This study aims to improve the thermal and mechanical properties of epoxy-based materials. For this purpose, the structure of epoxy resins was changed by chemical modification and epoxy resin containing urethane was synthesized. The synthesized resin was blended with commercial epoxy resin at the ratios of 25%, 50%, 75% by weight and hardened by curing. The thermal and mechanical properties of urethane-containing epoxy materials prepared in different proportions were compared with those produced from commercial epoxy resin. The structural characterization of the prepared materials was investigated by Fourier Transform Infrared Spectroscopy (FTIR) analysis, their thermal behavior was investigated by Thermogravimetric Analysis (TGA), and their mechanical properties were investigated by Dynamic Mechanical Analysis (DMA). TGA and DMA analyses of the materials showed that the presence of urethane in the structure of epoxy resins significantly changed the mechanical and thermal properties. It was observed that the storage and loss modulus values of urethane-containing resins increased approximately 2.5 times compared to commercial epoxy resins, and a decrease of approximately 10% in thermal degradation temperatures was observed.
Scientific Research Projects Coordination Unit of Istanbul University-Cerrahpasa
Proje Numarası
56922
Teşekkür
The authors would like to thank Prof. Dr. Ali Durmuş and Assoc. Prof. Dr. Alper Kaşgöz for their assistance in DMA analysis.
Kaynakça
Akovali, G. (2001). Handbook of Composite Fabrication. Smithers Rapra Publishing. https://books.google.com.tr/books?id=klcCAAAACAAJ
Anand Prabu, A., & Alagar, M. (2004). Mechanical and electrical studies of silicone modified polyurethane-epoxy intercrosslinked networks. Polymer Journal, 36(10), 848–855. https://doi.org/10.1295/polymj.36.848
Barcia, F. L., Amaral, T. P., & Soares, B. G. (2003). Synthesis and properties of epoxy resin modified with epoxy-terminated liquid polybutadiene. Polymer, 44(19), 5811–5819. https://doi.org/10.1016/S0032-3861(03)00537-8
Basnet, S., Otsuka, M., Sasaki, C., Asada, C., & Nakamura, Y. (2015). Functionalization of the active ingredients of Japanese green tea (Camellia sinensis) for the synthesis of bio-based epoxy resin. Industrial Crops and Products, 73, 63–72. https://doi.org/10.1016/j.indcrop.2015.03.091
Chen, K., Tian, C., Liang, S., Zhao, X., & Wang, X. (2018). Effect of stoichiometry on the thermal stability and flame retardation of polyisocyanurate foams modified with epoxy resin. Polymer Degradation and Stability, 150, 105–113. https://doi.org/10.1016/j.polymdegradstab.2018.02.015
Dağ, M. (2023). Obtaining Diatomite Reinforced Epoxy Composite and Determination of Its Thermophysical Properties. Journal of the Turkish Chemical Society Section B: Chemical Engineering, 6(1), 9–16. https://doi.org/10.58692/jotcsb.1174746
Demčenko, A., Koissin, V., & Korneev, V. A. (2014). Noncollinear wave mixing for measurement of dynamic processes in polymers: Physical ageing in thermoplastics and epoxy cure. Ultrasonics, 54(2), 684–693. https://doi.org/10.1016/j.ultras.2013.09.011
Dhevi, D. M., Prabu, A. A., Kim, H., Pathak, M. (2014). Studies on the toughening of epoxy resin modified with varying hyperbranched polyester-toluene diisocyanate content. Journal of Polymer Research, 21, Art.no. 503, https://doi.org/10.1007/s10965-014-0503-7.
