10.57647/inl.2025.1401.02

PMMA/TiO₂ Nanocomposite Derived Selective Surface Coatings for Improved Optical Properties with Cold Plasma Assisted

PDF
Supplementary information
  • Rasheed N. Abed1,
  • Hassan Hashim2,
  • Muataz Ali3,
  • Roaa T. Abdulla4,
  • Ali B. M. Ali5,
  • Mohammed Al-Baidhani4,
  • Kadhim A. Aadim6,
  • Abdulrahman H. Shaker6,
  • Khalid Zainulabdeen3,
  • Ahmed A. Alamiery7,
  • Muna S. Bufaroosha8,
  • Emad Yousif3,
  1. Department of Mechanical Engineering, College of Engineering, Al-Nahrain University, P.O. Box: 64040, Jadriyah, Baghdad, Iraq
  2. Department of Medical Physics, College of Science, Al-Nahrain University, P.O. Box: 64021, Jadriyah, Baghdad, Iraq
  3. Department of Chemistry, College of Science, Al-Nahrain University, P.O. Box: 64021, Jadriyah, Baghdad, Iraq
  4. Department of Physics, College of Science, Al-Nahrain University, P.O. Box: 64021, Jadriyah, Baghdad, Iraq
  5. Air conditioning Engineering, Faculty of Engineering, Warith Al-Anbiyaa University, Karbala 56001, Iraq
  6. Department of Physics, College of Science, University of Baghdad, Baghdad, Iraq
  7. Al-Ayen Scientific Research Center, Al-Ayen Iraqi University, AUIQ, Al-Nasiriyah, P.O. Box: 64004, Thi Qar, Iraq
  8. Department of Chemistry, College of Science, United Arab Emirates University, Al-Ain, United Arab Emirates
PMMA/TiO₂ Nanocomposite Derived Selective Surface Coatings for Improved Optical Properties with Cold Plasma Assisted

Copyright (c) 2025 Rasheed N. Abed, Hassan Hashim, Muataz Ali, Roaa T. Abdulla, Ali B. M. Ali, Mohammed Al-Baidhani, Kadhim A. Aadim, Abdulrahman H. Shaker, Khalid Zainulabdeen, Ahmed A. Alamiery, Muna S. Bufaroosha, Emad Yousif (Author)

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

How to Cite

Abed, R. N., Hashim, H., Ali, M., Abdulla, R. T., Ali, A. B. M., Al-Baidhani, M., Aadim, K. A., Shaker, A. H., Zainulabdeen, K., Alamiery, A. A., Bufaroosha, M. S., & Yousif, E. (2025). PMMA/TiO₂ Nanocomposite Derived Selective Surface Coatings for Improved Optical Properties with Cold Plasma Assisted. International Nano Letters. https://doi.org/10.57647/inl.2025.1401.02
Crossref
Scopus
Google Scholar
Europe PMC

PDF views: 62

Abstract

Progressive evolution of nanostructured coatings with costume-made structural and optical properties is of major interest for different high-tech applications. This work targeted the incorporation of titanium dioxide (TiO₂) nanoparticles to poly(methyl methacrylate) (PMMA) nanocomposite films across three concentrations (1%, 2%, and 3%) using the casting method. These films were later treated with cold dielectric barrier discharge (DBD) plasma to refine their structure and optical properties. Investigations were systematically studied through the work including the extinction coefficient, absorption coefficient, dielectric constant (real and imaginary), energy gap, Urbach energy, and refractive index. A significant increase resulted in the real dielectric constant, refractive index, and absorption coefficient, on the other hand, a decrease due to strong absorption was noted in the imaginary dielectric constant and extinction factor. Direct and indirect energy gap ranged from 4.7 to 4.5 eV, and 3.4 to 3.25 eV, respectively. Urbach energy data elevated from 366 to 395 meV, which suggests improved charge carrier transport attributed to structural modifications achieved by plasma induction. Also, cold DBD plasma treatment efficiently increased the roughness of the surface, and as a result, improved the film's optical absorption abilities. These findings were confirmed using structural analysis, X-ray diffraction (XRD) showed a mixture of semi-crystalline and amorphous phases. SEM examined revealed a uniform TiO₂ distribution across the PMMA accompanied by gaining a roughened morphology. AFM analysis also showed a boost in surface roughness from 0.828 to 3.04 nm after incorporating TiO₂ and applying plasma treatment. These results propose that PMMA/TiO₂ nanocomposite films showed encouraging potential for applications in fiber optics, optical sensors, photocatalysis, and light-emitting diodes (LEDs).

