ZİRKONYUM OKSİT İLAVESİNİN ELEKTROEĞİRME YÖNTEMİ İLE ÜRETİLEN POLİ(METİL METAKRİLAT) FİBERLERİN ÖZELLİKLERİ ÜZERİNE ETKİSİ

Öz

Bu çalışmanın amacı, elektroeğirme yöntemi ile poli(metil metakrilat) (PMMA)/zirkonyum oksit (ZrO2) kompozit fiberleri üretmek ve ZrO2 ilavesinin PMMA/ZrO2 fiberlerinin özellikleri üzerindeki etkisini araştırmaktır. Farklı miktarlarda ZrO2 nanopartikülleri (%1, 2,5 ve 5) içeren %10 ve %15 ağırlık oranlarında PMMA’dan oluşan fiberler optimize edilmiş bir elektrik alan potansiyelinde üretilmiştir. Fiberlerin kimyasal yapısı ve yüzey morfolojisi, SEM-EDS, XRD ve FTIR kullanılarak analiz edildi. ZrO2 nanopartikül ilavesinin fiberlerin termal özellikleri üzerindeki etkisi TGA ve DTG ile incelendi. Morfolojik gözlemler, ağırlıkça %2,5 ve %5 ZrO2 (PMMA-10/ZrO2-2.5 ve PMMA-10/ZrO2-5) nanopartiküllerinin, polimer zincir etkileşimi sayesinde ağırlıkça %10 PMMA içeren polimer matrisine iyi dağılabildiğini göstermiştir. Fiber oluşumu, PMMA-10 fiberlerine kıyasla ZrO2 miktarının artmasıyla iyileşme göstermiştir. Kuvars kristal mikro terazisi (QCM) sensörü, PMMA-10, PMMA-10/ZrO2-2.5 ve PMMA-10/ZrO2-5 fiberleriyle kaplanmış materyallerin pH 7.0'deki davranışını değerlendirmek için kullanılmıştır. Sonuçlar, PMMA-10/ZrO2-5 fiberleriyle kaplanmış QCM elektrodunun PMMA-10/ZrO2-2.5 fiberlerinden daha iyi performans sergilediğini göstermiştir.

Anahtar Kelimeler

• Elektroeğirme
• Fiber
• Poli(Metil Metakrilat)
• Kuvars Kristal Mikro Terazisi
• Zirkonyum Oksit

Proje Numarası

TDH-2019-7359

EFFECT OF ZIRCONIUM OXIDE ADDITION ON THE PROPERTIES OF POLY(METHYL METHACRYLATE) ELECTROSPUN FIBERS

Öz

The aim of this study was to produce poly(methyl methacrylate) (PMMA)/zirconium oxide (ZrO2) electrospun composite fibers and to investigate the effect of ZrO2 addition on the properties of PMMA/ZrO2 fibers. A series of fibers with 10 and 15 wt% of PMMA containing different amounts of ZrO2 nanoparticles (1, 2.5 and 5 wt%) were produced at an optimal electric field potential. The chemical structure and surface morphology of the fibers were analyzed using SEM-EDS, XRD, and FTIR. The effect of ZrO2 nanoparticles addition on the thermal properties of the fibers was studied with TGA and DTG. The morphological observations showed that 2.5 and 5 wt% ZrO2 (PMMA-10/ZrO2-2.5 and PMMA-10/ZrO2-5) nanoparticles could be well-dispersed into 10 wt% PMMA polymer matrix due to the polymer chain interaction. The formation of fibers showed improvement with the increase in the amount of ZrO2 compared to PMMA-10 fibers. A quartz crystal microbalance (QCM) sensor was utilized to evaluate the behavior of materials coated with PMMA-10, PMMA-10/ZrO2-2.5, and PMMA-10/ZrO2-5 fibers at pH 7.0. The results indicated that the QCM electrode coated with PMMA-10/ZrO2-5 fibers performed better than PMMA-10/ZrO2-2.5 fibers.

Anahtar Kelimeler

• Electrospinning
• Fiber
• Poly(Methyl Methacrylate)
• Quartz Crystal Microbalance
• Zirconium Oxide

Destekleyen Kurum

The Scientific Research Projects Unit of Süleyman Demirel University (BAP Project Number: TDH-2019-7359)

Proje Numarası

TDH-2019-7359

Etik Beyan

The authors declare that materials and methods used in this paper do not require ethics approval and/or permission.

Teşekkür

This study was funded by the Scientific Research Projects Unit of Süleyman Demirel University (BAP Project Number: TDH-2019-7359).

