Iranian Polymer Journal

, Volume 27, Issue 4, pp 239–252 | Cite as

Preparation and characterization of amidated graphene oxide and its effect on the performance of poly(lactic acid)

  • Lang Zheng
  • Weijun Zhen
Original Research


An improved Hummers method was used to prepare graphene oxide (GO). Then, the orthogonal experiment design methods were used to select the optimum conditions of the preparation for amidated graphene oxide (AGO) via amidation. The optimum scheme was followed by: reaction temperature 70 °C, reaction time 5 h and GO: benzohydrazide of 1:3 (g:g). The structure of AGO was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscope (TEM) techniques, which demonstrated that the amidation of GO was successful. Furthermore, poly(lactic acid) (PLA)/AGO nanocomposites were prepared by melt blending to improve the comprehensive performance of PLA. Mechanical properties, thermal stabilities, crystallization properties, and rheological behavior of PLA/AGO nanocomposites were investigated, which showed that the addition of 0.3 wt % of AGO increased the tensile strength, elongation-at-break, and impact strength of PLA/AGO nanocomposites by 7.68, 47.32 and 41.27%, respectively, compared with neat PLA. Scanning electron microscopy analysis showed ductile fracture of the PLA/AGO nanocomposites. TEM analysis showed that nano-AGO single layers were evenly dispersed in the PLA matrix, confirming the formation of an exfoliated nanocomposite structure. Differential scanning calorimetry demonstrated that AGO eliminated the cold crystallization of PLA matrix and improved the crystallinity of PLA by 34.1%. In all, this study provided an effective and feasible method for improving the comprehensive performance of PLA.


Poly(lactic acid) Graphene oxide Amidated graphene oxide Nanocomposites Performance 



Financial support from Key Laboratory Open Foundation (No. 2016D03010) of Xinjiang Uygur Autonomous Region of China is greatly acknowledged.

Supplementary material

13726_2018_604_MOESM1_ESM.docx (850 kb)
Supplementary material 1 (DOCX 850 kb)


