Improved thermal stability of methylsilicone resins by compositing with N-doped graphene oxide/Co3O4 nanoparticles

Research Paper


Nanoparticles play important roles in enhancing the thermal-resistance of hosting polymer resins. Despite tremendous efforts, developing thermally stable methylsilicone resin at high temperatures is still a challenge. Herein, we report a strategy to increase the activation energy to slow down the decomposition/degradation of methylsilicone resin using synergistic effects between the Co3O4 nanoparticles and the nitrogen doped graphene oxide. The N-doped graphene oxides composited with Co3O4 nanoparticles were prepared by hydrolysis of cobalt nitrate hexahydrate in the presence of graphene oxide and were incorporated into the methylsilicone resin. Two-stage decompositions were observed, i.e., 200–300 and 400–500 °C. The activation energy for the low temperature region was enhanced by 47.117 kJ/mol (vs. 57.76 kJ/mol for pure resin). The enhanced thermal stability was due to the fact that the nanofillers prevented the silicone hydroxyl chain ends ‘‘biting’’ to delay the degradation. The activation energy for high-temperature region was enhanced by 11.585 kJ/mol (vs. 171.95 kJ/mol for pure resin). The nanofillers formed a protective layer to isolate oxygen from the hosting resin. The mechanism for the enhanced thermal stability through prohibited degradation with synergism of these nitrogen-doped graphene oxide nanocomposites was proposed as well.

Graphical Abstract


Methylsilicone resin N-doped graphene oxide Co3O4 nanoparticles Activity energy Synergy effect Nanocomposite materials 



The authors acknowledge financial support from National Science Foundation of China (Grant No. 50903025), Fundamental Research Funds for the Central Universities (Grant No. HIT NSRIF 2013046, HIT.IBRSEM.201318) of China. Z. Guo appreciates the start-up fund from University of Tennessee.


