Advertisement

Journal of Polymer Research

, 26:42 | Cite as

Fluorinated functionalization of graphene oxide and its role as a reinforcement in epoxy composites

  • Husamelden E.
  • Hong FanEmail author
ORIGINAL PAPER
  • 41 Downloads

Abstract

This study was carried out to explore the effects of graphene oxide modified with fluorinated-diol (GOFO) on the properties of the epoxy resin. Fluorinated graphene oxide (GOFO) was prepared by one-step reaction with a fluorinated diol. The fluorinated functionalized graphene oxide was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Thermogravimetric analysis. Epoxy/ fluorinated graphene oxide composites were prepared by dispersing the prepared graphene material in epoxy resin based on Diglycidyl Ether of Bisphenol-A (DGEBA), followed by curing with 4, 4-diaminodiphenylsulfone (DDS). The epoxy composites were examined for its mechanical properties, thermal stability, water uptake, and the water contact angle. Results show that the addition of the proper content of GOFO can enhance the performances of epoxy resin. Epoxy composite tensile and flexural modulus increased by 12.52% and 62.85%, respectively with 0.5 wt.% GOFO loading. Epoxy composite with 0.3 wt.% GOFO shows high thermal stability. The T5%, T50%, and Tdec were 13 o C, 15 o C, and 13 o C, respectively, higher than pure epoxy. Besides that, the incorporation of 0.3 wt.% GOFO significantly decreases the water uptake from 0.432% for the pure epoxy to 0.304%. In addition, the water contact angle increases from 68.72o of pure epoxy to 98.65o for 0.3 wt.% epoxy composite.

Keywords

Graphene oxide Fluorinated diol Mechanical properties Thermal stability Water absorption 

Notes

Acknowledgments

The authors acknowledge funding from the Chinese Scholarship Council (CSC) and the State Key of Laboratory of Chemical Engineering, Zhejiang University.

Compliance with ethical standards

Conflict of interest

The authors declare that there is no conflict of interests regarding the publication of this paper.