Ellis, B. (Ed.). (1993). Chemistry and Technology of Epoxy Resins. Springer Netherlands. https://doi.org/10.1007/978-94-011-2932-9
Garcia, F. G., Soares, B. G., Pita, V. J. R. R., Sánchez, R., & Rieumont, J. (2007). Mechanical properties of epoxy networks based on DGEBA and aliphatic amines. Journal of Applied Polymer Science, 106(3), 2047–2055. https://doi.org/10.1002/app.24895
Hsieh, K. H., Han, J. L., Yu, C. T., & Fu, S. C. (2001). Graft interpenetrating polymer networks of urethane-modified bismaleimide and epoxy (I): Mechanical behavior and morphology. Polymer, 42(6), 2491–2500. https://doi.org/10.1016/S0032-3861(00)00641-8
Hsieh, T. H., Kinloch, A. J., Masania, K., Sohn Lee, J., Taylor, A. C., & Sprenger, S. (2010). The toughness of epoxy polymers and fibre composites modified with rubber microparticles and silica nanoparticles. Journal of Materials Science, 45(5), 1193–1210. https://doi.org/10.1007/s10853-009-4064-9
Huang, P., Zheng, S., Huang, J., Guo, Q., & Zhu, W. (1997). Miscibility and mechanical properties of epoxy resin/polysulfone blends. Polymer, 38(22), 5565–5571. https://doi.org/10.1016/S0032-3861(97)00104-3
Jiang, W., Jin, F.-L., & Park, S.-J. (2012). Thermo-mechanical behaviors of epoxy resins reinforced with nano-Al2O3 particles. Journal of Industrial and Engineering Chemistry, 18(2), 594–596. https://doi.org/10.1016/j.jiec.2011.11.140
Jin, F.-L., Liu, H.-C., Yang, B., & Park, S.-J. (2015). Synthesis and thermal properties of urethane-containing epoxy resin. Journal of Industrial and Engineering Chemistry, 24, 20–23. https://doi.org/10.1016/j.jiec.2014.10.006
Jin, F.-L., & Park, S.-J. (2008). Interfacial toughness properties of trifunctional epoxy resins/calcium carbonate nanocomposites. Materials Science and Engineering: A, 475(1–2), 190–193. https://doi.org/10.1016/j.msea.2007.04.046
Kirillov, A. N. (2014). Epoxy-urethane binders based on the blocked isocyanate Desmocap 11. Polymer Science Series D, 7(1), 14–18. https://doi.org/10.1134/S1995421214010079
Kricheldorf, H. R.; Nuyken, O.; Swift, G. (Ed.). (2004). Handbook of Polymer Synthesis. CRC Press.
Kunz, S. C., & Beaumont, P. W. R. (1981). Low-temperature behaviour of epoxy-rubber particulate composites. Journal of Materials Science, 16(11), 3141–3152. https://doi.org/10.1007/BF00540323
Lee, M., Kwon, W., Kwon, D., Lee, E., & Jeong, E. (2019). Fracture toughness of the novel in-situ polytriazolesulfone modified epoxy resin for carbon fiber/epoxy composites. Journal of Industrial and Engineering Chemistry, 77, 461–469. https://doi.org/10.1016/j.jiec.2019.05.012
Levita, G., Marchetti, A., & Butta, E. (1985). Influence of the temperature of cure on the mechanical properties of ATBN/epoxy blends. Polymer, 26(7), 1110–1116. https://doi.org/https://doi.org/10.1016/0032-3861(85)90238-1
May, C. (2018). Epoxy resins: chemistry and technology. Routledge.
Paul Swaraj. (1995). Surface Coatings Science Technology (2nd ed.). Wiley.
Prabu, A. A., & Alagar, M. (2004). Mechanical and thermal studies of intercross-linked networks based on siliconized polyurethane-epoxy/unsaturated polyester coatings. Progress in Organic Coatings, 49(3), 236–243. https://doi.org/10.1016/j.porgcoat.2003.09.018
Ramos, V. D., da Costa, H. M., Soares, V. L. P., & Nascimento, R. S. V. (2005). Modification of epoxy resin: a comparison of different types of elastomer. Polymer Testing, 24(3), 387–394. https://doi.org/10.1016/j.polymertesting.2004.09.010
Rath, S. K., Chavan, J. G., Sasane, S., Srivastava, A., Patri, M., Samui, A. B., Chakraborty, B. C., & Sawant, S. N. (2009). Coatings of PDMS-modified epoxy via urethane linkage: Segmental correlation length, phase morphology, thermomechanical and surface behavior. Progress in Organic Coatings, 65(3), 366–374. https://doi.org/10.1016/j.porgcoat.2009.02.007
Socrates, G. (2001). Infrared and Raman characteristic group frequencies. Tables and charts.
