Development of functionalized SiO2–TiO2 reinforced cardanol and caprolactam modified diamine based polybenzoxazine nanocomposites for high performance applications

  • T. Lakshmikandhan
  • Arumugam Hariharan
  • K. Sethuraman
  • Muthukaruppan AlagarEmail author


In the present work, three types of polybenzoxazines were synthesized using caprolactam-based diamine (CPA-NH2) and formaldehyde with different phenols, namely 4-fluorophenol, cardanol, and phenol, under appropriate experimental conditions. The molecular structure of the benzoxazine monomers was confirmed by FTIR, 1H, and 13C NMR spectroscopic techniques. Polybenzoxazines were obtained through ring-opening polymerization of benzoxazine monomers, and their formation was confirmed by FTIR spectroscopy. The elemental composition and morphological behavior of polybenzoxazines were characterized by SEM-EDAX and AFM techniques. The naturally occurring cardanol- and caprolactam-based diamine (CPA-NH2)-based benzoxazine was selected for detailed studies. The synthesized SiO2–TiO2 nanohybrid reinforcement was functionalized with 3-aminopropyltrimethoxysilane (3-APS) and reinforced with cardanol-based benzoxazine (CPBz) monomer. The resulted nanocomposites were studied for their corrosion protection behavior against mild steel surface along with thermomechanical (TGA and DMA) and morphological (SEM, XRD, and TEM) properties. The results obtained from electrochemical impedance analysis indicate that the 5 wt% of F–SiO2–TiO2 of reinforced CPBz exhibits an effective corrosion-resistant behavior toward surface of steel specimen than that of other samples.


Cardanol-based benzoxazine Functionalized SiO2–TiO2 Thermomechanical properties Nanocomposites Storage modulus Glass transition temperature Anticorrosion properties 


Supplementary material

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Supplementary material 1 (DOCX 1306 kb)


