Skip to main content
Log in

Surface functionalized carbon nanotubes and its effects on the mechanical properties of epoxy based composites at cryogenic temperature

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

Epoxies have a wide range of applications in fuel tank fabrication, aerospace, electrical, electronic, and automobile industries. However, these resins are quite brittle, showing poor mechanical performance, especially at cryogenic temperature. The properties of functionalized multi-walled carbon nanotube (MWCNTs)-reinforced epoxy composites were investigated to develop advanced composites for cryogenic use. Two methods were adopted to modify MWCNTs. MWCNTs were first treated by acid mixture, and then maleic anhydride (MA) and isophorone diisocyanate (IPDI) grafting was carried out. At last, the functionalized MWCNTs were integrated into epoxy to prepare MWCNT-reinforced epoxy composites. Raman and XPS analysis proved the effectiveness of acid mixture treatment and confirmed the grafting reaction of MA and IPDI with MWCNTs. TEM analysis indicated that MA and IPDI had been grafted onto the surface of MWCNTs and formed a thin layer. The tensile strength, Young’s modulus, and impact strength of composites at liquid nitrogen temperature (77 K) are all enhanced by the addition of MWCNTs. Results of dynamic mechanical analysis indicated that introducing a small amount of functionalized MWCNTs to epoxy can enhance their storage modulus at 77 K and glass-transition temperature of composites. The results indicated that surface modified MWCNTs can be effectively utilized to enhance the properties of epoxy-based composites at cryogenic temperature.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13

Similar content being viewed by others

References

  1. Shanmugharaj AM, Choi WS, Ryu SH (2011) Physical properties of phenol-anchored multiwall carbon nanotube/epoxy nanocomposite. Polym Bull 67:1721–1730

    Article  CAS  Google Scholar 

  2. Heydenreich R (1998) Cryotanks in future vehicles. Cryogenics 8:125–130

    Article  Google Scholar 

  3. Kong KTS, Mariatti M, Rashid AA, Busfield JJC (2012) Effect of processing methods and functional groups on the properties of multi-walled carbon nanotube filled poly(dimethyl siloxane) composites. Polym Bull 69:937–953

    Article  CAS  Google Scholar 

  4. Wang SR, Liang ZY, Gonnet P, Liao YH, Wang B, Zhang C (2007) Effect of nanotube functionalization on the coefficient of thermal expansion of nanocomposites. Adv Funct Mater 17(1):87–92

    Article  CAS  Google Scholar 

  5. Bechel VT, Camping JD, Kim RY (2005) Cryogenic/elevated temperature cycling induced leakage paths in PMCs. Compos Part B 36:171–182

    Article  Google Scholar 

  6. Kim JK, Baillie C, Poh J, Mai YW (1992) Fracture toughness of CFRP with modified epoxy matrices. Compos Sci Technol 43:283–297

    Article  CAS  Google Scholar 

  7. Yu MF, Lourie O, Dyer MJ, Moloni K, Kelly TF, Ruoff RS (2000) Strength and breaking mechanism of multiwalled carbon nanotubes under tensile load. Science 287:637–640

    Article  CAS  Google Scholar 

  8. Li C, Chou TW (2003) Elastic moduli of muti-walled carbon nanotubes and the effect of van der Waals forces. Compos Sci Technol 63:1517–1524

    Article  CAS  Google Scholar 

  9. Jin ZX, Pramoda KP, Xu GQ, Goh SH (2001) Dynamic mechanical behavior of melt-processed multi-walled carbon nanotube/poly(methyl methacrylate) composites. Chem Phys Lett 337:43–47

    Article  CAS  Google Scholar 

  10. Cooper CA, Ravich D, Lips D, Mayer J, Wagner HD (2002) Distribution and alignment of carbon nanotubes and nanofibrils in a polymer matrix. Compos Sci Technol 62:1105–1112

