The influence of nanosilica surface modifications with CH3- and NH2-groups on the properties of epoxy-silica composites
DOI:
https://doi.org/10.15407/hftp17.01.106Keywords:
epoxy composite, nanosilica, surface modification, compressive strength, shrinkage, fire resistance, swelling in acetone, 55 % H2O2, microscopyAbstract
The influence of the chemical nature of functional groups immobilized on the surface of silica nanoparticles on the physicochemical and mechanical properties of epoxy composites has been examined. Our work was formed on the basis of the assumption about the high role of the nature of the filler surface in the formation of the mechanical properties of polyepoxide. Modification of nanosilica with amino-groups (–NH2) should contribute to improving the characteristics of the composite due to the reactive affinity for epoxy and amine fragments of the matrix. In contrast, methyl groups (–CH?) should increase compatibility with the organic phase (oleophilicity), but due to chemical inertness, reduce the ability to interact in the polymer network. It was experimentally found that the introduction of 1–4 wt. % of unmodified nanosilica leads to a decrease in compressive strength, a decrease in chemical stability in acetone and an increase in the brittleness of the composite. At the same time, the indicators of shrinkage, thermal stability and resistance to an oxidizing environment remained unchanged or improved slightly. Modification of silica nanoparticles with methyl groups (at filling of 1–2 wt. %) provided partial recovery of compressive strength, increased thermal resistance and plasticity of the composite, but did not provide a significant improvement in solution stability or reduction in shrinkage. The most pronounced positive effects were achieved when using amino-nanosilica (modified with amino groups): a significant increase in compressive strength was observed to the level or higher than that of the unfilled resin, an increase in the elastic modulus, as well as a significant improvement in resistance to aggressive environments, fire resistance and reduction in shrinkage. Microscopic studies (optical microscopy, scanning electron microscopy, atomic force microscopy) confirmed that the introduction of unmodified nanofiller causes a decrease in transparency, the appearance of agglomerates and zones of heterogeneity. On the contrary, functionalization, especially with amino groups, provides a more homogeneous distribution of particles in the polymer matrix. The results obtained confirm the key role of the physicochemical properties of the nanosilica surface in the processes of structure formation of epoxy composites. Thus, optimal modification of the filler surface with chemically active groups opens up opportunities for targeted control of the properties of composites.
References
1. Surface Chemistry of Silica. 1-2 Vols. Ed. Acad. O.O. Chuiko. (Kyiv: NASU, 2003). [in Russian].
2. Tertykh V., Belyakova L. Chemical reactions on the surface of silica. (Kyiv: Naukova Dumka, 1985). [in Russian].
3. Ogbonna V.E., Popoola A.P., Popoola O.M. A review on recent advances on the mechanical and conductivity properties of epoxy nanocomposites for industrial applications. Polym. Bull. 2023. 80: 3449. https://doi.org/10.1007/s00289-022-04249-4
4. Parameswaranpillaj J., Pulikkalparambil H., Sanjay M.R., Siengchin S. Epoxy Composites: Fabrication, Characterization and Applications. (WiLEY-VCH, Weinheim, 2021). https://doi.org/10.1002/9783527824083
5. Chernin I., Smekhov F., Zherdev Yu. Epoxy polymers and compositions. (Moscow: Khimiya, 1982). [in Russian].
6. Kuzema P.O., Starokadomsky D.L., Tkachenko O.O., Tertykh V.A. Reinforcement of epoxy polymers with hydride-silylated fumed silica. Him. Fiz. Tehnol. Poverhni. 2020. 11(4): 484. https://doi.org/10.15407/hftp11.04.484
7. Kocijan A., Conradi M., Zorko M. Surface modification of nanosilica fillers for the preparation of silica/epoxy nanocoposites. Mater. Technol. 2012. 46(6): 657.
8. Starokadomskyy D., Voronin Ye., Reshetnyk M., Siharyova N. Morphology, Strength, Thermal and Chemical Stability of Epoxy Resin-Based Nanosystems with Pyrogenic Nanosilica A-300 and Its Compacted Analogue 'Densil' (with Original and Modified Surface). Nanosystems, Nanomaterials, Nanotechnologies. 2021. 19(1): 0071. https://doi.org/10.15407/nnn.19.01.071
9. Taylor A., Kinloch A., Masania K., Mohammed R. Toughness of nanopartice-modified epoxy and fibre composites. Conf. Paper. 2016. P. 9.