Kaynakça

1. Adhikari, J., Biswas, B., Chabri, S., Bandyapadhyay, N. R., Sawai, P., Mitra, B. C., Sinha, A., 2017. Effect of Functionalized Metal Oxides Addition on the Mechanical, Thermal and Swelling Behaviour of Polyester/Jute Composites. Engineering Science and Technology, an International Journal, 20(2), 760–774.
2. Akparanta, D. A., Shull, K. R., Sun, Y., 2010. Measurement of the Kinetics of Swelling and Deswelling Behavior of Poly(methacrylic acid) with Quartz Crystal Microbalance and Ellipsometry. Nanoscape, 7(1), 28–32.
3. Alamgir, M., Mallick, A., Nayak, G. C., Tiwari, S. K., 2019. Development of PMMA/TiO₂ Nanocomposites as Excellent Dental Materials. Journal of Mechanical Science and Technology, 33(10), 4755–4760.
4. Alharbi, N. D., Moselhy, M. T. H., Guirguis, O. W., 2025. Impact of Doping Different Concentrations of TiO2 Nanoparticles to PMMA on Its Structural, Thermal and Optical Properties for Optical Applications. Journal of Non-Crystalline Solids, 661, 123558.
5. Aydogdu, M. O., Oprea, A. E., Trusca, R., Surdu, A. V., Ficai, A., Holban, A. M., Iordache, F., Paduraru, A. V., Filip, D. G., Altun, E., Ekren, N., Oktar, F. N., Gunduz, O., 2018. Production and Characterization of Antimicrobial Electrospun Nanofibers Containing Polyurethane, Zirconium Oxide and Zeolite. BioNanoScience, 8, 154–165.
6. Aziz, S. B., Abdullah, O. G., Hussein, A. M., Ahmed, H. B., 2017. From Insulating PMMA Polymer to Conjugated Double Bond Behavior: Green Chemistry as a Novel Approach to Fabricate Small Band Gap Polymers. Polymers, 9(11), 626.
7. Burcea, A., Bănățeanu, A. M., Poalelungi, C. V., Forna, N., Cumpătă, C. N., 2024. Enhanced Properties and Multifaceted Applications of Polymethyl Methacrylate (PMMA) in Modern Medicine and Dentistry. Romanian Journal of Oral Rehabilitation, 16(4), 108–123.
8. Chen, L., Huang, Z. M., Dong, G. H., He, C. L., Liu, L., Hu, Y. Y., Li, Y., 2009. Development of A Transparent PMMA Composite Reinforced with Nanofibers. Polymer Composites, 30(3), 239–247.

