Journal of Materials Science

, Volume 54, Issue 6, pp 5101–5111 | Cite as

A comparative study on 3D printed silicone-epoxy/acrylate hybrid polymers via pure photopolymerization and dual-curing mechanisms

  • Tingting Zhao
  • Ran YuEmail author
  • Xinpan Li
  • Ying Zhang
  • Xin Yang
  • Xiaojuan Zhao
  • Wei HuangEmail author


A type of silicone-epoxy resin has been synthesized and compounded with acrylates to obtain hybrid inks for stereolithography 3D printing. Two approaches of printing have been developed: one approach is pure photopolymerization through the addition of free radical and cationic photoinitiators to the hybrid resin; the other approach untilizes a photo-thermal dual-curing system with free radical photoinitiator for acrylates and thermal curing agent for epoxy resin. The results of hardness, gel content, FTIR and SEM measurements show that both systems get highly crosslinked and interpenetrating polymer network structures, but with different extent of phase separation due to different curing processes. Thermalmechanical and mechanical tests demonstrate that 3D objects from the dual-curing system have higher glass transition temperatures, higher printing efficiency and much enhanced mechanical properties compared with these from the pure photopolymerization system. In addition, both of the systems get 3D objects with high printing accuracy and good thermal stability. The dual-curing mechanism, therefore, has distinct advantages over the pure photopolymerization method.



This study is financially supported by the National Natural Science Foundation of China (Nos. 51603208 and 51573189) and the National Key Research and Development Program of China (No. 2017YFB0404800).

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.