  1. 1.
    Wan Y-J, Tang L-C, Gong L-X, Yan D, Li Y-B, Wu L-B, Jiang J-X, Lai G-Q (2014) Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties. Carbon 69:467–480CrossRefGoogle Scholar
  2. 2.
    Han M, Yun J, Kim H-I, Lee Y-S (2012) Effect of surface modification of graphene oxide on photochemical stability of poly(vinyl alcohol)/graphene oxide composites. J Ind Eng Chem 18:752–756CrossRefGoogle Scholar
  3. 3.
    Hegab HM, Wimalasiri Y, Ginic-Markovic M, Zou L (2015) Improving the fouling resistance of brackish water membranes via surface modification with graphene oxide functionalized chitosan. Desalination 365:99–107CrossRefGoogle Scholar
  4. 4.
    Liu H, Bandyopadhyay P, Kim NH, Moon B, Lee JH (2016) Surface modified graphene oxide/poly(vinyl alcohol) composite for enhanced hydrogen gas barrier film. Polym Test 50:49–56CrossRefGoogle Scholar
  5. 5.
    Liu Z, Robinson JT, Sun X, Dai H (2008) Pegylated nanographene oxide for delivery of water-insoluble cancer drugs. J Am Chem Soc 130:10876–10877CrossRefGoogle Scholar
  6. 6.
    Tang X-Z, Li W, Yu Z-Z, Rafiee MA, Rafiee J, Yavari F, Koratkar N (2011) Enhanced thermal stability in graphene oxide covalently functionalized with 2-amino-4,6-didodecylamino-1,3,5-triazine. Carbon 49:1258–1265CrossRefGoogle Scholar
  7. 7.
    Chen B-K, Shen C-H, Chen A-F (2012) Preparation of ductile PLA materials by modification with trimethyl hexamethylene diisocyanate. Polym Bull 69:313–322CrossRefGoogle Scholar
  8. 8.
    Kawamoto N, Sakai A, Horikoshi T, Urushihara T, Tobita E (2007) Nucleating agent for poly(l-lactic acid)—an optimization of chemical structure of hydrazide compound for advanced nucleation ability. J Appl Polym Sci 103:198–203CrossRefGoogle Scholar
  9. 9.
    Wang T, Yang Y, Zhang C, Tang Z, Na H, Zhu J (2013) Effect of 1,3,5-trialkyl-benzenetricarboxylamide on the crystallization of poly(lactic acid). J Appl Polym Sci 130:1328–1336CrossRefGoogle Scholar
  10. 10.
    Harris AM, Lee EC (2008) Improving mechanical performance of injection molded PLA by controlling crystallinity. J Appl Polym Sci 107:2246–2255CrossRefGoogle Scholar
  11. 11.
    Cai Y, Yan S, Yin J, Fan Y, Chen X (2011) Crystallization behavior of biodegradable poly(L-lactic acid) filled with a powerful nucleating agent: N,N′-bis(benzoyl)suberic acid dihydrazide. J Appl Polym Sci 121:1408–1416CrossRefGoogle Scholar
  12. 12.
    Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339CrossRefGoogle Scholar
  13. 13.
    Zhen W, Lu C (2012) Surface modification of thermoplastic poly(vinyl alcohol)/saponite nanocomposites via surface-initiated atom transfer radical polymerization enhanced by air dielectric discharges barrier plasma treatment. Appl Surf Sci 258:6969–6976CrossRefGoogle Scholar
  14. 14.
    Janssen D, De Palma R, Verlaak S, Heremans P, Dehaen W (2006) Static solvent contact angle measurements, surface free energy and wettability determination of various self-assembled monolayers on silicon dioxide. Thin Solid Films 515:1433–1438CrossRefGoogle Scholar
  15. 15.
    Stankovich S, Piner RD, Nguyen SBT, Ruoff RS (2006) Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets. Carbon 44:3342–3347CrossRefGoogle Scholar
  16. 16.
    Rani S, Kumar M, Kumar R, Kumar D, Sharma S, Singh G (2014) Characterization and dispersibility of improved thermally stable amide functionalized graphene oxide. Mater Res Bull 60:143–149CrossRefGoogle Scholar
  17. 17.
    Zhen W, Lu C, Li C, Liang M (2012) Structure and properties of thermoplastic saponite/poly(vinyl alcohol) nanocomposites. Appl Clay Sci 57:64–70CrossRefGoogle Scholar
  18. 18.
    Yang H, Li F, Shan C, Han D, Zhang Q, Li N, Ivaska A (2009) Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement. J Mater Chem 19:4632–4638CrossRefGoogle Scholar
  19. 19.
    Subrahmanyam KS, Vivekchand SRC, Govindaraj A, Rao CNR (2008) A study of graphenes prepared by different methods: characterization, properties and solubilization. J Mater Chem 18:1517–1523CrossRefGoogle Scholar
  20. 20.
    Shalaby A, Nihtianova D, Markov P, Staneva AD, Iordanova RS, Dimitriev YB (2015) Structural analysis of reduced graphene oxide by transmission electron microscopy. Bulg Chem Commun 47:291–295Google Scholar