Highlights

·       The study targeted the incorporation of titanium dioxide (TiO₂) nanoparticles into poly(methyl methacrylate) (PMMA) nanocomposite films across three concentrations (1%, 2%, and 3%) using the casting method.

·       The investigations were systematically studied through the work, including the optical properties and Urbach energy.

·       The direct and indirect energy gap decreased from 4.7 to 4.5 eV, and from 3.4 to 3.25 eV, respectively. Urbach energy data elevated from 366 to 395 meV, suggesting an improvement in charge carrier transport due to structural modifications achieved by plasma induction.

·       The SEM examination revealed a uniform TiO₂ distribution across the PMMA accompanied by a roughened morphology. AFM analysis also showed a boost in surface roughness from 0.828 to 3.04 nm after incorporating TiO₂ and applying plasma treatment.

·       The innovative results of PMMA/TiO₂ nanocomposite films showed encouraging potential for applications in fiber optics, optical sensors, photocatalysis, and light-emitting diodes (LEDs).

Keywords

  • Cold DBD plasma,
  • Titanium oxide (TiO2),
  • Poly(methyl methacrylate) (PMMA),
  • Nanocomposite films (PMMA/TiO2),
  • Optical conductivity and Urbach energy
PDF
Supplementary information

References

  1. Mani AD, Reddy PMK, Srinivaas M, Ghosal P: Xanthopoulos N, Subrahmanyam C, "Facile Synthesis of Efficient Visible Active C-Doped TiO2 Nanomaterials with High Surface Area for the Simultaneous Removal of Phenol and Cr(VI). Mater. Res. Bull. 61, 391–399 (2015). https://doi.org/10.1016/j.materresbull.2014.10.051.
  2. Entradas TJ, Cabrita JF, Barrocas B, Nunes MR, Silvestre AJ, Monteiro OC: Synthesis of Titanate Nanofibers Co-Sensitized with ZnS and Bi2S3 Nanocrystallites and Their Application on Pollutants Removal. Mater. Res. Bull. 72, 20–28 (2015). https://doi.org/10.1016/j.materresbull.2015.07.008.
  3. Karunakaran C, Abiramasundari G, Gomathisankar P, Manikandan G, Anandi V: Preparation and Characterization of ZnO–TiO2 Nanocomposite for Photocatalytic Disinfection of Bacteria and Detoxification of Cyanide under Visible Light. Mater. Res. Bull. 46, 1586–1592 (2011). https://doi.org/10.1016/j.materresbull.2011.06.019.
  4. Cacciato G, Bayle M, Pugliara A, Bonafos C, Zimbone M, Privitera V, Grimaldi MG, Carles R: Enhancing Carrier Generation in TiO2 by a Synergistic Effect between Plasmon Resonance in Ag Nanoparticles and Optical Interference. Nanoscale 7, 13468–13476 (2015). https://doi.org/10.1039/C5NR02406D.
  5. Nicosia A, Vento F, Di Mari GM, D’Urso L, Mineo PG: TiO2-Based Nanocomposites Thin Film Having Boosted Photocatalytic Activity for Xenobiotics Water Pollution Remediation. Nanomaterials 11 (400), 1-11 (2021). https://doi.org/10.3390/nano11020400.
  6. Wang P, Wang J, Yu H, Zhao L, Yu J: Hierarchically Macro–Mesoporous TiO2 Film via Self-Assembled Strategy for Enhanced Efficiency of Dye-Sensitized Solar Cells. Mater. Res. Bull. 74, 380–386 (2016). https://doi.org/10.1016/j.materresbull.2015.11.004.
  7. Shengyuan Y, Peining Z, Nair AS, Ramakrishna S: Rice Grain-Shaped TiO2 Mesostructures—Synthesis, Characterization, and Applications in Dye-Sensitized Solar Cells and Photocatalysis. J. Mater. Chem. 21, 6541–6548 (2011). https://doi.org/10.1039/C0JM04512H.
