Hydrophobically modified graphene oxide as a barrier and antibacterial agent for polystyrene packaging

  • 24 Accesses


Numerous works have been reported in order to enhance the barrier properties of the polystyrene (PS). In this work, hydrophilic graphene oxide (GO), prepared by the Hummer method, was surface-grafted with hydrophobic poly(4-vinylbenzyl chloride), p(VBC), via in situ radical polymerization approach. The graphene oxide/poly(4-vinylbenzyl chloride), GP(VBC), was then dispersed in the polystyrene matrix in order to obtain nano-composite thin films of different filler ratios (5, 10, 15, 20, and 25) wt%. The modified GO and its corresponding films were characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscope, field emission scanning electron microscope, thermal gravimetric analysis, and contact angle. Mechanical properties of the films were studied as well. The results indicated that the surface modification step improved the dispersion of GO within the polystyrene film due to the hydrophobic nature of modified GO. Consequently, an obvious enhancement of thermal stability and mechanical properties of the PS films loaded with GP(VBC) compared with the pure films was noticed. The rate of water vapor permeability showed an abrupt decrease even at the lowest loading percentage of the filler, which is 5 wt%. The antimicrobial activity of the fabricated polystyrene nano-composite films was also investigated against deleterious pathogens. As a net result, the composite films revealed superior properties thanks to the inclusion of the GP(VBC). This present work paves the way for the next generation of high barrier and bactericide polystyrene packaging with an economic impact.

Graphical Abstract

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

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 199

This is the net price. Taxes to be calculated in checkout.

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7


  1. 1

    Bharech S, Kumar R (2015) A review on the properties and applications of graphene. J Mater Sci Mech Eng 2(10):70

  2. 2

    Allen MJ, Tung VC, Kaner RB (2009) Honeycomb carbon: a review of graphene. Chem Rev 110(1):132–145

  3. 3

    Manawi Y, Samara A, Al-Ansari T, Atieh M (2018) A review of carbon nanomaterials’ synthesis via the chemical vapor deposition (CVD) method. Materials 11(5):822

  4. 4

    Geim AK, Novoselov KS (2010) The rise of graphene, nanoscience and technology: a collection of reviews from nature journals. World Scientific, Singapore, pp 11–19

  5. 5

    Lee C, Wei X, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321(5887):385–388

  6. 6

    Lu Q, Huang R (2009) Nonlinear mechanics of single-atomic-layer graphene sheets. Int J Appl Mech 1(03):443–467

  7. 7

    Kuzmenko AB, Van Heumen E, Carbone F, Van Der Marel D (2008) Universal optical conductance of graphite. Phys Rev Lett 100(11):117401

  8. 8

    Bonaccorso F, Colombo L, Yu G, Stoller M, Tozzini V, Ferrari AC, Pellegrini V (2015) Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage. Science 347(6217):1246501

  9. 9

    Loryuenyong V, Saewong C, Aranchaiya C, Buasri A (2015) The improvement in mechanical and barrier properties of poly (vinyl alcohol)/graphene oxide packaging films. Packag Technol Sci 28(11):939–947

  10. 10

    Gaska K, Kádár R, Rybak A, Siwek A, Gubanski S (2017) Gas barrier, thermal, mechanical and rheological properties of highly aligned graphene-LDPE nanocomposites. Polymers 9(7):294

  11. 11

    Gatti T, Vicentini N, Mba M, Menna E (2016) Organic functionalized carbon nanostructures for functional polymer-based nanocomposites. Eur J Org Chem 2016(6):1071–1090

  12. 12

    Huang HD, Ren PG, Xu JZ, Xu L, Zhong GJ, Hsiao BS, Li ZM (2014) Improved barrier properties of poly (lactic acid) with randomly dispersed graphene oxide nanosheets. J Membr Sci 464:110–118

  13. 13

    Goh K, Heising JK, Yuan Y, Karahan HE, Wei L, Zhai S, Fane AG (2016) Sandwich-architectured poly (lactic acid)–graphene composite food packaging films. ACS Appl Mater Interfaces 8(15):9994–10004

  14. 14

    Montes S, Etxeberria A, Mocholi V, Rekondo A, Grande H, Labidi J (2018) Effect of combining cellulose nanocrystals and graphene nanoplatelets on the properties of poly (lactic acid) based films. Express Polym Lett 12(6):543–555

  15. 15

    Vicentini N, Gatti T, Salerno M, Gomez YSH, Bellon M, Gallio S, Menna E (2018) Effect of different functionalized carbon nanostructures as fillers on the physical properties of biocompatible poly (l-lactic acid) composites. Mater Chem Phys 214:265–276