  1. Anderson SE, Mitchell C, Haddad TS, Vij A, Schwab JJ, Bowers MT (2006) Structural characterization of POSS siloxane dimer and trimer. Chem Mater 18:1490–1497CrossRefGoogle Scholar
  2. Fang W, Zeng X, Lai X, Li H, Chen W, Zhang Y (2015) Thermal degradation mechanism of addition-cure liquid silicone rubber with urea-containing silane. Thermochim Acta 605:28–36CrossRefGoogle Scholar
  3. Fei H, Dong J, Arellano-Jiménez MJ, Ye G, Kim ND, Samuel EL, Yacaman MJ (2015) Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat Commun 6:8668–8868CrossRefGoogle Scholar
  4. Gan Y, Jiang X, Yin J (2014) Thiol–ene photo-curable hybrid silicone resin for LED encapsulation: enhancement of light extraction efficiency by facile self-keeping hemisphere coating. J Mater Chem C 28:5533–5539CrossRefGoogle Scholar
  5. He T, Chen D, Jiao X (2004) Controlled synthesis of Co3O4 nanoparticles through oriented aggregation. Chem Mater 16:737–743CrossRefGoogle Scholar
  6. Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339CrossRefGoogle Scholar
  7. Iso Y, Takeshita S, Isobe T (2014) Electrophoretic deposition and characterization of transparent nanocomposite films of YVO4: Bi3+, Eu3+ nanophosphor and silicone-modified acrylic resin. Langmuir 30:1465–1471CrossRefGoogle Scholar
  8. Ito Y, Cong W, Fujita T, Tang Z, Chen M (2015) High catalytic activity of nitrogen and sulfur Co-doped nanoporous graphene in the hydrogen evolution reaction. Angew Chem Int Ed 54:2131–2136CrossRefGoogle Scholar
  9. Lee JK, Char K, Rhee HW, Ro HW, Yoo DY, Yoon DY (2001) Synthetic control of molecular weight and microstructure of processible poly (methylsilsesquioxane) s for low-dielectric thin film applications. Polymer 42:9085–9089CrossRefGoogle Scholar
  10. Liu YR, Huang YD, Liu L (2006) Effects of TriSilanolIsobutyl-POSS on thermal stability of methylsilicone resin. Polym Degrad Stabil 91:2731–2738CrossRefGoogle Scholar
  11. Liu YR, Huang YD, Liu L (2007) Thermal stability of POSS/methylsilicone nanocomposites. Compos Sci Tech 67:2864–2876CrossRefGoogle Scholar
  12. Ma CY, Mu Z, Li JJ, Jin YG, Cheng J, Lu GQ, Qiao SZ (2010) Mesoporous Co3O4 and Au/Co3O4 catalysts for low-temperature oxidation of trace ethylene. J Am Chem Soc 132:2608–2613CrossRefGoogle Scholar
  13. Mutin PH (1999) Control of the composition and structure of silicon oxycarbide and oxynitride glasses derived from polysiloxane precursors. J Sol-Gel Sci Technol 14:27–38CrossRefGoogle Scholar
  14. Naveen AN, Manimaran P, Selladurai S (2015) Cobalt oxide (Co3O4)/graphene nanosheets (GNS) composite prepared by novel route for supercapacitor application. J Mater Sci 26:8988–9000Google Scholar
  15. Nie RF, Shi JJ, Du WC, Ning WS, Hou ZY, Xiao FS (2013) A sandwich N-doped graphene/Co3O4 hybrid: an efficient catalyst for selective oxidation of olefins and alcohols. J Mater Chem A 1:9037–9045CrossRefGoogle Scholar
  16. Pradhan B, Roy S, Srivastava SK, Saxena A (2015) Synergistic effect of carbon nanotubes and clay platelets in reinforcing properties of silicone rubber nanocomposites. J Appl Polym Sci 132:41818CrossRefGoogle Scholar
  17. Qing Y, Zhou W, Luo F, Zhu D (2010) Epoxy-silicone filled with multi-walled carbon nanotubes and carbonyl iron particles as a microwave absorber. Carbon 48:4074–4080CrossRefGoogle Scholar
  18. Sahoo S, Bae SH, Lee YS, Lee JM, Ahn JM, Kim CG, Oh IK (2015) Defect-engineered mesoporous ternary nanoarchitecture of zinc-cobalt-oxide/nitrogen-doped graphene as anode material in lithium ion batteries. Carbon 94:455–463CrossRefGoogle Scholar
  19. Schmidt DF, Giannelis EP (2009) Silicate dispersion and mechanical reinforcement in polysiloxane/layered silicate nanocomposites. Chem Mater 22:167–174CrossRefGoogle Scholar
  20. Sun JT, Huang YD, Gong GF, Cao HL (2006) Thermal degradation kinetics of poly (methylphenylsiloxane) containing methacryloyl groups. Polym Degrad Stabil 91:339–346CrossRefGoogle Scholar
  21. Suryanto BHR, Lu X, Zhao C (2013) Layer-by-layer assembly of transparent amorphous Co3O4 nanoparticles/graphene composite electrodes for sustained oxygen evolution reaction. J Mater Chem A 1:12726–12731CrossRefGoogle Scholar
  22. Susanta KB, Nikhil RJ (2014) Reduced graphene oxide-silver nanoparticle composite as visible light photocatalyst for degradation of colorless endocrine disruptors. ACS Appl Mater Interfaces 6:20085–20092CrossRefGoogle Scholar
  23. Tamura K, Yokoyama S, Pascua CS, Yamada H (2008) New age of polymer nanocomposites containing dispersed high-aspect-ratio silicate nanolayers. Chem Mater 20:2242–2246CrossRefGoogle Scholar
  24. Tang CW, Wang CB, Chien SH (2008) Characterization of cobalt oxides studied by FT-IR, Raman, TPR and TG-MS. Thermochim Acta 473:68–73CrossRefGoogle Scholar
  25. Verdejo R, Barroso-Bujans F, AngeláRodriguez-Perez M, de Saja JA, AngeláLopez-Manchado M (2008) Functionalized graphene sheet filled silicone foam nanocomposites. J Mater Chem 18:2221–2226CrossRefGoogle Scholar
  26. Weickmann H, Gurr M, Meincke O, Thomann R, Mülhaupt R (2010) A versatile solvent-free “one-pot” route to polymer nanocomposites and the in situ formation of calcium phosphate/layered silicate hybrid nanoparticles. Adv Funct Mater 20:1778–1786CrossRefGoogle Scholar
  27. Xu C, Wang X, Zhu J, Yang X, Lu L (2008) Deposition of Co3O4 nanoparticles onto exfoliated graphite oxide sheets. J Mater Chem 18:5625–5629CrossRefGoogle Scholar
  28. Yang Y, Li WN, Luo YS, Xiao HM, Fu SY, Mai YW (2010) Novel ultraviolet-opaque, visible-transparent and light-emitting ZnO-QD/silicone composites with tunable luminescence colors. Polymer 51:2755–2762CrossRefGoogle Scholar
  29. Yoon C, Kim T, Shin MH, Song YG, Shin K, Kim YJ, Lee K (2015) Highly luminescent and stable white light-emitting diodes created by direct incorporation of Cd-free quantum dots in silicone resin using the thiol group. J Mater Chem C 3:6908–6915CrossRefGoogle Scholar
  30. Yu Q, Xu J, Wan C, Wu C, Guan L (2015) Porous cobalt–nitrogen-doped hollow graphene spheres as a superior electrocatalyst for enhanced oxygen reduction in both alkaline and acidic solutions. J Mater Chem A 3:16419–16423CrossRefGoogle Scholar
  31. Yuan C, Yang L, Hou L, Li J, Sun Y, Zhang X, Lou XWD (2012) Flexible hybrid paper made of monolayer Co3O4 microsphere arrays on rGO/CNTs and their application in electrochemical capacitors. Adv Funct Mater 22:2560–2566CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  • Bo Jiang
    • 1
  • Liwei Zhao
    • 1
  • Jiang Guo
    • 2
  • Xingru Yan
    • 2
  • Daowei Ding
    • 2
  • Changcheng Zhu
    • 1
  • Yudong Huang
    • 1
  • Zhanhu Guo
    • 2
  1. 1.Polymer Materials and Engineering DepartmentHarbin Institute of TechnologyHarbinPeople’s Republic of China
  2. 2.Integrated Composites Laboratory (ICL) Department of Chemical and Biomolecular EngineeringUniversity of TennesseeKnoxvilleUSA

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