Stefani, P. M., Moschiar, S. M., & Aranguren, M. I. (2001). Epoxy-urethane copolymers: Relation between morphology and properties. Journal of Applied Polymer Science, 82(10), 2544–2552. https://doi.org/10.1002/app.2105
Wazarkar, K., Kathalewar, M., & Sabnis, A. (2016). Development of epoxy-urethane hybrid coatings via non-isocyanate route. European Polymer Journal, 84, 812–827. https://doi.org/10.1016/j.eurpolymj.2016.10.021
Yang, K., & Gu, M. (2009). Fabrication, morphology and cure behavior of triethylenetetramine-grafted multiwalled carbon nanotube/epoxy nanocomposites. Polymer Journal, 41(9), 752–763. https://doi.org/10.1295/polymj.PJ2009064
Zhou, S., Yang, C., Hu, J., He, X., & Zhang, R. (2018). Damping analysis of some inorganic particles on poly(butyl-methacrylate). Materials, 11(6), 1–12. https://doi.org/10.3390/ma11060992
Akovali, G. (2001). Handbook of Composite Fabrication. Smithers Rapra Publishing. https://books.google.com.tr/books?id=klcCAAAACAAJ
Anand Prabu, A., & Alagar, M. (2004). Mechanical and electrical studies of silicone modified polyurethane-epoxy intercrosslinked networks. Polymer Journal, 36(10), 848–855. https://doi.org/10.1295/polymj.36.848
Barcia, F. L., Amaral, T. P., & Soares, B. G. (2003). Synthesis and properties of epoxy resin modified with epoxy-terminated liquid polybutadiene. Polymer, 44(19), 5811–5819. https://doi.org/10.1016/S0032-3861(03)00537-8
Basnet, S., Otsuka, M., Sasaki, C., Asada, C., & Nakamura, Y. (2015). Functionalization of the active ingredients of Japanese green tea (Camellia sinensis) for the synthesis of bio-based epoxy resin. Industrial Crops and Products, 73, 63–72. https://doi.org/10.1016/j.indcrop.2015.03.091
Chen, K., Tian, C., Liang, S., Zhao, X., & Wang, X. (2018). Effect of stoichiometry on the thermal stability and flame retardation of polyisocyanurate foams modified with epoxy resin. Polymer Degradation and Stability, 150, 105–113. https://doi.org/10.1016/j.polymdegradstab.2018.02.015
Dağ, M. (2023). Obtaining Diatomite Reinforced Epoxy Composite and Determination of Its Thermophysical Properties. Journal of the Turkish Chemical Society Section B: Chemical Engineering, 6(1), 9–16. https://doi.org/10.58692/jotcsb.1174746
Demčenko, A., Koissin, V., & Korneev, V. A. (2014). Noncollinear wave mixing for measurement of dynamic processes in polymers: Physical ageing in thermoplastics and epoxy cure. Ultrasonics, 54(2), 684–693. https://doi.org/10.1016/j.ultras.2013.09.011
Dhevi, D. M., Prabu, A. A., Kim, H., Pathak, M. (2014). Studies on the toughening of epoxy resin modified with varying hyperbranched polyester-toluene diisocyanate content. Journal of Polymer Research, 21, Art.no. 503, https://doi.org/10.1007/s10965-014-0503-7.
Ellis, B. (Ed.). (1993). Chemistry and Technology of Epoxy Resins. Springer Netherlands. https://doi.org/10.1007/978-94-011-2932-9
Garcia, F. G., Soares, B. G., Pita, V. J. R. R., Sánchez, R., & Rieumont, J. (2007). Mechanical properties of epoxy networks based on DGEBA and aliphatic amines. Journal of Applied Polymer Science, 106(3), 2047–2055. https://doi.org/10.1002/app.24895
Hsieh, K. H., Han, J. L., Yu, C. T., & Fu, S. C. (2001). Graft interpenetrating polymer networks of urethane-modified bismaleimide and epoxy (I): Mechanical behavior and morphology. Polymer, 42(6), 2491–2500. https://doi.org/10.1016/S0032-3861(00)00641-8
Hsieh, T. H., Kinloch, A. J., Masania, K., Sohn Lee, J., Taylor, A. C., & Sprenger, S. (2010). The toughness of epoxy polymers and fibre composites modified with rubber microparticles and silica nanoparticles. Journal of Materials Science, 45(5), 1193–1210. https://doi.org/10.1007/s10853-009-4064-9
Huang, P., Zheng, S., Huang, J., Guo, Q., & Zhu, W. (1997). Miscibility and mechanical properties of epoxy resin/polysulfone blends. Polymer, 38(22), 5565–5571. https://doi.org/10.1016/S0032-3861(97)00104-3
Jiang, W., Jin, F.-L., & Park, S.-J. (2012). Thermo-mechanical behaviors of epoxy resins reinforced with nano-Al2O3 particles. Journal of Industrial and Engineering Chemistry, 18(2), 594–596. https://doi.org/10.1016/j.jiec.2011.11.140
Jin, F.-L., Liu, H.-C., Yang, B., & Park, S.-J. (2015). Synthesis and thermal properties of urethane-containing epoxy resin. Journal of Industrial and Engineering Chemistry, 24, 20–23. https://doi.org/10.1016/j.jiec.2014.10.006
Jin, F.-L., & Park, S.-J. (2008). Interfacial toughness properties of trifunctional epoxy resins/calcium carbonate nanocomposites. Materials Science and Engineering: A, 475(1–2), 190–193. https://doi.org/10.1016/j.msea.2007.04.046
Kirillov, A. N. (2014). Epoxy-urethane binders based on the blocked isocyanate Desmocap 11. Polymer Science Series D, 7(1), 14–18. https://doi.org/10.1134/S1995421214010079
Kricheldorf, H. R.; Nuyken, O.; Swift, G. (Ed.). (2004). Handbook of Polymer Synthesis. CRC Press.