  16. 16

    Wu LL, Wang JJ, He X, Zhang T, Sun H (2014) Using graphene oxide to enhance the barrier properties of poly (lactic acid) film. Packag Technol Sci 27(9):693–700

  17. 17

    Ahmad H, Fan M, Hui D (2018) Graphene oxide incorporated functional materials: a review. Compos B Eng 145:270–280

  18. 18

    Gudarzi MM, Aboutalebi SH, Sharif F (2016) Graphene oxide-based composite materials. In: Graphene oxide: fundamentals and applications, p 314

  19. 19

    Scheirs J, Priddy D (eds) (2003) Modern styrenic polymers: polystyrenes and styrenic copolymers, vol 6. Wiley, New York

  20. 20

    Christian B, Bart B, Thomas G (2017) Packaging materials 2. Polystyrene for food packaging applications, report, commissioned by the ILSI Europe packaging materials task force

  21. 21

    Van Alfen NK (2014) Encyclopedia of agriculture and food systems. Elsevier, Amsterdam

  22. 22

    Madani M, Sharifi-Sanjani N, Hasan-Kaviar A, Choghazardi M, Faridi-Majidi R, Hamouda AS (2013) PS/TiO2 (polystyrene/titanium dioxide) composite nanofibers with higher surface to volume ratio prepared by electrospinning: morphology and thermal properties. Polym Eng Sci 53(11):2407–2412

  23. 23

    Chae DW, Kim BC (2005) Characterization on polystyrene/zinc oxide nanocomposites prepared from solution mixing. Polym Adv Technol 16(11–12):846–850

  24. 24

    Nazarenko S, Meneghetti P, Julmon P, Olson BG, Qutubuddin S (2007) Gas barrier of polystyrene montmorillonite clay nanocomposites: effect of mineral layer aggregation. J Polym Sci B Polym Phys 45(13):1733–1753

  25. 25

    Patole AS, Patole SP, Yoo JB, An JH, Kim TH (2013) Fabrication of polystyrene/multiwalled carbon nanotube composite films synthesized by in situ microemulsion polymerization. Polym Eng Sci 53(6):1327–1336

  26. 26

    Stankovich S, Dikin DA, Dommett GH, Kohlhaas KM, Zimney EJ, Stach EA, Ruoff RS (2006) Graphene-based composite materials. Nature 442(7100):282

  27. 27

    Yu YH, Lin YY, Lin CH, Chan CC, Huang YC (2014) High-performance polystyrene/graphene-based nanocomposites with excellent anti-corrosion properties. Polym Chem 5(2):535–550

  28. 28

    Liu Y, Zhang Y, Duan L, Zhang W, Su M, Sun Z, He P (2016) Polystyrene/graphene oxide nanocomposites synthesized via Pickering polymerization. Prog Org Coat 99:23–31

  29. 29

    Tolasz J, Stengl V, Ecorchard, P (2014) The preparation of composite material of graphene oxide–polystyrene. In: 3rd international conference on environment, chemistry and biology, IPCBEE, vol 78, IACSIT Press, Singapore.

  30. 30

    Li Y, Jackson AC, Beyer FL, Knauss DM (2014) Poly(2, 6-dimethyl-1, 4-phenylene oxide) blended with poly(vinylbenzyl chloride)-b-polystyrene for the formation of anion exchange membranes. Macromolecules 47(19):6757–6767

  31. 31

    Cong L, Li X, Ma L, Peng Z, Yang C, Han P, Song G (2018) High-performance graphene oxide/carbon nanotubes aerogel-polystyrene composites: preparation and mechanical properties. Mater Lett 214:190–193

  32. 32

    Park W, Hu J, Jauregui LA, Ruan X, Chen YP (2014) Electrical and thermal conductivities of reduced graphene oxide/polystyrene composites. Appl Phys Lett 104(11):113101

  33. 33

    Ruan K, Guo Y, Tang Y, Zhang Y, Zhang J, He M, Gu J (2018) Improved thermal conductivities in polystyrene nanocomposites by incorporating thermal reduced graphene oxide via electrospinning-hot press technique. Compos Commun 10:68–72

  34. 34

    Ghanem A, Abdel Rehim M (2018) Assisted tip sonication approach for graphene synthesis in aqueous dispersion. Biomedicines 6(2):63

  35. 35

    Grumezescu A (2016) Food packaging, 1st edn. Elsevier, Amsterdam

  36. 36

    Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80(6):1339

  37. 37

    Yu R, Zhang S, Luo Y, Bai R, Zhou J, Song H (2015) Synthetic possibility of polystyrene functionalization based on hydroxyl groups of graphene oxide as nucleophiles. New J Chem 39(7):5096–5099