  8. Qu A, Xu X, Xie H, Zhang Y, Li Y, Wang J: Effects of Calcining Temperature on Photocatalysis of G-C3N4/TiO2 Composites for Hydrogen Evolution from Water. Mater Res Bull 80, 167–176 (2016). https://doi.org/10.1016/j.materresbull.2016.03.043.
  9. Etacheri V, Di Valentin C, Schneider J, Bahnemann D, Pillai SC: Visible-Light Activation of TiO2 Photocatalysts: Advances in Theory and Experiments. J Photochem Photobiol C Photochem Rev. 25, 1–29 (2015). https://doi.org/10.1016/j.jphotochemrev.2015.08.003.
  10. Weon S, Choi W: TiO2 Nanotubes with Open Channels as Deactivation-Resistant Photocatalyst for the Degradation of Volatile Organic Compounds. Environ Sci Technol. 50, 2556–2563 (2016). https://doi.org/10.1021/acs.est.5b05418.
  11. Gao L, Wang Y, Yan Y, Li Q, Hao C, Ma T: Enhanced Photoactivities of TiO2 Particles Induced by Bio-Inspired Micro-Nanoscale Substrate. J Colloid Interface Sci. 470, 10–13 (2016). https://doi.org/10.1016/j.jcis.2016.02.029.
  12. Arabzadeh A, Salimi A: One Dimensional CdS Nanowire@TiO2 Nanoparticles Core-Shell as High-Performance Photocatalyst for Fast Degradation of Dye Pollutants under Visible and Sunlight Irradiation. J Colloid Interface Sci. 479, 43–54 (2016). https://doi.org/10.1016/j.jcis.2016.06.036.
  13. Zhang J, Li L, Xiao Z, Liu D, Wang S, Zhang J, Hao Y, Zhang W: Hollow Sphere TiO2–ZrO2 Prepared by Self-Assembly with Polystyrene Colloidal Template for Both Photocatalytic Degradation and H2 Evolution from Water Splitting. ACS Sustain Chem Eng. 4, 2037–2046 (2016). https://doi.org/10.1021/acssuschemeng.5b01359.
  14. Enculescu M., Costas A., Evanghelidis A., Enculescu I.: Fabrication of ZnO and TiO2 Nanotubes via Flexible Electro-Spun Nanofibers for Photocatalytic Applications. Nanomaterials. 11, 1305 (2021). https://doi.org/10.3390/nano11051305.
  15. Md Alamgir A, Mallick GC, Nayak SK, Tiwari S: Development of PMMA/TiO2 nanocomposites as excellent dental materials. JMST 33(10), 4755–4760 (2019). https://doi.org/10.1007/s12206-019-0916-7.
  16. Thakur V K, Kessler M R: Self-healing polymer nanocomposite materials: A review, Polym. 69, 369–383 (2015). DOI: 10.1016/j.polymer.2015.04.086
  17. Sheng CK, Amin KAM, Hong LL, Hassan MF, Ismail M: Investigation of Morphological, Structural and Electrical Properties of Cds/PMMA Nanocomposite Film Prepared by Solution Casting Method. Int J Electrochem Sci. 12, 10023–10031 (2017). https://doi.org/10.20964/2017.11.75.
  18. Jordan J, Jacob KI, Tannenbaum R, Sharaf MA, Jasiuk I: Experimental Trends in Polymer Nanocomposites-A Review. Mater Sci Eng A 393, 1–11 (2005). https://doi.org/10.1016/j.msea.2004.09.044.
  19. Hafizah NN, Mamat MH, Said CMS, Abidin MH, Rusop M: Thermal Degradation of Nanocomposited PMMA/TiO2 Nanocomposites. IOP Conf Ser: Mater Sci Eng. 46, 1-8 (2013). https://doi.org/10.1088/1757-899X/46/1/012045.
  20. Hassanien AS, Sharma I: Band-gap engineering, conduction and valence band positions of thermally evaporated amorphous Ge15-x Sbx Se50 Te35 thin films: Influences of Sb upon some optical characterizations and physical parameters. J Alloys Compd. 79, 750–763 (2019). https://doi.org/10.1016/j.jallcom.2019.05.252
