0718421
Usman, A., Zhang, C., Zhao, J., Peng, H., Kurniawan, N. D., Fu, C., Hill, D. J. T., & Whittaker, A. K. (2021). Tuning the thermoresponsive properties of PEG-based fluorinated polymers and stimuli responsive drug release for switchable 19F magnetic resonance imaging. Polymer Chemistry, 12(38), 5438-5448. https://doi.org/10.1039/D1PY00602A
Vatansever, F., Burtovyy, R., Zdyrko, B., Ramaratnam, K., Andrukh, T., Minko, S., Owens, J. R., Kornev, K. G., & Luzinov, I. (2012). Toward fabric-based flexible microfluidic devices: Pointed surface modification for pH sensitive liquid transport. ACS Applied Materials & Interfaces, 4(9), 4541-4548. https://doi.org/10.1021/am3008664
Wei, L., Demir, T., Grant, A., Tsukruk, V., Brown, P. J., & Luzinov, I. (2018). Attainment of water and oil repellency for engineering thermoplastics without long-chain perfluoroalkyls: Perfluoropolyether-based triblock polyester additives. Langmuir, 34(43), 12934-12946. https://doi.org/10.1021/acs.langmuir.8b02628
Wu, Z., Tang, L., Dai, J., & Qu, J. (2019). Synthesis and properties of fluorinated non-isocyanate polyurethanes coatings with good hydrophobic and oleophobic properties. Journal of Coatings Technology and Research, 16(5), 1233-1241. https://doi.org/10.1007/s11998-019-00195-5
Xia, W., & Zhang, Z. (2018). PVDF-based dielectric polymers and their applications in electronic materials. IET Nanodielectrics, 1(1), 17-31. https://doi.org/10.1049/ietnde.2018.0001
Xie, S., Liao, X., Fan, Y., Li, J., Jiang, Q., Zheng, Y., Huang, Z., & Li, S. (2025). Fluoro-silicon modified polythiourethane copolymer for marine antifouling coatings. Coatings, 15(5). https://doi.org/10.3390/coatings15050588
Xu, H., Chen, C., Hu, S., Chen, Y., Duan, D., Liang, G., & Zhong, X. (2025). Highly transparent anti-smudge coatings for self-cleaning, controllable liquid transport, and corrosion resistance. polymers, 17(3). https://doi.org/10.3390/polym17030302
Xu, X., Zhang, Z., & Liu, W. (2009). Fabrication of superhydrophobic surfaces with perfluorooctanoic acid modified TiO2/polystyrene nanocomposites coating. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 341(1), 21-26. https://doi.org/10.1016/j.colsurfa.2009.03.028
Zdyrko, B., & Luzinov, I. (2011). Polymer brushes by the “Grafting to” method. Macromolecular Rapid Communications, 32(12), 859-869. https://doi.org/10.1002/marc.201100162
Zdyrko, B., Swaminatha Iyer, K., & Luzinov, I. (2006). Macromolecular anchoring layers for polymer grafting: comparative study. Polymer, 47(1), 272-279. https://doi.org/10.1016/j.polymer.2005.11.029
Zhang, J., Li, J., Han, Y. (2004). Superhydrophobic PTFE surfaces by extension. Macromol. Rapid Commun, 25, 1105– 1108. https://doi.org/ 10.1002/marc.200400065

Ayrıntılar

Birincil Dil

Türkçe

Konular

Malzeme Bilimi ve Teknolojileri , Polimer Bilimi ve Teknolojileri , Malzeme Karekterizasyonu

Bölüm

Araştırma Makalesi

Yazarlar

Tugba Demir Çalışkan ^*
0000-0003-2935-0525
Türkiye

Yayımlanma Tarihi

3 Mart 2026

Gönderilme Tarihi

13 Kasım 2025

Kabul Tarihi

13 Ocak 2026

Yayımlandığı Sayı

Yıl 2026 Cilt: 29 Sayı: 1

DOI

https://doi.org/10.17780/ksujes.1822763

IZ

https://izlik.org/JA93XW42PX

Kaynak Göster

RIS / Bibtex

APA

Demir Çalışkan, T. (2026). PFDoA KAPLI YÜZEYLERİN AMFİFOBİK ÖZELLİKLERİNİN İNCELENMESİ. Kahramanmaraş Sütçü İmam Üniversitesi Mühendislik Bilimleri Dergisi, 29(1), 330-343. https://doi.org/10.17780/ksujes.1822763