  1. 1.
    Foyet, A, Wu, TH, van der Ven, L, Kodentsov, A, de With, G, van Benthem, R, “Influence of Mixing Ratio on the Permeability of Water and the Corrosion Performance of Epoxy/Amine Coated Un-pretreated Al-2024 Evaluated by Impedance Spectroscopy.” Prog. Org. Coat., 64 138–141 (2009)CrossRefGoogle Scholar
  2. 2.
    Meis, NN, van der Ven, LG, van Benthem, RA, de With, G, “Extreme Wet Adhesion of a Novel Epoxy-Amine Coating on Aluminum Alloy 2024-T3.” Prog. Org. Coat., 77 (1) 176–183 (2014)CrossRefGoogle Scholar
  3. 3.
    Ishida, H, Allen, DJ, “Physical and Mechanical Characterization of Near-Zero Shrinkage Polybenzoxazines.” J. Polym. Sci. Part B Polym. Phys., 34 (6) 1019–1030 (1996)CrossRefGoogle Scholar
  4. 4.
    Arumugam, H, Krishnan, S, Chavali, M, Muthukaruppan, A, “Cardanol Based Benzoxazine Blends and Bio-silica Reinforced Composites: Thermal and Dielectric Properties.” New J. Chem., 42 (6) 4067–4080 (2018)CrossRefGoogle Scholar
  5. 5.
    Ariraman, M, Alagar, M, “Design of Lamellar Structured POSS/BPZ Polybenzoxazine Nanocomposites as a Novel Class of Ultra Low-k Dielectric Materials.” RSC Adv., 4 (37) 19127–19136 (2014)CrossRefGoogle Scholar
  6. 6.
    Ishida, H, Rodriguez, Y, “Curing Kinetics of a New Benzoxazine-Based Phenolic Resin by Differential Scanning Calorimetry.” Polymer, 36 (16) 3151–3158 (1995)CrossRefGoogle Scholar
  7. 7.
    Ghosh, NN, Kiskan, B, Yagci, Y, “Polybenzoxazines—New High Performance Thermosetting Resins: Synthesis and Properties.” Prog. Polym. Sci., 32 (11) 1344–1391 (2007)CrossRefGoogle Scholar
  8. 8.
    Dumas, L, Bonnaud, L, Olivier, M, Poorteman, M, Dubois, P, “Facile Preparation of a Novel High Performance Benzoxazine–CNT Based Nano-hybrid Network Exhibiting Outstanding Thermo-mechanical Properties.” Chem. Commun., 49 (83) 9543–9545 (2013)CrossRefGoogle Scholar
  9. 9.
    Huang, K, Zhang, Y, Li, M, Lian, J, Yang, X, Xia, J, “Preparation of a Light Color Cardanol-Based Curing Agent and Epoxy Resin Composite: Cure-Induced Phase Separation and Its Effect on Properties.” Prog. Org. Coat., 74 (1) 240–247 (2012)CrossRefGoogle Scholar
  10. 10.
    Sultania, M, Rai, JS, Srivastava, D, “Process Modeling, Optimization and Analysis of Esterification Reaction of Cashew Nut Shell Liquid (CNSL)-Derived Epoxy Resin Using Response Surface Methodology.” J. Hazard. Mater., 185 (2–3) 1198–1204 (2011)CrossRefGoogle Scholar
  11. 11.
    Ikeda, R, Tanaka, H, Uyama, H, Kobayashi, S, “Synthesis and Curing Behaviors of a Crosslinkable Polymer from Cashew Nut Shell Liquid.” Polymer, 43 (12) 3475–3481 (2002)CrossRefGoogle Scholar
  12. 12.
    Balgude, D, Sabnis, AS, “CNSL: An Environment Friendly Alternative for the Modern Coating Industry.” J. Coat. Technol. Res., 11 (2) 169–183 (2014)CrossRefGoogle Scholar
  13. 13.
    Xu, GM, Shi, T, Liu, J, Wang, Q, “Preparation of a Liquid Benzoxazine Based on Cardanol and the Thermal Stability of Its Graphene Oxide Composites.” J. Appl. Polym. Sci., 131 (11) 40353–40361 (2014)Google Scholar
  14. 14.
    Sethuraman, K, Alagar, M, “Thermo-mechanical and Dielectric Properties of Graphene Reinforced Caprolactam Cardanol Based Benzoxazine–Epoxy Nanocomposites.” RSC Adv., 5 (13) 9607–9617 (2014)CrossRefGoogle Scholar
  15. 15.
    Liu, L, Hu, JM, Leng, WH, Zhang, JQ, Cao, CN, “Novel Bis-silane/TiO2 Bifunctional Hybrid Films for Metal Corrosion Protection Both Under Ultraviolet Irradiation and in the Dark.” Scr. Mater., 57 (6) 549–552 (2007)CrossRefGoogle Scholar
  16. 16.
    Shen, GX, Chen, YC, Lin, CJ, “Corrosion Protection of 316 L Stainless Steel by a TiO2 Nanoparticle Coating Prepared by Sol–Gel Method.” Thin Solid Films, 489 (1–2) 130–136 (2005)CrossRefGoogle Scholar
  17. 17.
    Jalili, MM, Moradian, S, Dastmalchian, H, Karbasi, A, “Investigating the Variations in Properties of 2-Pack Polyurethane Clear Coat through Separate Incorporation of Hydrophilic and Hydrophobic Nano-silica.” Prog. Org. Coat., 59 (1) 81–87 (2007)CrossRefGoogle Scholar
  18. 18.
    Zhou, C, Lu, X, Xin, Z, Liu, J, Zhang, Y, “Polybenzoxazine/SiO2 Nanocomposite Coatings for Corrosion Protection of Mild Steel.” Corros. Sci., 80 269–275 (2014)CrossRefGoogle Scholar
  19. 19.
    Zhou, C, Lu, X, Xin, Z, Liu, J, “Corrosion Resistance of Novel Silane-Functional Polybenzoxazine Coating on Steel.” Corros. Sci., 70 145–151 (2013)CrossRefGoogle Scholar
  20. 20.