References

  1. 1.
    Zong PS, Fu JF, Chen LY, Yin JT, Dong X, Yuan S, Shi LY, Deng W (2016) Effect of aminopropylisobutyl polyhedral oligomeric silsesquioxane functionalized graphene on the thermal conductivity and electrical insulation properties of epoxy composites. RSC Adv 6(13):10498–10506.  https://doi.org/10.1039/c5ra24885j CrossRefGoogle Scholar
  2. 2.
    Hou GX, Gao JG, Xie JQ, Li B (2016) Preparation and properties characterization of gallic acid epoxy resin/succinic anhydride bionanocomposites modified by green reduced graphene oxide. Soft Mater 14(1):27–37.  https://doi.org/10.1080/1539445X.2015.1098704 CrossRefGoogle Scholar
  3. 3.
    Saleem H, Edathil A, Ncube T, Pokhrel J, Khoori S, Abraham A, Mittal V (2016) Mechanical and thermal properties of thermoset-graphene nanocomposites. Macromol Mater Eng 301(3):231–259.  https://doi.org/10.1002/mame.201500335 CrossRefGoogle Scholar
  4. 4.
    Yu ZX, Di HH, Ma Y, He Y, Liang L, Lv L, Ran X, Pan Y, Luo Z (2015) Preparation of graphene oxide modified by titanium dioxide to enhance the anti-corrosion performance of epoxy coatings. Surf Coat Tech 276:471–478.  https://doi.org/10.1016/j.surfcoat.2015.06.027 CrossRefGoogle Scholar
  5. 5.
    Liu TX, Zhao ZS, Tjiu WW, Lv J, Wei C (2014) Preparation and characterization of epoxy nanocomposites containing surface-modified graphene oxide. J Appl Polym Sci 131(9).  https://doi.org/10.1002/app.40236
  6. 6.
    Yu ZX, Lv L, Ma Y, Di HH, He Y (2016) Covalent modification of graphene oxide by metronidazole for reinforced anti-corrosion properties of epoxy coatings. RSC Adv 6(22):18217–18226.  https://doi.org/10.1039/c5ra23595b CrossRefGoogle Scholar
  7. 7.
    Chowdhury I, Duch MC, Mansukhani ND, Hersam MC, Bouchard D (2014) Interactions of graphene oxide nanomaterials with natural organic matter and metal oxide surfaces. Environ Sci Technol 48(16):9382–9390.  https://doi.org/10.1021/es5020828 CrossRefPubMedGoogle Scholar
  8. 8.
    Que XF, Yan YR, Qiu ZM, Wang Y (2016) Synthesis and characterization of trifluoromethyl-containing polyimide-modified epoxy resins. J Mater Sci 51(24):10833–10848.  https://doi.org/10.1007/s10853-016-0294-9 CrossRefGoogle Scholar
  9. 9.
    Wang BC, Li JJ, Liu YN, Gao Y (2017) Reduced graphene oxide/carbon nanotubes nanohybrids as preformed reinforcement for polystyrene composites. J Appl Polym Sci 134(28).  https://doi.org/10.1002/App.45054
  10. 10.
    King JA, Klimek DR, Miskioglu I, Odegard GM (2013) Mechanical properties of graphene nanoplatelet/epoxy composites. J Appl Polym Sci 128(6):4217–4223.  https://doi.org/10.1002/app.38645 CrossRefGoogle Scholar
  11. 11.
    Chen L, Li WB, Liu YJ, Leng JS (2015) Epoxy shape-memory polymer reinforced by thermally reduced graphite oxide: influence of processing techniques. J Appl Polym Sci 132(38).  https://doi.org/10.1002/App.42502
  12. 12.
    Ban FY, Majid SR, Huang NM, Lim HN (2012) Graphene oxide and its electrochemical performance. Int J Electrochem Sc 7(5):4345–4351Google Scholar
  13. 13.
    Abdelkader AM, Valles C, Cooper AJ, Kinloch IA, Dryfe RAW (2014) Alkali reduction of graphene oxide in molten halide salts: production of corrugated graphene derivatives for high-performance supercapacitors. ACS Nano 8(11):11225–11233.  https://doi.org/10.1021/nn505700x CrossRefPubMedGoogle Scholar
  14. 14.