  1. 1.
    Eckel ZC, Zhou C, Martin JH, Jacobsen AJ, Carter WB, Schaedler TA (2016) 3D printing additive manufacturing of polymer-derived ceramics. Science 351(6268):58–62. Google Scholar
  2. 2.
    Martin JH, Yahata BD, Hundley JM, Mayer JA, Schaedler TA, Pollock TM (2017) 3D printing of high-strength aluminium alloys. Nature 549(7672):365–369. Google Scholar
  3. 3.
    Seitz H, Rieder W, Irsen S, Leukers B, Tille C (2005) Three-dimensional printing of porous ceramic scaffolds for bone tissue engineering. J Biomed Mater Res B 74B(2):782–788. Google Scholar
  4. 4.
    Choudhari CM, Patil VD (2016) Product development and its comparative analysis by SLA, SLS and FDM rapid prototyping processes. IOP Conf Ser Mater Sci Eng 149(1):012009Google Scholar
  5. 5.
    Gu DD, Meiners W, Wissenbach K, Poprawe R (2012) Laser additive manufacturing of metallic components: materials, processes and mechanisms. Int Mater Rev 57(3):133–164. Google Scholar
  6. 6.
    Zeng Y, Yan Y, Yan H, Liu C, Li P, Dong P, Zhao Y, Chen J (2018) 3D printing of hydroxyapatite scaffolds with good mechanical and biocompatible properties by digital light processing. J Mater Sci 53(9):6291–6301. Google Scholar
  7. 7.
    Karim MN, Afroj S, Rigout M, Yeates SG, Carr C (2015) Towards UV-curable inkjet printing of biodegradable poly (lactic acid) fabrics. J Mater Sci 50(13):4576–4585. Google Scholar
  8. 8.
    Ming L, Yang H, Zhang W, Zeng X, Xiong D, Xu Z, Wang H, Chen W, Xu X, Wang M, Duan J, Cheng Y-B, Zhang J, Bao Q, Wei Z, Yang S (2014) Selective laser sintering of TiO2 nanoparticle film on plastic conductive substrate for highly efficient flexible dye-sensitized solar cell application. J Mater Chem A 2(13):4566–4573. Google Scholar
  9. 9.
    Sandoval JH, Soto KF, Murr LE, Wicker RB (2007) Nanotailoring photocrosslinkable epoxy resins with multi-walled carbon nanotubes for stereolithography layered manufacturing. J Mater Sci 42(1):156–165. Google Scholar
  10. 10.
    Chakraborty P, Zhou C, Chung DDL (2018) Piezoelectric behavior of three-dimensionally printed acrylate polymer without filler or poling. J Mater Sci 53(9):6819–6830. Google Scholar
  11. 11.
    Lurie SA, Solyaev YO, Rabinskiy LN, Polyakov PO, Sevostianov I (2018) Mechanical behavior of porous Si3N4 ceramics manufactured with 3D printing technology. J Mater Sci 53(7):4796–4805. Google Scholar
  12. 12.
    Yang J, Jiao J, Wang L, Li B (2017) Spark plasma sintering of silicon carbide powders with carbon and boron as additives. In: Singh M, Ohji T, Dong S, Koch D, Shimamura K, Clauss B, Heidenreich B, Akedo J (eds) Advances in high temperature ceramic matrix compo sites and materials for sustainable development; ceramic transactions, vol CCLXIII. Wiley, New York, pp 137–143. Google Scholar
  13. 13.
    Chan V, Zorlutuna P, Jeong JH, Kong H, Bashir R (2010) Three-dimensional photopatterning of hydrogels using stereolithography for long-term cell encapsulation. Lab Chip 10(16):2062–2070. Google Scholar
  14. 14.
    Park S, Lee D-H, Ryoo H-I, Lim T-W, Yang D-Y, Kim D-P (2009) Fabrication of three-dimensional SiC ceramic microstructures with near-zero shrinkage via dual crosslinking induced stereolithography. Chem Commun 32:4880–4882. Google Scholar
  15. 15.
    Sinh LH, Harri K, Marjo L, Minna M, Luong ND, Jürgen W, Torsten W, Matthias S, Jukka S (2016) Novel photo-curable polyurethane resin for stereolithography. RSC Adv 6(56):50706–50709. Google Scholar
  16. 16.
    Yu R, Yang X, Zhang Y, Zhao X, Wu X, Zhao T, Zhao Y, Huang W (2017) Three-dimensional printing of shape memory composites with epoxy-acrylate hybrid photopolymer. ACS Appl Mater Interfaces 9(2):1820–1829. Google Scholar
  17. 17.
    Zhao TT, Li XP, Yu R, Zhang Y, Yang X, Zhao XJ, Wang L, Huang W (2018) Silicone-epoxy-based hybrid photopolymers for 3D printing. Macromol Chem Phys 219(10):10. Google Scholar
  18. 18.
    Winfield RJ, O’Brien S (2011) Two-photon polymerization of an epoxy-acrylate resin material system. Appl Surf Sci 257(12):5389–5392. Google Scholar
  19. 19.
    Putzien S, Louis E, Nuyken O, Crivello JV, Kuehn FE (2012) UV curing of epoxy functional hybrid silicones. J Appl Poly Sci 126(4):1188–1197. Google Scholar
  20. 20.
    Jang M, Crivello JV (2003) Synthesis and cationic photopolymerization of epoxy-functional siloxane monomers and oligomers. J Polym Sci Polym Chem 41(19):3056–3073. Google Scholar
  21. 21.
    Crivello JV, Song KY, Choshal R (2001) Synthesis and photoinitiated cationic polymerization of organic-inorganic hybrid resins. Chem Mater 13(5):1932–1942. Google Scholar
  22. 22.
    Crivello JV, Lee JL (1990) The synthesis, characterization, and photoinitiated cationic polymerization of silicon-containing epoxy-resins. J Polym Sci Polym Chem 28(3):479–503. Google Scholar
  23. 23.
    Crivello JV, Mao ZB (1997) Synthesis of novel multifunctional siloxane oligomers using sol-gel techniques and their photoinitiated cationic polymerization. Chem Mater 9(7):1554–1561. Google Scholar
  24. 24.
    Renault T, Ogale AA, Charan R, Bagchi A (1996) Selective reinforcement of photoresins with continuous fibers using 3-D composite photolithography. J Adv Mater 27(4):8–12Google Scholar
  25. 25.
    Baikerikar KK, Scranton AB (2001) Photopolymerizable liquid encapsulants for microelectronic devices. Polymer 42(2):431–441. Google Scholar
  26. 26.
    Gupta A, Ogale AA (2002) Dual curing of carbon fiber reinforced photoresins for rapid prototyping. Polym Compos 23(6):1162–1170. Google Scholar
  27. 27.
    Griffini G, Invernizzi M, Levi M, Natale G, Postiglione G, Turri S (2016) 3D-printable CFR polymer composites with dual-cure sequential IPNs. Polymer 91:174–179. Google Scholar
  28. 28.
    Invernizzi M, Natale G, Levi M, Turri S, Griffini G (2016) UV-assisted 3D printing of glass and carbon fiber-reinforced dual-cure polymer composites. Materials. Google Scholar
  29. 29.
    Chen K, Kuang X, Li V, Kang G, Qi HJ (2018) Fabrication of tough epoxy with shape memory effects by UV-assisted direct-ink write printing. Soft Matter 14(10):1879–1886. Google Scholar
  30. 30.
    Kuang X, Zhao Z, Chen K, Fang D, Kang G, Qi HJ (2018) High-speed 3D printing of high-performance thermosetting polymers via two-stage curing. Macromol Rapid Commun 1700809:1–8. Google Scholar
  31. 31.
    Decker C (2002) Kinetic study and new applications of UV radiation curing. Macromol Rapid Commun 23(18):1067–1093. Google Scholar
  32. 32.
    Tsujimoto T, Ohta E, Uyama H (2015) Plant oil-based shape memory polymer using acrylic monolith. Express Polym Lett 9(9):757–763. Google Scholar
  33. 33.
    Ligon-Auer SC, Schwentenwein M, Gorsche C, Stampfl J, Liska R (2016) Toughening of photo-curable polymer networks: a review. Polym Chem 7(2):257–286. Google Scholar

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Authors and Affiliations

  1. 1.Institute of ChemistryChinese Academy of SciencesBeijingPeople’s Republic of China
  2. 2.University of Chinese Academy of SciencesBeijingPeople’s Republic of China

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