  21. Ali U, Karim KJBA, Buang NA: A Review of the Properties and Applications of Poly (Methyl Methacrylate) (PMMA). Polym Rev. 55, 678–705 (2015 https://doi.org/10.1080/15583724.2015.1031377.
  22. Pandey N, Khaling R, Verma P, Pendke P, Patel A: Characterization of TiO2 Doped Poly (Methyl Methacrylate) PMMA Thin Films Using XRD. AIP Conf Proc. 2100, 020151 (2019). https://doi.org/10.1063/1.5098705.
  23. Ghosh S, Mallik AK, Basu RN: Enhanced Photocatalytic Activity and Photoresponse of Poly(3,4-Ethylenedioxythiophene) Nanofibers Decorated with Gold Nanoparticle under Visible Light. Sol Energy 159, 548–560 (2018). https://doi.org/10.1016/j.solener.2017.11.036.
  24. Abdullah AM, Alwan LH, Ahmed AA, Abed RN: Optical properties of polystyrene with carbon nanotube and carbon nano incorporated and surface morphology studies. Int Nano Lett. 13, 165–176 (2023). https://doi.org/10.1007/s40089-023-00398-0.
  25. Rezaei F, Shokri B, Sharifian M: Atmospheric-pressure DBD plasma-assisted surface modification of poly methyl methacrylate: A study on cell growth/proliferation and antibacterial properties. Appl Surf Sci. 164, 471–481 (2015). DOI: 10.1016/j.apsusc.2015.11.036
  26. Taha SK, Mazhir SN, Khalaf MK: A Comparative Study on the Electrical Characteristics of Generating Plasma by Using Different Target Sources. Baghdad Sci J. 15, 436–440 (2018). http://dx.doi.org/10.21123/bsj.2018.15.4.0436.
  27. Wieland F, Bruch R, Bergmann M, Partel S, Urban GA, Can DC: Enhanced Protein Immobilization on Polymers-A Plasma Surface Activation Study. Polymers MDPI 12, 104 (2020). https://doi.org/10.3390/polym12010104.
  28. Ali U, Garima Nagpal, Ishu Sharma, S.K. Tripathi: The effect of substitution of Sb with Zn on the optical and physical properties of Se90Sb10-xZnx (x = 0, 2, 4, 6, 10 at. %) thin films. Optik 207, 164460 (2020). https://doi.org/10.1016/j.ijleo.2020.164460
  29. Mahdi S M, Habeeb M A: Tailoring the structural and optical features of (PEO–PVA)/(SrTiO3–CoO) polymeric nanocomposites for optical and biological applications. Polym Bull. 80, 12741–12760 (2023). https://doi.org/10.1007/s00289-023-04676-x.
  30. Abed RN, Sattar MA, Hameed SS et al.: Optical and morphological properties of poly(vinyl chloride)-nano-chitosan composites doped with TiO2 and Cr2O3 nanoparticles and their potential for solar energy applications. Chem Pap. 77, 757–769 (2023). https://doi.org/10.1007/s11696-022-02512-6.
  31. Aadim, K. A.: Spectroscopic study the plasma parameters for SnO2 doped ZnO prepared by pulse Nd: YAG laser deposition. IJP 17(42), 125-135 (2019). https://doi.org/10.30723/ijp.v17i42.447
  32. Akatsuka, H.: Optical Emission Spectroscopic (OES) Analysis for Diagnostics of Electron Density and Temperature in Non-Equilibrium Argon Plasma Based on Collisional- Radiative Model. Adv. Phys.: X, 4(1), 1592707, 1-26 (2019). https://doi.org/10.1080/23746149.2019.1592707
  33. Jaber, Z. S., Habeeb, M. A., & Radi, W. H.: Synthesis and Characterization of (PVA-CoO-ZrO2) Nanostructures for Nano optoelectronic Fields. EEJP: 2, 228-233 (2023). https://doi.org/10.26565/2312-4334-2023-2-25
