Features of formation, structure and properties of Langmuir–Blodgett films of poly(vinyl carbаzole) with inorganic nanoparticles

A technique for the forming of thin-film nanostructured coatings based on poly(vinyl carbazole) (PVCz) with silicon dioxide and zinc oxide nanoparticles using the Langmuir−Blodgett (LB) method has been developed. Based on the analysis of the PVCz monolayer compression isotherm and atomic force microscopy data on the structural and morphological characteristics of LB films formed by horizontal deposition on the surface of hydrophilized silicon substrates at different values of surface pressure (π), it has been established that the densest PVCz-based coatings are formed at π = 15 mN/m. The optimal content of nanoparticles (per 1 mol of polymer) in suspensions for obtaining uniform nanostructured coatings is up to 24.44 ‧ 10³ mol (for SiO₂) and up to 4.53 ‧ 10³ mol (for ZnO). The effect of the introduction of nanoparticles on the structure, wettability and local mechanical characteristics of the formed composite coatings is described. Based on the calculated values of the compression modulus of PVCz, PVCz–SiO₂, PVCz–ZnO monolayers and a set of experimental data obtained during the work, it is shown that the compression modulus of polymer and nanocomposite LB monolayers can be used as a quantitative criterion for assessing the density of the formed coatings.

1. A Comprehensive review on polymer nanocomposites; classification, properties and potential applications / A. Khan, S. Iqbal, M. Khan [et al.] // Journal of Nanoscope. – 2023. – Vol. 4, N 1. – P. 45–74. https://doi.org/10.52700/jn.v4i1.88

2. Ganesan, V. Some issues in polymer nanocomposites: Theoretical and modeling opportunities for polymer physics / V. Ganesan // Journal of Polymer Science. Part B: Polymer Physics. – 2008. – Vol. 46, N 24. – P. 2666–2671. https://doi.org/10.1002/polb.21587

3. Hanemann, T. Polymer-nanoparticle composites: from synthesis to modern applications / T. Hanemann, D. V. Szabó // Materials. – 2010. – Vol. 3, N 6. – P. 3468–3517. https://doi.org/10.3390/ma3063468

4. Martín-García, B. Block copolymer assisted self-assembly of nanoparticles into Langmuire–Blodgett films: Effect of polymer concentration / B. Martín-García, M. Mercedes Velázquez // Materials Chemistry and Physics. – 2013. – Vol. 141, N 1. – P. 324–332. https://doi.org/10.1016/j.matchemphys.2013.05.017

5. Conjugated polymers as Langmuir and Langmuir–Blodgett films: Challenges and applications in nanostructured devices / R. Da Rocha Rodrigues, R. L. C. G. da Silva, L. Caseli, L. O. Peres // Advances in Colloid and Interface Science. – 2020. – Vol. 285. – Art. 102277. https://doi.org/10.1016/j.cis.2020.102277

6. Structure and characterization of nanocomposite Langmuir−Blodgett films of poly(maleic monoester)/Fe3O4 nanoparticle complexes / D. K. Lee, Yo. S. Kang, Ch. S. Lee, P. Stroeve // Journal of Physical Chemistry B. – 2002. – Vol. 106, N 29. – P. 7267–7271. https://doi.org/10.1021/jp014446t

7. Synthesis of uniformly dispersed large area polymer/AgNPs thin film at air-liquid interface for electronic application / R. Mishra, R. K. Pandey, S. Jana [et al.] // Materials Today Communications. – 2020. – Vol. 24. – Art. 101191. https://doi.org/10.1016/j.mtcomm.2020.101191

8. Phase transitions in polymer monolayers: Application of the Clapeyron equation to PEO in PPO–PEO Langmuir films / L. Deschênes, J. Lyklema, C. Danis, F. Saint-Germain // Advances in Colloid and Interface Science. – 2015. – Vol. 222. – P. 199–214. https://doi.org/10.1016/j.cis.2014.11.002

9. Jun-Fu, Liu. Langmuir–Blodgett films of poly-N-vinylcarbazole prepared by radical polymerization method / JunFu Liu, Zu-Hong Lu, Kong-Zhang Yang // Thin Solid Films. – 1998. – Vol. 322, N 1–2. – P. 308–313. https://doi.org/10.1016/S0040-6090(97)00942-5

10. Room temperature operated ammonia gas sensor using polycarbazole Langmuir–Blodgett film / V. Saxena, S. Choud-hury, S. C. Gadkari [et al.] // Sensors and Actuators B: Chemical. – 2005. – Vol. 107, N 1. – P. 277–282. https://doi.org/10.1016/j.snb.2004.10.011

11. Sapsaliou D. V., Melnikova G. B., Lapitskaya V. А., Tolstaya T. N., Kuznetsova T. A., Kotov D. A., Chizhik S. A. Thin composite polymethyl methacrylate films with silicon dioxide nanoparticles. Zhurnal Belorusskogo gosudarstvennogo universiteta. Khimiya = Journal of the Belarusian State University. Chemistry, 2021, no. 2, pp. 36-49 (in Russian). https://doi. org/10.33581/2520-257X-2021-2-36-49

12. Gorbachev I. A., Smirnov A. V., Shamsutdinova E. S., Kashin V. V., Anisimkin V. I., Kolesov V. V., Kuznetsova I. E., Yudin S. G. Studying the structural and piezoelectric properties of PVDF films obtained using Langmuir–Blodgett technology. Bulletin of the Russian Academy of Sciences: Physics, 2021, vol. 85, no. 6, pp. 603–607. https://doi.org/10.3103/s1062873821060101

13. A Langmuir–Schaefer approach for the synthesis of highly ordered organoclay thin films / L. M. Toma, R. Y. N. Gengler, E. B. Prinsen [et al.] // Physical Chemistry Chemical Physics. – 2010. – Vol. 12, N 38. – P. 12188–12197. https://doi.org/10.1039/c0cp00286k

14. Johnson, K. L. Surface energy and the contact of elastic solids / K. L. Johnson, K. Kendall, A. D. Roberts // Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences. – 1971. – Vol. 324, N 1558. – P. 301–313. https://doi.org/10.1098/rspa.1971.0141

15. Kaelble, D. H. Dispersion-polar surface tension properties of organic solids / D. H. Kaelble // Journal of Adhesion. – 1970. – Vol. 2, N 2. – Р. 66–81. https://doi.org/10.1080/0021846708544582