    Galpaya D, Wang M, George G, Motta N, Waclawik E, Yan C (2014) Preparation of graphene oxide/epoxy nanocomposites with significantly improved mechanical properties. J Appl Phys 116(5).  https://doi.org/10.1063/1.4892089
  15. 15.
    Shtein M, Pri-Bar I, Varenik M, Regev O (2015) Characterization of graphene-nanoplatelets structure via thermogravimetry. Anal Chem 87(8):4076–4080.  https://doi.org/10.1021/acs.analchem.5b00228 CrossRefPubMedGoogle Scholar
  16. 16.
    Akhavan O, Bijanzad K, Mirsepah A (2014) Synthesis of graphene from natural and industrial carbonaceous wastes. RSC Adv 4(39):20441–20448.  https://doi.org/10.1039/c4ra01550a CrossRefGoogle Scholar
  17. 17.
    Wang D, Wen PY, Wang J, Song L, Hu Y (2017) The effect of defect-rich molybdenum disulfide nanosheets with phosphorus, nitrogen and silicon elements on mechanical, thermal, and fire behaviors of unsaturated polyester composites. Chem Eng J 313:238–249.  https://doi.org/10.1016/j.cej.2016.12.045 CrossRefGoogle Scholar
  18. 18.
    Ghaleb ZA, Mariatti M, Ariff ZM, Ervina J (2018) Preparation and properties of amine functionalized graphene filled epoxy thin film nano composites for electrically conductive adhesive. J Mater Sci-Mater El 29(4):3160–3169.  https://doi.org/10.1007/s10854-017-8249-8 CrossRefGoogle Scholar
  19. 19.
    Zhang B, Wang J, Tan HY, Su XG, Huo SQ, Yang S, Chen W, Wang JP (2018) Synthesis of Fe@Ni nanoparticles-modified graphene/epoxy composites with enhanced microwave absorption performance. J Mater Sci-Mater El 29(4):3348–3357.  https://doi.org/10.1007/s10854-017-8270-y CrossRefGoogle Scholar
  20. 20.
    Atif R, Shyha I, Inam F (2016) The degradation of mechanical properties due to stress concentration caused by retained acetone in epoxy nanocomposites. RSC Adv 6(41):34188–34197.  https://doi.org/10.1039/c6ra00739b CrossRefGoogle Scholar
  21. 21.
    Ganesan Y, Salahshoor H, Peng C, Khabashesku V, Zhang JN, Cate A, Rahbar N, Lou J (2014) Fracture toughness of the sidewall fluorinated carbon nanotube-epoxy interface. J Appl Phys 115(22).  https://doi.org/10.1063/1.4881882
  22. 22.
    Wan YJ, Tang LC, Gong LX, Yan D, Li YB, Wu LB, Jiang JX, Lai GQ (2014) Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties. Carbon 69:467–480.  https://doi.org/10.1016/j.carbon.2013.12.050 CrossRefGoogle Scholar
  23. 23.
    Sharmila TKB, Antony JV, Jayakrishnan MP, Beegum PMS, Thachil ET (2016) Mechanical, thermal and dielectric properties of hybrid composites of epoxy and reduced graphene oxide/iron oxide. Mater Design 90:66–75CrossRefGoogle Scholar
  24. 24.
    Yang Y, Mikes F, Yang L, Liu WH, Koike Y, Okamoto Y (2006) Investigation of homopolymerization rate of perfluoro-4,5-substituted-2-methylene-1,3-dioxolane derivatives and properties of the polymers. J Fluor Chem 127(2):277–281.  https://doi.org/10.1016/j.jfluchem.2005.12.004 CrossRefGoogle Scholar
  25. 25.
    Roitman JN, Pittman AG (1972) Wetting Properties of Acrylic Polymers Containing Perfluoro-T-Butyl Side Chains. J Polym Sci Pol Lett 10(7):499.  https://doi.org/10.1002/pol.1972.110100703 CrossRefGoogle Scholar
  26. 26.
    Wang JP, Wang J, Zhang B, Sun Y, Chen W, Wang T (2016) Combined use of lightweight magnetic Fe3O4-coated hollow glass spheres and electrically conductive reduced graphene oxide in an epoxy matrix for microwave absorption. J Magn Magn Mater 401:209–216CrossRefGoogle Scholar
  27. 27.