    Article  CAS  Google Scholar 

  11. Xu XJ, Thwe MM, Shearwood C, Liao K (2002) Mechanical properties and interfacial characteristics of carbon-nanotube-reinforced epoxy thin films. Appl Phys Lett 81:2833–2835

    Article  CAS  Google Scholar 

  12. Yang JP, Chen ZK, Feng QP, Deng YH, Liu Y, Ni QQ (2012) Cryogenic mechanical behaviors of carbon nanotube reinforced composites based on modified epoxy by poly(ethersulfone). Compos B 43:22–26

    Article  CAS  Google Scholar 

  13. Chen ZK, Yang JP, Ni QQ, Fu SY, Huang YG (2009) Reinforcement of epoxy resins with multi-walled carbon nanotubes for enhancing cryogenic mechanical properties. Polymer 50:4753–4759

    Article  CAS  Google Scholar 

  14. Seok IY, Victor L, Johannes N, Joel D, Robert AR (2010) Morphology of composite particles of single wall carbon nanotubes/biodegradable polyhydroxyalkanoates prepared by spray drying. Polym Bull 64:99–106

    Article  Google Scholar 

  15. Wang S, Liang Z, Liu T, Wang B, Zhang C (2006) Effective amino-functionalization of carbon nanotubes for reinforcing epoxy polymer composites. Nanotechnology 17:1551–1557

    Article  CAS  Google Scholar 

  16. Geng HZ, Rosen R, Zheng B, Shimoda H, Fleming L, Liu J (2002) Fabrication and properties of composites of poly(ethylene oxide) and functionalized carbon nanotubes. Adv Mater 14:1387–1390

    Article  CAS  Google Scholar 

  17. Wang M, Pramonda KP, Goh SH (2005) Enhancement of the mechanical properties of poly(styrene-co-acrylonitrile) with poly(methyl methacrylate)-grafted multiwalled carbon nanotubes. Polymer 46:11510–11516

    Article  CAS  Google Scholar 

  18. Paiva MC, Zhou B, Fernando KA, Lin Y, Kennedy JM, Sun YP (2004) Mechanical and morphological characterization of polymer–carbon nanocomposites from functionalized carbon nanotubes. Carbon 42:2849–2854

    Article  CAS  Google Scholar 

  19. Zhu J, Peng HQ, Rodriguez-Macias F, Margrave JL, Khabashesku VN, Imam AM (2004) Reinforcing epoxy polymer composites through covalent integration of functionalized nanotubes. Adv Funct Mater 14(7):643–648

    Article  CAS  Google Scholar 

  20. Yang K, Gu MY, Guo YP, Pan XF, Mu GH (2009) Effects of carbon nanotube functionalization on the mechanical and thermal properties of epoxy composites. Carbon 47:1723–1737

    Article  CAS  Google Scholar 

  21. Lu C, Hu XN, He YX, Huang XH, Liu JC, Zhang YQ (2012) Triple percolation behavior and positive temperature coefficient effect of conductive polymer composites with especial interface morphology. Polym Bull 68:2071–2087

    Article  CAS  Google Scholar 

  22. He YX, Ma JZ, Zhang L, Zhang YQ (2008) Preparation and Characterization of Graft Copolymer EVA-g-PU. Polym Plast Technol Eng 47:1214–1219

    Article  CAS  Google Scholar 

  23. McNally T, Pötschke P, Halley P, Murphy M, Martin D, Bell SEJ (2005) Polyethylene multiwalled carbon nanotube composites. Polymer 46(19):8222–8232

    Article  CAS  Google Scholar 

  24. Guadagno L, De Vivo B, Di Bartolomeo A, Lamberti P, Sorrentino A, Tucci V (2011) Effect of functionalization on the thermo-mechanical and electrical behavior of multi-wall carbon nanotube/epoxy composites. Carbon 49:1919–1930

    Article  CAS  Google Scholar 

  25. Datsyuk V, Kalyva M, Papagelis K, Parthenios J, Tasis D, Siokou A (2008) Chemical oxidation of multiwalled carbon nanotubes. Carbon 46:833–840