10. Guild F.J., Kinloch A.J., Masania K., Sprenger S. The fracture of thermosetting epoxy polymers containing silica nanoparticles. Strength Fract. Complexity. 2018. 11: 137. https://doi.org/10.3233/SFC-180219
11. Starokadomsky D.L., Telegeev I.G. Resistance of epoxy-polymer with 2-5 wt. % nanosilica in aggressive acid medium. Open J. Polym. Chem. 2012. 2(3): 117. https://doi.org/10.4236/ojpchem.2012.23016
12. Serekpayeva M., Ibzhanova A., Niyazbekova R., Aldabergenova S. Properties of epoxy resins?based composite materials with the addition of microspheres. Chem. Eng. Technol. 2023. 46(6): 1170. https://doi.org/10.1002/ceat.202200463
13. Sahu P.K., Mahanwar P.A., Bambole V.A. Effect of hollow glass microspheres and cenospheres on insulation properties of coatings. Pigmt. Resin. Technol. 2013. 42(4): 223. https://doi.org/10.1108/PRT-10-2011-0083
14. Adnan M.M., Tveten E.G., Miranti R., Hvidsten S., Glomm Ese M.-H., Glaum J., Einarsrud M.-A. In situ synthesis of epoxy nanocomposites with hierarchical surface-modified SiO2 Clusters. J. Sol-Gel Sci. Technol. 2020. 95: 783. https://doi.org/10.1007/s10971-020-05220-3
15. Uvida M., Almeida A., Pulcinelli S., Santilli C.V., Hammer P. Structural properties of epoxy-silica barrier coatings for corrosion protection of reinforcing steel. Polymer. 2022. 14(17): 3474. https://doi.org/10.3390/polym14173474
16. Zhang D., Wang J., Wen S., Wang P., Yin Ch., Du Zh. Preparation of silica powder in epoxy resin wear-resistant coating. Adv. Mater. Phys. Chem. 2015. 5(2): 60. https://doi.org/10.4236/ampc.2015.52009
17. Starokadomsky D. Technical note on surface modification of silica by epoxy resin. Appl. Chem. Chem. Eng. 2018. 2: 53.
18. Abd El-Fattaha M., Ashraf M. El Saeedb, Rasha A. El-Ghazawy. Chemical interaction of different sized fumed silica with epoxy via ultrasonication for improved coating. Prog. Org. Coat. 2019. 129: 1. https://doi.org/10.1016/j.porgcoat.2018.12.023
19. Mat?jka L., Du?ek K., Ple?til J., K??? J., Lednick? F. Formation and structure of the epoxy-silica hybrids. Polymer. 1999. 40(1): 171. https://doi.org/10.1016/S0032-3861(98)00214-6
20. Chao W., Chu C., Liao Y. Ultrahigh-solid-content silica/epoxy composite for high-performance semiconductor packaging. Composites, Part A. 2025. 192: 108757. https://doi.org/10.1016/j.compositesa.2025.108757
21. Deng F., Wang L., Zhou Y., Gong X., Zhao X., Hu T., Wu Ch. Effect of nanosilica content on the corrosion inhibition of composite coatings of a filled epoxy resin grafted with a hydrophobic fluoroalkylsilane: a dual critical concentrations interpretation. RSC Adv. 2017. 7(77): 48876. https://doi.org/10.1039/C7RA10315H
22. Ali A., Morteza E., Hadi J., Ahmadi Sh. The effect of nanosilica on mechanical, thermal and morphological properties of epoxy coating. Prog. Org. Coat. 2012. 75(4): 543. https://doi.org/10.1016/j.porgcoat.2012.05.013
23. Alavi Nikje M.M., Khanmohammadi M., Bagheri Garmarudi A. Interpretation of mechanical and thermal properties of heavy duty epoxy based floor coating doped by nanosilica. Nanotechnology in Construction. 2009. 3: 163. https://doi.org/10.1007/978-3-642-00980-8_21
24. Jumahata A., Soutisb C., Azam S., Kasolang S. Tensile properties of nanosilica/Epoxy Nanocomposites. Procedia Eng. 2012. 41: 1634. https://doi.org/10.1016/j.proeng.2012.07.361
25. Kanga Y., Chenb X., Songa S., Yu L., Zhang P. Friction and wear behavior of nanosilica-filled epoxy resin composite coatings. Appl. Surf. Sci. 2012. 258(17): 6384. https://doi.org/10.1016/j.apsusc.2012.03.046
26. Shohide M., Ahmed M. Influence of silica nanoparticles on the properties of nanocomposite based on epoxy as concrete protective coating. Mater. Sci. Forum. 2023. 1089: 153. https://doi.org/10.4028/p-p961bu
27. Starokadomsky D., Reshetnyk M. Effect of surface modification of nanosilica by hydride-groups on morphology, strength and resistance of epoxy-composites. Results Surf. Interfaces. 2023. 13: 100152. https://doi.org/10.1016/j.rsurfi.2023.100152
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Copyright (c) 2026 Д.Л. Старокадомський, Р.Б. Козакевич, Р.В. Лаврик, О.В. Ситніков, С.В. Севостьянов, М.М. Решетник, Н.В. Сігарьова, О.В. Хора, О.Б. Радченко, Н.С. Бодюл

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