  34. Ibrahim K. A., Aadim K. A: Spectroscopic Diagnosis of Cobalt Plasma Produced by OES Technique and Influence of Applied Voltage on Plasma Parameters. IJS 64(5), 2271-2281 (2023). https://doi.org/10.24996/ijs.2023.64.5.15
  35. Mohammed, A. A., & Habeeb, M. A.: Effect of Si3N4/TaC nanomaterials on the structural and electrical characteristics of poly methyl methacrylate for electrical and electronics applications. EEJP: 2, 157-164 (2023). https://doi.org/10.26565/2312-4334-2023-2-15
  36. Abed RN, Rashad AA, Rahman MH, Basem A, Al-Ani A, Husain A, Jumaah NS, Hashim H, Bufaroosha MS, Yousif E, Hadawey A: Synthesis, Structural, and Optical Properties of Modified Poly(vinyl Chloride) Thin Films by Ethylenediamine Loaded with Metal Oxide Nanoparticles. ChemistrySelect: 9, 1–17 (2024). https://doi.org/10.1002/slct.202401717.
  37. Abdullah AM, Alwan LH, Ahmed AA, Abed RN: Optical and Physical Properties for the Nanocomposite Poly(vinyl chloride) with Affected of Carbon Nanotube and Nano Carbon. PCCC: 16, 331–345 (2023 https://doi.org/10.30509/PCCC.2023.167082.1198.
  38. A. J. K. Algidsawi, A. Hashim, A. Hadi, M. A. Habeeb: Exploring the characteristics of SnO2 nanoparticles doped organic blend for low cost nanoelectronics applications. SPQEO: 24 (4), 472-477 (2021) DOI: https://doi.org/10.15407/spqeo24.03.472
  39. Abed RN, Zainulabdeen K, Abdallh M, Yousif E, Rashad AA: The optical properties behavior of modified poly(methyl methacrylate) nanocomposite thin films during solar energy absorption. J Non-Cryst Solids: 609, 122257 (2023). https://doi.org/10.1016/j.jnoncrysol.2023.122257.
  40. Abdullah AM, Alwan LH, Ahmed AA, Abed RN: Physical Study of PVA Filled with Carbon Nanotube and Nano Carbon with Roughness Morphology. J Phys Chem Res 11, 747–760 (2023). https://doi.org/10.22036/PCR.2022.362088.2195.
  41. Abed RN, Al-Sahib NK, Khalifa AJN: Energy Gap Demeanor for Carbon Doped with Chrome Nanoparticle to Increase Solar Energy Absorption. PCCC 13, 143–154 (2020). https://doi.org/10.30509/PCCC.2020.81613.
  42. Hashim H, Ali M, Abdulla RT, Abed RN, Basem A, Rashad AA, Al-Baidhani M, Aadim KA, Shaker AH, Bufaroosha MS, Yousif E: Influence of cold plasma treatment on the PS/TiO2 film’s optical properties of nanocomposite surfaces. Mater Lett 373, 137077 (2024). https://doi.org/10.1016/j.matlet.2024.137077.
  43. Abed, R. N., Al-Mashhadani, M. H., Yousif, E. et al. Organosilane-doped PVC lattice thin film for optoelectronic applications. J Opt. 53, 2247–2261 (2024). https://doi.org/10.1007/s12596-023-01351-2
  44. Hassanien AS, Akl AA: Effect of Se addition on optical and electrical properties of chalcogenide CdSSe thin films. Superlattice Microst. 89, 153–169 (2016). https://doi.org/10.1016/j.spmi.2015.10.044
  45. Abed RN, Yousif E, Abed ARN, Rashad AA: Synthesis Thin Films of Poly(Vinyl Chloride) Doped by Aromatic Organosilicon to Absorb the Incident Light. Silicon 14, 11829–11845 (2022). https://doi.org/10.1007/s12633-022-01893-3
  46. Al-Azzawi ZM, Al-Baidhani M, Abed ARN, Abed RN: Influence of Nano Silicon Carbide (SiC) Embedded in Poly(Vinyl Alcohol) (PVA) Lattice on the Optical Properties. Silicon 14, 5719–5732 (2022). https://doi.org/10.1007/s12633-021-01325-8