    Arukula R, Narayan R, Sreedhar B, Rao CRK (2016) High corrosion resistant - redox active - moisture curable - conducting polyurethanes. Prog Org Coat 94:79–89.  https://doi.org/10.1016/j.porgcoat.2016.01.022 CrossRefGoogle Scholar
  28. 28.
    Sha M, Zhang D, Pan RM, Xing P, Jiang B (2015) Synthesis and surface properties study of novel fluorine-containing homopolymer and copolymers for coating applications. Appl Surf Sci 349:496–502.  https://doi.org/10.1016/j.apsusc.2015.04.219 CrossRefGoogle Scholar
  29. 29.
    Guo YJ, Liu WQ, Yan ZL (2015) Synthesis and characterization of fluorinated acrylic polymer and the properties of epoxy thermosets modified with it. J Macromol Sci A 52(10):838–846.  https://doi.org/10.1080/10601325.2015.1067044 CrossRefGoogle Scholar
  30. 30.
    Psarski M, Pawlak D, Grobelny J, Celichowski G (2015) Hydrophobic and superhydrophobic surfaces fabricated by plasma polymerization of perfluorohexane, perfluoro(2-methylpent-2-ene), and perfluoro(4-methylpent-2-ene). J Adhes Sci Technol 29(19):2035–2048.  https://doi.org/10.1080/01694243.2015.1048131 CrossRefGoogle Scholar
  31. 31.
    Ameduri B, Bongiovanni R, Sangermano M, Priola A (2009) Fluorinated Hydroxytelechelic polybutadiene as additive in cationic Photopolymerization of an epoxy resin. J Polym Sci Pol Chem 47(11):2835–2842.  https://doi.org/10.1002/pola.23376 CrossRefGoogle Scholar
  32. 32.
    Yan ZL, Liu WQ, Gao N, Wang HL, Su K (2013) Synthesis and properties of a novel UV-cured fluorinated siloxane graft copolymer for improved surface, dielectric and tribological properties of epoxy acrylate coating. Appl Surf Sci 284:683–691.  https://doi.org/10.1016/j.apsusc.2013.07.156 CrossRefGoogle Scholar
  33. 33.
    Wang CZ, Zuo Y (2009) Improvement of surface and moisture resistance of epoxy resins with fluorinated Glycidyl ether. J Appl Polym Sci 114(4):2528–2532.  https://doi.org/10.1002/app.30803 CrossRefGoogle Scholar
  34. 34.
    Yin M, Yang L, Li XY, Ma HB (2013) Synthesis and properties of methyl hexahydrophthalic anhydride-cured fluorinated epoxy resin 2,2-bisphenol hexafluoropropane diglycidyl ether. J Appl Polym Sci 130(4):2801–2808.  https://doi.org/10.1002/app.39517 CrossRefGoogle Scholar
  35. 35.
    Ye XY, Liu XH, Yang ZG, Wang ZF, Wang HG, Wang JQ, Yang SR (2016) Tribological properties of fluorinated graphene reinforced polyimide composite coatings under different lubricated conditions. Compos Part a-Appl S 81:282–288.  https://doi.org/10.1016/j.compositesa.2015.11.029 CrossRefGoogle Scholar
  36. 36.
    Zhang PP, Zhao JP, Zhang K, Bai R, Wang YM, Hua CX, Wu YY, Liu XX, Xu HB, Li Y (2016) Fluorographene/polyimide composite films: mechanical, electrical, hydrophobic, thermal and low dielectric properties. Compos Part a-Appl S 84:428–434.  https://doi.org/10.1016/j.compositesa.2016.02.019 CrossRefGoogle Scholar
  37. 37.
    Yang K, Huang X, Fang L, He J, Jiang P (2014) Fluoro-polymer functionalized graphene for flexible ferroelectric polymer-based high-k nanocomposites with suppressed dielectric loss and low percolation threshold. Nanoscale 6(24):14740–14753.  https://doi.org/10.1039/c4nr03957b CrossRefPubMedGoogle Scholar
  38. 38.
    Moo JGS, Khezri B, Webster RD, Pumera M (2014) Graphene oxides prepared by Hummers', Hofmann's, and Staudenmaier's methods: dramatic influences on heavy-metal-ion adsorption. Chemphyschem 15(14):2922–2929.  https://doi.org/10.1002/cphc.201402279 CrossRefPubMedGoogle Scholar