    Yang, LH, Liu, FC, Han, EH, “Effects of P/B on the Properties of Anticorrosive Coatings with Different Particle Size.” Prog. Org. Coat., 53 (2) 91–98 (2005)CrossRefGoogle Scholar
  21. 21.
    Ramezanzadeh, B, Attar, MM, “An Evaluation of the Corrosion Resistance and Adhesion Properties of an Epoxy-Nanocomposite on a Hot-Dip Galvanized Steel (HDG) Treated by Different Kinds of Conversion Coatings.” Surf. Coat. Technol., 205 (19) 4649–4657 (2011)CrossRefGoogle Scholar
  22. 22.
    Behzadnasab, M, Mirabedini, SM, Kabiri, K, Jamali, S, “Corrosion Performance of Epoxy Coatings Containing Silane Treated ZrO2 Nanoparticles on Mild Steel in 3.5% NaCl Solution.” Corros. Sci., 53 (1) 89–98 (2011)CrossRefGoogle Scholar
  23. 23.
    Dhoke, SK, Khanna, AS, “Effect of Nano-Fe2O3 Particles on the Corrosion Behavior of Alkyd Based Waterborne Coatings.” Corros. Sci., 51 (1) 6–20 (2009)CrossRefGoogle Scholar
  24. 24.
    Lakshmikandhan, T, Alagar, M, “Development and Characterization of Functionalized TiO2-Reinforced Schiff Base Epoxy Nanocomposites.” High Perform. Polym., 27 (7) 813–823 (2015)CrossRefGoogle Scholar
  25. 25.
    Selvaraj, V, Jayanthi, KP, Lakshmikandhan, T, Alagar, M, “Development of a Polybenzoxazine/TSBA-15 Composite from the Renewable Resource Cardanol for Low-k Applications.” RSC Adv., 5 (60) 48898–48907 (2015)CrossRefGoogle Scholar
  26. 26.
    Thiripuranthagan, S, Raj, D, Kannan, K, “Photocatalytic Degradation of Congored on Silica Supported Ag Impregnated TiO2.” J. Nanosci. Nanotechnol., 15 (6) 4727–4733 (2015)CrossRefGoogle Scholar
  27. 27.
    Riazian, M, Bahari, A, “Synthesis and Nanostructural Investigation of TiO2 Nanorods Doped by SiO2.” Pramana, 78 (2) 319–331 (2012)CrossRefGoogle Scholar
  28. 28.
    Zhang, X, Zheng, H, “Synthesis of TiO2-Doped SiO2 Composite Films and Its Applications.” Bull. Mater. Sci., 31 (5) 787–790 (2008)CrossRefGoogle Scholar
  29. 29.
    Rubab, Z, Afzal, A, Siddiqi, HM, Saeed, S, “Preparation, Characterization, and Enhanced Thermal and Mechanical Properties of Epoxy-Titania Composites.” Sci. World J., 1 1–7 (2014). CrossRefGoogle Scholar
  30. 30.
    Takeichi, T, Kawauchi, T, Agag, T, “High Performance Polybenzoxazines as a Novel Type of Phenolic Resin.” Polym. J., 40 (12) 1121–1131 (2008)CrossRefGoogle Scholar
  31. 31.
    Rajabi, L, Mohammadi, Z, Derakhshan, AA, “Thermal Stability and Dynamic Mechanical Properties of Nano and Micron-TiO2 Particles Reinforced Epoxy Composites: Effect of Mixing Method.” Iran. J. Chem. Eng., 10 16–29 (2013)Google Scholar
  32. 32.
    Liu, M, Guo, B, Du, M, Lei, Y, Jia, D, “Natural Inorganic Nanotubes Reinforced Epoxy Resin Nanocomposites.” J. Polym. Res., 15 (3) 205–212 (2008)CrossRefGoogle Scholar
  33. 33.
    Mandhakini, M, Lakshmikandhan, T, Chandramohan, A, Alagar, M, “Effect of Nanoalumina on the Tribology Performance of C4-Ether-Linked Bismaleimide-Toughened Epoxy Nanocomposites.” Tribol. Lett., 54 (1) 67–79 (2014)CrossRefGoogle Scholar
  34. 34.
    Fei, Z, Long, C, Qingyan, P, Shugao, Z, “Influence of Carbon Black on Crosslink Density of Natural Rubber.” J. Macromol. Sci. Part B Phys., 51 1208–1217 (2012)CrossRefGoogle Scholar
  35. 35.
    Xu, SH, Gu, J, Luo, YF, Jia, DM, “Effects of Partial Replacement of Silica with Surface Modified Nanocrystalline Cellulose on Properties of Natural Rubber Nanocomposites.” Express Polym. Lett., 6 (1) 14–25 (2012)CrossRefGoogle Scholar
  36. 36.
    Thirukumaran, P, Shakila Parveen, A, Sarojadevi, M, Kim, SC, “Replacing Bisphenol-A with Bisguaiacol-F to Synthesize Polybenzoxazines for Pollution-Free Environment.” New J. Chem., 40 9313–9319 (2016)CrossRefGoogle Scholar
  37. 37.
    Escobar, J, Poorteman, M, Dumas, L, Bonnaud, L, Dubois, P, Olivier, MG, “Thermal Curing Study of Bisphenol A Benzoxazine for Barrier Coating Applications on 1050 Aluminum Alloy.” Prog. Org. Coat., 79 53–61 (2015)CrossRefGoogle Scholar
  38. 38.
    Fina, A, Tabuani, D, Frache, A, Camino, G, “Polypropylene–Polyhedral Oligomeric Silsesquioxanes (POSS) Nanocomposites.” Polymer, 46 (19) 855–866 (2005)CrossRefGoogle Scholar

Copyright information

© American Coatings Association 2019

Authors and Affiliations

  1. 1.Department of ChemistryBharath Institute of Higher Education and ResearchSelaiyur, ChennaiIndia
  2. 2.Polymer Engineering LaboratoryPSG Institute of Technology and Applied ResearchNeelambur, CoimbatoreIndia
  3. 3.Polymer Composite Laboratory, Department of Chemical EngineeringAnna UniversityChennaiIndia

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