Kunz, S. C., & Beaumont, P. W. R. (1981). Low-temperature behaviour of epoxy-rubber particulate composites. Journal of Materials Science, 16(11), 3141–3152. https://doi.org/10.1007/BF00540323
Lee, M., Kwon, W., Kwon, D., Lee, E., & Jeong, E. (2019). Fracture toughness of the novel in-situ polytriazolesulfone modified epoxy resin for carbon fiber/epoxy composites. Journal of Industrial and Engineering Chemistry, 77, 461–469. https://doi.org/10.1016/j.jiec.2019.05.012
Levita, G., Marchetti, A., & Butta, E. (1985). Influence of the temperature of cure on the mechanical properties of ATBN/epoxy blends. Polymer, 26(7), 1110–1116. https://doi.org/https://doi.org/10.1016/0032-3861(85)90238-1
May, C. (2018). Epoxy resins: chemistry and technology. Routledge.
Paul Swaraj. (1995). Surface Coatings Science Technology (2nd ed.). Wiley.
Prabu, A. A., & Alagar, M. (2004). Mechanical and thermal studies of intercross-linked networks based on siliconized polyurethane-epoxy/unsaturated polyester coatings. Progress in Organic Coatings, 49(3), 236–243. https://doi.org/10.1016/j.porgcoat.2003.09.018
Ramos, V. D., da Costa, H. M., Soares, V. L. P., & Nascimento, R. S. V. (2005). Modification of epoxy resin: a comparison of different types of elastomer. Polymer Testing, 24(3), 387–394. https://doi.org/10.1016/j.polymertesting.2004.09.010
Rath, S. K., Chavan, J. G., Sasane, S., Srivastava, A., Patri, M., Samui, A. B., Chakraborty, B. C., & Sawant, S. N. (2009). Coatings of PDMS-modified epoxy via urethane linkage: Segmental correlation length, phase morphology, thermomechanical and surface behavior. Progress in Organic Coatings, 65(3), 366–374. https://doi.org/10.1016/j.porgcoat.2009.02.007
Socrates, G. (2001). Infrared and Raman characteristic group frequencies. Tables and charts.
Stefani, P. M., Moschiar, S. M., & Aranguren, M. I. (2001). Epoxy-urethane copolymers: Relation between morphology and properties. Journal of Applied Polymer Science, 82(10), 2544–2552. https://doi.org/10.1002/app.2105
Wazarkar, K., Kathalewar, M., & Sabnis, A. (2016). Development of epoxy-urethane hybrid coatings via non-isocyanate route. European Polymer Journal, 84, 812–827. https://doi.org/10.1016/j.eurpolymj.2016.10.021
Yang, K., & Gu, M. (2009). Fabrication, morphology and cure behavior of triethylenetetramine-grafted multiwalled carbon nanotube/epoxy nanocomposites. Polymer Journal, 41(9), 752–763. https://doi.org/10.1295/polymj.PJ2009064
Zhou, S., Yang, C., Hu, J., He, X., & Zhang, R. (2018). Damping analysis of some inorganic particles on poly(butyl-methacrylate). Materials, 11(6), 1–12. https://doi.org/10.3390/ma11060992
Yüksel, O., Yıldırım, E., Yücel, O., Emik, S. (2023). Synthesis and Investigation of Thermal and Dynamic Mechanical Properties of Urethane-Containing Epoxy Resins. Journal of the Turkish Chemical Society Section B: Chemical Engineering, 6(2), 95-106. https://doi.org/10.58692/jotcsb.1309480