  39. 39.
    Cao N, Zhang Y (2015) Study of Reduced Graphene Oxide Preparation by Hummers’ Method and Related Characterization. J Nanomater.  https://doi.org/10.1155/2015/168125
  40. 40.
    Akgul O, Alver U, Tanriverdi A (2016) Characterization of Graphene Oxide Produced by Hummers Method and its Supercapacitor Applications. 9th International Physics Conference of the Balkan Physical Union (Bpu-9) 1722.  https://doi.org/10.1063/1.4944280
  41. 41.
    Ye XY, Gong PW, Wang JQ, Wang HG, Ren SL, Yang SR (2015) Fluorinated graphene reinforced polyimide films with the improved thermal and mechanical properties. Compos Part a-Appl S 75:96–103.  https://doi.org/10.1016/j.compositesa.2015.04.005 CrossRefGoogle Scholar
  42. 42.
    Bai LH, Yan HX, Yuan LX, Liu C (2016) Synthesis of functionalized GO for improving the dielectric properties of bismaleimide-triazine resin. J Polym res 23(8).  https://doi.org/10.1007/s10965-016-1071-9
  43. 43.
    Wan YJ, Gong LX, Tang LC, Wu LB, Jiang JX (2014) Mechanical properties of epoxy composites filled with silane-functionalized graphene oxide. Compos Part a-Appl S 64:79–89CrossRefGoogle Scholar
  44. 44.
    Chen L, Li WB, Liu YJ, Leng JS (2016) Nanocomposites of epoxy-based shape memory polymer and thermally reduced graphite oxide: mechanical, thermal and shape memory characterizations. Compos Part B-Eng 91:75–82.  https://doi.org/10.1016/j.compositesb.2016.01.019 CrossRefGoogle Scholar
  45. 45.
    Liu RQ, Liang SM, Tang XZ, Yan D, Li XF, Yu ZZ (2012) Tough and highly stretchable graphene oxide/polyacrylamide nanocomposite hydrogels. J Mater Chem 22(28):14160–14167.  https://doi.org/10.1039/c2jm32541a CrossRefGoogle Scholar
  46. 46.
    Gerani K, Mortaheb HR, Mokhtarani B (2017) Enhancement in performance of sulfonated PES cation-exchange membrane by introducing pristine and sulfonated graphene oxide Nanosheets synthesized through hummers and Staudenmaier methods. Polym-Plast Technol 56(5):543–555.  https://doi.org/10.1080/03602559.2016.1233260 CrossRefGoogle Scholar
  47. 47.
    Frankberg EJ, George L, Efimov A, Honkanen M, Pessi J, Levanen E (2015) Measuring synthesis yield in graphene oxide synthesis by modified hummers method. Fuller Nanotub Car N 23(9):755–759.  https://doi.org/10.1080/1536383x.2014.993754 CrossRefGoogle Scholar
  48. 48.
    Hu XL, Qi RR, Zhu J, Lu JQ, Luo Y, Jin JY, Jiang PK (2014) Preparation and properties of dopamine reduced graphene oxide and its composites of epoxy. J Appl Polym Sci 131(2).  https://doi.org/10.1002/App.39754
  49. 49.
    Xing RG, Li YN, Yu HT (2016) Preparation of fluoro-functionalized graphene oxide via the Hunsdiecker reaction. Chem Commun 52(2):390–393.  https://doi.org/10.1039/c5cc08252h CrossRefGoogle Scholar
  50. 50.
    Liu FD, Wu L, Song YJ, Xia WG, Guo KK (2015) Effect of molecular chain length on the properties of amine-functionalized graphene oxide nanosheets/epoxy resins nanocomposites. RSC Adv 5(57):45987–45995.  https://doi.org/10.1039/c5ra02013a CrossRefGoogle Scholar
  51. 51.
    Kulkarni H, Tambe P, Joshi G (2017) High concentration exfoliation of graphene in ethyl alcohol using block copolymer surfactant and its influence on properties of epoxy nanocomposites. Fuller Nanotub Car N 25(4):241–249.  https://doi.org/10.1080/1536383X.2017.1283616 CrossRefGoogle Scholar
  52. 52.