  47. Abed RN, Abed ARN, Yousif E: Carbon Surfaces Doped with (Co3O4-Cr2O3) Nanocomposite for High-Temperature Photo Thermal Solar Energy Conversion Via Spectrally Selective Surfaces. PCCC 14 (4), 301–315 (2020). DOI: 10.30509/PCCC.2021.166749.1098
  48. Omer RM, Al-Tikrity ETB, Abed RN, Kadhom M, Jawad AH, Yousif E.: Electrical conductivity and surface morphology of PVB films doped with different nanoparticles. PCCC 15 (3), 191–202 (2022). DOI: 10.30509/PCCC.2021.166839.1120
  49. Ahmed A, Abed RN, Kadhom M, Hashim H, Akram E, Jawad A, Yousif E: Modification of poly (vinyl chloride) thin films with organic compound and nanoparticles for solar energy applications. J Polym Res 30, 03654-1 (2023). https://doi.org/10.1007/s10965-023-03654-1.
  50. Zainulabdeen K, Abed RN, Yousif E: Optical systematic and morphological characterization of PMMA thin films containing copper(II) and zinc(II) chloride additives for selective surfaces. Phys Chem Res 12, 1091–1110 (2024). https://doi.org/10.22036/pcr.2024.477090.257.
  51. A. Hashim, A. J. Kadham, A. Hadi, and M. A. Habeeb: Determination of Optical Parameters of Polymer Blend/Nanoceramics for Electronics Applications. Nanosist. Nanomat. Nanotehnol.: 19 (2), 327–336 (2021). https://doi.org/10.15407/nnn.19.02.327
  52. Hamza, R. S. A., Habeeb, M. A.: Reinforcement of morphological, structural, optical, and antibacterial characteristics of PVA/CMC bioblend filled with SiO2/Cr2O3 hybrid nanoparticles for optical nanodevices and food packing industries. Polym. Bull.: 81, 4427–4448 (2024). https://doi.org/10.1007/s00289-023-04913-3
  53. Oreibi, I., Ali Habeeb, M. & Abdul Hamza, R.S. Polymer nanocomposites comprising PVA matrix and Ag–BaTiO3 nanofillers: a comparative study of structural, dielectric and optical characteristics for optics and quantum nanoelectronic applications. Opt. Quant. Electron.: 56 (119) 05685 (2024). https://doi.org/10.1007/s11082-023-05685-w
  54. Salam A M, Rahimi M Y, Mohammed A, Rasheed A, Dina S A, Ahmed A A, Ahmed A A, Basheer A, Emad Y: Additives Aid Switch to Protect the Photodegradation of Plastics in Outdoor Construction. NJES 22(4), 277-282 (2019). https://doi.org/10.29194/NJES.22040277
  55. Zageer, D., Al-Taa'y, W., Ibraheem, H., Hasan, A., Yousif, E.: Optical Properties and Morphological Study of New Films Derived From Poly(Vinyl Chloride)-Phenyl Phrine HCl Acid Complexes. ANJS 19, 51-57 (2016). DOI: 10.22401/JNUS.19.2.07
  56. Emir P, Kuru D: Boron nitride quantum dots/polyvinyl butyral nanocomposite films for the enhanced photoluminescence and UV shielding properties. J. Appl. Poly. Sci. 141, 55171 (2024). https://doi.org/10.1002/app.55171
  57. Habeeb, M. A., Mahdi, S. M.: Influence of ZrC nanofiler on the structural, dielectric and optical features of the PVA–PVP blend for electronic and optical nanodevices. Opt. Quant. Electron.: 55 (1076) 05426 (2023). https://doi.org/10.1007/s11082-023-05426-z
  58. Essam, M., Elsayed, A., Nasser, A. et al.: Processing of Ti–5Al–4W–2Fe Alloy Using Different Powder Metallurgy Routes to Improve Its Implementation in Structural Applications. Arab J Sci Eng (2025). https://doi.org/10.1007/s13369-024-09834-5