9. Cho, Y., Baek, J. W., Sagong, M., Ahn, S., Nam, J. S., Kim, I.-D., 2025. Electrospinning and Nanofiber Technology: Fundamentals, Innovations, and Applications. Advanced Materials, 37, 2500162.
10. Devikala, S., Kamaraj, P., Arthanareeswari, M., 2018. AC Conductivity Studies of PMMA/TiO2 Composites. Materials Today: Proceedings, 5, 8678-8682.
11. Díaz, M., Fuente, S., Mariana, A., Zubieta, C., 2024. Theoretical–Experimental Study of Fe–ZrO₂ and Co–ZrO₂ Oxidative Degradation of Methyl Orange Azo Dye. Results in Surfaces and Interfaces, 16, 100269.
12. Easley, A. D., Ma, T., Eneh, C. I., Yun, J., Thakur, R. M., Lutkenhaus, J. L., 2022. A Practical Guide to Quartz Crystal Microbalance with Dissipation Monitoring of Thin Polymer Films, Journal of Polymer Science, 60, 1090–1107.
13. Elmadani, A. A., Tomić, N., Radović, I., Vuksanovic, M. M., Stojanovic, D., Heinemann, R. J., Radojevic, V., 2019. Salt Template Zirconia Reinforcing Particles as Possible Reinforcement for PMMA Matrix Composite. Advanced Composites Letters, 28, 1–7.
14. Fontainha, C. C. P., Neto, A. T. B., Santos, A. P., & Faria, L. O., 2016. P(VDF-TrFE)/ZrO₂ Polymer-Composites for X-Ray Shielding. Materials Research, 19(2), 426–433.
15. Gautam, C., Joyner, J., Gautam, A., Rao, J., Vajtai, R., 2016. Zirconia-Based Dental Ceramics: Structure, Mechanical Properties, Biocompatibility and Applications. Dalton Transactions, 45(48), 19194–19215.
16. Gazquez, G. C., Smulders, V., Veldhuis, S. A., Wieringa, P., Moroni, L., Boukamp, B. A., Elshof, J. E., 2017. Influence of Solution Properties and Process Parameters on the Formation and Morphology of YSZ and NiO Ceramic Nanofibers by Electrospinning. Nanomaterials, 7(1), 1–15.
17. Haldorai, Y., Zong, T., Shim, J., 2012. Core–Shell ZrO₂/PMMA Composites Via Dispersion Polymerization in Supercritical Fluid: Synthesis, Characterization and Mechanism. Journal of Applied Polymer Science, 123, 1176–1183.
18. Hashem, M., Rez, M. F. A., Fouad, H., Elsarnagawy, T., Elsharawy, M. A., Umar, A., Assery, M., Ansari, S. G., 2017. Influence of Titanium Oxide Nanoparticles on the Physical and Thermomechanical Behavior of PMMA: A Denture Base Resin. Science of Advanced Materials, 9(6), 938–944.
19. He, X., Qu, Y., Peng, J., Peng, T., Qian, Z., 2017. A Novel Botryoidal Aramid Fiber Reinforcement of a PMMA Resin for a Restorative Biomaterial. Biomaterials Science, 5(4), 808–816.
20. Horti, N. C., Mathapati, S. I., Banapurmath, N. R., Pujari, V. S., Inamdar, S. R., Kamatagi, M. D., 2025. Investigation of Structural, Optical and Mechanical Properties of Poly(methyl methacrylate)/Zirconium Oxide (PMMA/ZrO₂) Nanocomposite Films. Polymer Bulletin, 82, 4879–4900.
21. Hu, Y., Gu, G., Zhou, S., Wu, L., 2011. Preparation and Properties of Transparent PMMA/ZrO₂ Nanocomposites Using 2-Hydroxyethyl Methacrylate as a Coupling Agent. Polymer, 52(1), 122–129.
22. Huang, X., Bai, Q., Hu, J., Hou, D., 2017. A Practical Model of Quartz Crystal Microbalance in Actual Applications. Sensors, 17, 1785.
23. Im, Y. M., Oh, T. H., Cha, J. W., Seo, Y. H., Hwang, J. S., Nathanael, J. A., Han, S. S., Jang, S. H., 2014. Preparation of Poly(vinyl alcohol)/ZrO₂ Composite Nanofibers Via Co-Axial Electrospinning with Higher ZrO₂ Particle Content. Fibers and Polymers, 15(10), 2066–2071.
24. Kalluri, L., Duan, Y., Janorkar, A. V., 2024. Electrospun Polymeric Nanofibers for Dental Applications. Journal of Applied Polymer Science, 141, e55224.
25. Kim, D. H., Park, M. S., Cho, H. H., Park, J. T., Kim, J. H., 2016. Synthesis of Organized Mesoporous Metal Oxide Films Templated by Amphiphilic PVA–PMMA Comb Copolymer. RSC Advances, 6(72), 67849–67857.
26. Kumari, S., Hussain, A., Rao, J., Singh, K., Avinashi, S. K., Gautam, C., 2023. Structural, Mechanical and Biological Properties of PMMA–ZrO₂ Nanocomposites for Denture Applications. Materials Chemistry and Physics, 295, 127089.
27. Li, S., Zhang, Y. M., Zhou, Y. F., 2012. Preparation and Characterization of Sol–Gel Derived Zirconia Coated Carbon Fiber. Surface and Coatings Technology, 206(23), 4720–4724.