    Article  CAS  Google Scholar 

  26. Yang Y, Xie X, Wu J, Yang Z, Wang X, Mai YW (2006) Multiwalled carbon nanotubes functionalized by hyperbranched poly(urea-urethane)s by a one-pot polycondensations. Macromol Rapid Commun 27:1695–1701

    Article  CAS  Google Scholar 

  27. Zhang Y, Broekhuis AA, Stuart MCA, Landaluce FT, Fausti D, Rudolf P (2008) Cross-linking of multiwalled carbon nanotubes with polymeric amines. Macromolecules 41:6141–6146

    Article  CAS  Google Scholar 

  28. Okpalugo TIT, Papakonstantinou P, Murphy H, McLaughlim J, Brown NMD (2005) High resolution XPS characterization of chemical functionalized MWCNTs and SWCNTs. Carbon 43:153–161

    Article  CAS  Google Scholar 

  29. Papagelis K, Kalyva M, Tasis D, Parthenios J, Siokou A, Galiotis C (2007) Covalently functionalized carbon nanotubes as macroinitiators for radical polymerization. Phys Stat Sol 244(11):4046–4050

    Article  CAS  Google Scholar 

  30. Zhang GX, Sun SH, Yang DQ, Dodelet JP, Sacher E (2008) The surface analytical characterization of carbon fibers functionalized by H2SO4/HNO3 treatment. Carbon 46(2):196–205

    Article  CAS  Google Scholar 

  31. Xia W, Wang Y, Bergsträßer R, Kundu S, Muhler M (2007) Surface characterization of oxygen-functionalized multi-walled carbon nanotubes by high-resolution X-ray photoelectron spectroscopy and temperature-programmed desorption. Appl Surf Sci 254(1):247–250

    Article  CAS  Google Scholar 

  32. Kathi J, Rhee KY (2008) Surface modification of multi-walled carbon nanotubes using 3-aminopropyltriethoxysilane. J Mater Sci 43:33–37

    Article  CAS  Google Scholar 

  33. Chiu WM, Chang YA (2008) Chemical modification of multi-walled carbon nanotube with the liquid phase method. J Appl Polym Sci 107:1655–1660

    Article  CAS  Google Scholar 

  34. Jeong WJ, Kessler MR (2008) Toughness enhancement in ROMP functionalized carbon nanotube/polydicyclopentadiene composites. Chem Mater 20:7060–7068

    Article  CAS  Google Scholar 

  35. Fu SY, Feng XQ, Lauke B, Mai YW (2008) Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites. Compos B 39:933–961

    Article  Google Scholar 

  36. Fu SY, Lauke B (1998) The elastic modulus of misaligned short fiber reinforced polymers. Compos Sci Technol 58:389–400

    Article  CAS  Google Scholar 

  37. Fu SY, Lauke B (1998) An analytical characterization of the anisotropy of the elastic modulus of misaligned short-fiber-reinforced polymers. Compos Sci Technol 58:1961–1972

    Article  CAS  Google Scholar 

  38. Lee JH, Rhee KY, Park SJ (2011) Silane modification of carbon nanotubes and its effects on the material properties of carbon/CNT/epoxy three-phase composites. Compos A 42:478–483

    Article  Google Scholar 

Download references

Acknowledgments

This project was financially supported by Excellent Talents Innovation Foundation (No. 074200510019) and Project of Education (No. 13A430248) of Henan Province and Youth Foundation of Henan University of Science and Technology of China (2010QN0013).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yuxin He.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

He, Y., Zhang, L., Chen, G. et al. Surface functionalized carbon nanotubes and its effects on the mechanical properties of epoxy based composites at cryogenic temperature. Polym. Bull. 71, 2465–2485 (2014). https://doi.org/10.1007/s00289-014-1202-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-014-1202-6

Keywords

Navigation