  21. 21.
    Chen N, Ren Y, Kong P, Tan L, Feng H, Luo Y (2017) In situ one-pot preparation of reduced graphene oxide/polyaniline composite for high-performance electrochemical capacitors. Appl Surf Sci 392:71–79CrossRefGoogle Scholar
  22. 22.
    Zhou YF, Song YN, Zhen WJ, Wang WT (2015) The effects of structure of inclusion complex between β-cyclodextrin and poly(L-lactic acid) on its performance. Macromol Res 23:1103–1111CrossRefGoogle Scholar
  23. 23.
    Ismail H, Shuhelmy S, Edyham MR (2002) The effects of a silane coupling agent on curing characteristics and mechanical properties of bamboo fibre filled natural rubber composites. Eur Polym J 38:39–47CrossRefGoogle Scholar
  24. 24.
    Kaiser MR, Anuar HB, Samat NB, Razak SBA (2013) Effect of processing routes on the mechanical, thermal and morphological properties of PLA-based hybrid biocomposite. Iran Polym J 22:123–131CrossRefGoogle Scholar
  25. 25.
    Wang W, Zhen W, Bian S, Xi X (2015) Structure and properties of quaternary fulvic acid–intercalated saponite/poly(lactic acid) nanocomposites. Appl Clay Sci 109–110:136–142CrossRefGoogle Scholar
  26. 26.
    Ansari MNM, Ismail H (2009) The effect of silane coupling agent on mechanical properties of feldspar filled polypropylene composites. J Reinf Plast Compos 28:3049–3060CrossRefGoogle Scholar
  27. 27.
    Mohamed A, Gordon SH, Biresaw G (2007) Poly(lactic acid)/polystyrene bioblends characterized by thermogravimetric analysis, differential scanning calorimetry, and photoacoustic infrared spectroscopy. Appl Polym Sci 106:1689–1696CrossRefGoogle Scholar
  28. 28.
    Xu Z, Niu Y, Yang L, Xie W, Li H, Gan Z, Wang Z (2010) Morphology, rheology and crystallization behavior of polylactide composites prepared through addition of five-armed star polylactide grafted multiwalled carbon nanotubes. Polymer 51:730–737CrossRefGoogle Scholar
  29. 29.
    Dobreva T, Pereña JM, Pérez E, Benavente R, García M (2010) Crystallization behavior of poly(L-lactic acid)-based ecocomposites prepared with kenaf fiber and rice straw. Polym Compos 31:974–984CrossRefGoogle Scholar
  30. 30.
    Solarski S, Ferreira M, Devaux E (2005) Characterization of the thermal properties of PLA fibers by modulated differential scanning calorimetry. Polymer 46:11187–11192CrossRefGoogle Scholar
  31. 31.
    Manafi P, Ghasemi I, Manafi MR, Ehsaninamin P, Hassanpour Asl F (2017) Non-isothermal crystallization kinetics assessment of poly(lactic acid)/graphene nanocomposites. Iran Polym J 26:377–389CrossRefGoogle Scholar
  32. 32.
    Raquez J-M, Habibi Y, Murariu M, Dubois P (2013) Polylactide (PLA)-based nanocomposites. Prog Polym Sci 38:1504–1542CrossRefGoogle Scholar
  33. 33.
    Li H, Lu X, Yang H, Hu J (2015) Non-isothermal crystallization of P(3HB- co -4HB)/PLA blends. J Therm Anal Calorim 122:817–829CrossRefGoogle Scholar
  34. 34.
    Huang J-M, Yang S-J (2005) Studying the miscibility and thermal behavior of polybenzoxazine/poly(ε-caprolactone) blends using DSC, DMA, and solid state 13C NMR spectroscopy. Polymer 46:8068–8078CrossRefGoogle Scholar
  35. 35.
    Cheng S, Lau K-T, Liu T, Zhao Y, Lam P-M, Yin Y (2009) Mechanical and thermal properties of chicken feather fiber/PLA green composites. Compos B Eng 40:650–654CrossRefGoogle Scholar
  36. 36.
    Caro S, Sánchez DB, Caicedo B (2015) Methodology to characterise non-standard asphalt materials using DMA testing: application to natural asphalt mixtures. Int J Pavement Eng 16:1–10CrossRefGoogle Scholar
  37. 37.
    Zhen W, Wang W (2016) Structure, properties and rheological behavior of thermoplastic poly(lactic acid)/quaternary fulvic acid-intercalated saponite nanocomposites. Polym Bull 73:1015–1035CrossRefGoogle Scholar
  38. 38.
    Xu Y-Q, Qu J-P (2009) Mechanical and rheological properties of epoxidized soybean oil plasticized poly(lactic acid). J Appl Polym Sci 112:3185–3191CrossRefGoogle Scholar

Copyright information

© Iran Polymer and Petrochemical Institute 2018

Authors and Affiliations

  1. 1.Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education and Xinjiang Uygur RegionXinjiang UniversityÜrümqiChina

Personalised recommendations