28. Li, Y., He, J-H., 2019. Fabrication and Characterization of ZrO2 Nanofibers by Critical Bubble Electrospinning for High-Temperature-Resistant Adsorption and Separation. Adsorption Science & Technology, 37(5-6), 425–437.
29. Lin, C. K., Xie, J. W., Tsai, P. J., Wang, H. Y., Lu, Z. W., Lin, T. Y., Kuo, C. Y., 2024. The Effects of Different Blending Methods on the Thermal, Mechanical, and Optical Properties of PMMA/SiO2 Composites. Journal of Composites Science, 8(9), 369.
30. Maji, P., Choudhary, R. B., Majhi, M., 2016. Structural, Optical and Dielectric Properties of ZrO₂ Reinforced Polymeric Nanocomposite Films of Polymethylmethacrylate (PMMA). Optik, 127(11), 4848–4853.
31. Motaung, T. E., Luyt, A. S., Saladino, M. L., Martino, D. C., Caponetti, E., 2012. Morphology, Mechanical Properties and Thermal Degradation Kinetics of PMMA–Zirconia Nanocomposites Prepared by Melt Compounding. Express Polymer Letters, 6(11), 871–881.
32. Murthe, S. S., Saheed, M. S. M., Perumal, V., Saheed, M. S. M., Mohamed, N. M., 2019. Electrospun Nanofibers for Biosensing Applications. In: Gopinath SCB, Lakshmipriya T, editors. Nanobiosensors for Biomolecular Targeting. p. 253-267. Amsterdam (Netherlands): Elsevier.
33. Nabiyev, A. A., Islamov, A. K., Maharramov, A. M., Nuriyev, M. A., Ismayilova, R. S., Doroshkevic, A. S., Pawlukojc, A., Turchenko, V. A., Olejniczak, A., Rulev, M. İ., Almasan, V., Kuklin, A. I., 2018. Structural Studies of Dielectric HDPE+ZrO2 Polymer Nanocomposites: Filler Concentration Dependences. In Journal of Physics: Conference Series, 3rd International Summer School and Workshop ‘Complex and Magnetic Soft Matter Systems: Physico-Mechanical Properties and Structure’, Russia, Dubna. 994(1), 012011.
34. Neamah, Z. J., Mahdi, S. H., 2023. Effect of zirconia addition on thermal and mechanical properties of poly-methyl methacrylate composites. Digest Journal of Nanomaterials and Biostructure, 18(3), 927–932.
35. Nohut Maslakci, N., Ulusoy, S., Uygun Oksuz, A., 2017. Investigation of The Effects of Plasma-Treated Chitosan Electrospun Fibers onto Biofilm Formation. Sensors and Actuators B: Chemical, 246, 887-895.
36. Rodaev, V. V., Razlivalova, S. S., Zhigachev, A. O., Vasyukov, V. M., Golovin, Y. I., 2019. Preparation of Zirconia Nanofibers by Electrospinning and Calcination with Zirconium Acetylacetonate as Precursor. Polymers, 11(6), 1067.
37. Saligheh, O., Khajavi, R., Yazdanshenas, M.E., Rashidi, A., 2016. Production and Characterization of Zirconia (ZrO2) Ceramic Nanofibers by Using Electrospun Poly(vinyl alcohol)/Zirconium Acetate Nanofibers as a Precursor. Journal of Macromolecular Science, Part B Physics, 55(6), 605-616.
38. Sang, T., Ye, Z., Fischer, N. G., Skoe, E. P., Echeverría, C., Wu, J., Aparicio, C., 2020. Physical-Chemical İnteractions Between Dental Materials Surface, Salivary Pellicle and Streptococcus Gordonii. Colloids and surfaces. B: Biointerfaces, 190, 110938.
39. Wang, H., Liu, Q., Yang, Q., Li, Y., Wang, W., Sun, L., Zhang, C., Li, Y., 2010a. Electrospun Poly(methyl methacrylate) Nanofibers and Microparticles. Journal of Materials Science, 45, 1032–1038.
40. Wang, X., Pan, S., Zhang, M., Qi, J., Sun, X., Gu, C., Wang, L., Li, J., 2019. Modified Hydrous Zirconium Oxide/PAN Nanofibers for Efficient Defluoridation from Groundwater. Science of the Total Environment, 685, 401–409.
41. Wang, X., Wu, L., Li, J., 2010b. Influence of Nanozirconia on the Thermal Stability of Poly(methyl methacrylate) Prepared by In Situ Bulk Polymerization. Journal of Applied Polymer Science, 117, 163–170.
42. Weber F., Barrantes A., 2017. Real-time formation of salivary films onto polymeric materials for dental applications: Differences between unstimulated and stimulated saliva. Colloids and Surfaces B: Biointerfaces, 154, 203–209.
43. Zafar, M., Najeeb, S., Khurshid, Z., Vazirzadeh, M., Zohaib, S., Najeeb, B., Sefat, F., 2016. Potential of Electrospun Nanofibers for Biomedical and Dental Applications. Materials, 9(2), 73.
44. Zhu, G., Ding, Y., Zhao, D., Jiang, Y., Zheng, J., 2018. Effect of Flake Size on Thermal Properties of Graphene Oxide/Poly(methyl methacrylate) Composites Prepared via In Situ Polymerization. Journal of Applied Polymer Science, 135(21), 46290.