    Pan LL, Ban JF, Lu SR, Chen GX, Yang J, Luo QY, Wu LY, Yu JH (2015) Improving thermal and mechanical properties of epoxy composites by using functionalized graphene. RSC Adv 5(74):60596–60607.  https://doi.org/10.1039/c5ra09410k CrossRefGoogle Scholar
  53. 53.
    Cai LP, Zhan RY, Pu KY, Qi XY, Zhang H, Huang W, Liu B (2011) Butterfly-shaped conjugated Oligoelectrolyte/graphene oxide integrated assay for light-up visual detection of heparin. Anal Chem 83(20):7849–7855.  https://doi.org/10.1021/ac2016135 CrossRefPubMedGoogle Scholar
  54. 54.
    Qi B, Yuan ZK, Lu SR, Liu K, Li SR, Yang LP, Yu JH (2014) Mechanical and thermal properties of epoxy composites containing graphene oxide and liquid crystalline epoxy. Fiber Polym 15(2):326–333.  https://doi.org/10.1007/s12221-014-0326-5 CrossRefGoogle Scholar
  55. 55.
    Chen X, Huang HH, Shu X, Liu SM, Zhao JQ (2017) Preparation and properties of a novel graphene fluoroxide/polyimide nanocomposite film with a low dielectric constant. RSC Adv 7(4):1956–1965.  https://doi.org/10.1039/c6ra25343a CrossRefGoogle Scholar
  56. 56.
    Li KY, Kuan CF, Kuan HC, Chen CH, Shen MY, Yang JM, Chiang CL (2014) Preparation and properties of novel epoxy/graphene oxide nanosheets (GON) composites functionalized with flame retardant containing phosphorus and silicon. Mater Chem Phys 146(3):354–362.  https://doi.org/10.1016/j.matchemphys.2014.03.037 CrossRefGoogle Scholar
  57. 57.
    Olowojoba GB, Kopsidas S, Eslava S, Gutierrez ES, Kinloch AJ, Mattevi C, Rocha VG, Taylor AC (2017) A facile way to produce epoxy nanocomposites having excellent thermal conductivity with low contents of reduced graphene oxide. J Mater Sci 52(12):7323–7344.  https://doi.org/10.1007/s10853-017-0969-x CrossRefGoogle Scholar
  58. 58.
    Wang R, Zhuo DX, Weng ZX, Wu LX, Cheng XY, Zhou Y, Wang JL, Xuan BW (2015) A novel nanosilica/graphene oxide hybrid and its flame retarding epoxy resin with simultaneously improved mechanical, thermal conductivity, and dielectric properties. J Mater Chem A 3(18):9826–9836.  https://doi.org/10.1039/c5ta00722d CrossRefGoogle Scholar
  59. 59.
    Saharudin MS, Atif R, Inam F (2017) Effect of short-term water exposure on the mechanical properties of Halloysite nanotube-multi layer graphene reinforced polyester nanocomposites. Polymers-Basel 9(1).  https://doi.org/10.3390/Polym9010027
  60. 60.
    Gao J, Shen KY, Bao F, Yin J, Wang DF, Ma R, Yan CJ, Chen T, Wang GZ, Liu X, Zhang X, Zhang DB (2013) Preparation and characterization of a graphene oxide film modified by the covalent attachment of Polysiloxane. Polym-Plast Technol 52(6):553–557.  https://doi.org/10.1080/03602559.2012.762378 CrossRefGoogle Scholar
  61. 61.
    Plengudomkit R, Okhawilai M, Rimdusit S (2016) Highly filled graphene-Benzoxazine composites as bipolar plates in fuel cell applications. Polym Compos 37(6):1715–1727.  https://doi.org/10.1002/pc.23344 CrossRefGoogle Scholar
  62. 62.
    Lu H, Zhang ST, Li WH, Cui YA, Yang T (2017) Synthesis of graphene oxide-based sulfonated Oligoanilines coatings for synergistically enhanced corrosion protection in 3.5% NaCl solution. Acs Appl Mater Inter 9(4):4034–4043.  https://doi.org/10.1021/acsami.6b13722 CrossRefGoogle Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Chemical Engineering, College of Chemical and Biological EngineeringZhejiang UniversityHangzhouChina

Personalised recommendations