  38. 38

    Camps M, Chatzopoulos M, Camps JM, Montheard JP (1987) Chloromethylation of polystyrenes and styrene copolymers. Applications. J Macromol Sci 27(3–4):505–557

  39. 39

    Emiru TF, Ayele DW (2017) Controlled synthesis, characterization and reduction of graphene oxide: a convenient method for large scale production. Egypt J Basic Appl Sci 4(1):74–79

  40. 40

    Jung JM, Jung CH, Oh MS, Hwang IT, Jung CH, Shin K, Choi JH (2014) Rapid, facile, and eco-friendly reduction of graphene oxide by electron beam irradiation in an alcohol–water solution. Mater Lett 126:151–153

  41. 41

    Park S, An J, Jung I, Piner RD, An SJ, Li X, Ruoff RS (2009) Colloidal suspensions of highly reduced graphene oxide in a wide variety of organic solvents. Nano Lett 9(4):1593–1597

  42. 42

    Zhang SP, Song HO (2012) Supramolecular graphene oxide-alkylamine hybrid materials: variation of dispersibility and improvement of thermal stability. New J Chem 36(9):1733–1738

  43. 43

    Ghanem AF, Williams RL, Rehim MA, Tian ZR (2014) Tuning a hydrophilic nanobelt’s crystal lattice for interface-tailored nanocompositing with a hydrophobic polymer. J Mater Sci 49(21):7382–7390.

  44. 44

    Lee YS, Byoun YS (2002) Poly (styrene-co-4-vinylbenzyl chloride) conjugated with 3-(dimethylamino) phenol: synthesis and antibacterial activity. Bull Korean Chem Soc 23(12):1833–1835

  45. 45

    Brown PS, Bhushan B (2017) Mechanically durable liquid-impregnated honeycomb surfaces. Sci Rep 7(1):6083

  46. 46

    Good RJ, Kotsidas ED (1978) The contact angle of water on polystyrene: a study of the cause of hysteresis. J Colloid Interface Sci 66(2):360–362

  47. 47

    Bansal SA, Singh AP, Kumar S (2018) Synergistic effect of graphene and carbon nanotubes on mechanical and thermal performance of polystyrene. Mater Res Express 5(7):075602

  48. 48

    Heeder N, Chakraborty I, Bose A, Shukla A (2015) Electro-mechanical behavior of graphene–polystyrene composites under dynamic loading. J Dyn Behav Mater 1(1):43–54

  49. 49

    Li Y, Porwal H, Huang Z, Zhang H, Bilotti E, Peijs T (2016) Enhanced thermal and electrical properties of polystyrene-graphene nanofibers via electrospinning. J Nanomater 2016:18

  50. 50

    Chiu F-C, Li M-T (2003) Miscibility, thermal properties and polymorphism of syndiotactic polystyrene/poly(styrene-co-α-methyl styrene) blends. Polymer 44:8013

  51. 51

    Hahladakis JN, Iacovidou E (2018) Closing the loop on plastic packaging materials: what is quality and how does it affect their circularity? Sci Total Environ 630:1394–1400

  52. 52

    Stukalin EB, Douglas JF, Freed KF (2010) Plasticization and antiplasticization of polymer melts diluted by low molar mass species. J Chem Phys 132(8):084504

  53. 53

    Pant BG, Kulkarni SS, Panse DG, Joshi SG (1994) Modification of polystyrene barrier properties. Polymer 35(12):2549–2553

  54. 54

    Paul K, Richard K (2017) Water vapor permeation in plastics. Pacific Northwest National Laboratory, U.S. Department of Energy Contract DE-AC05-76RL01830

  55. 55

    Huang K, Liu G, Jin W (2017) Vapor transport in graphene oxide laminates and their application in pervaporation. Curr Opin Chem Eng 16:56–64

  56. 56

    Nair RR, Wu HA, Jayaram PN, Grigorieva IV, Geim AK (2012) Unimpeded permeation of water through helium-leak–tight graphene-basedmembranes. Science 335(6067):442–444

  57. 57

    Kumar Kannam S, Todd BD, Hansen JS, Daivis PJ (2012) Slip length of water on graphene: limitations of non-equilibrium molecular dynamics simulations. J Chem Phys 136(2):024705

  58. 58

    Maeda Y, Paul DR (1987) Effect of antiplasticization on selectivity and productivity of gas separation membranes. J Membr Sci 30(1):1–9

  59. 59

    Kamal MR, Jinnah IA, Utracki LA (1984) Permeability of oxygen and water vapor through polyethylene/polyamide films. Polym Eng Sci 24(17):1337–1347

  60. 60

    Akhavan O, Ghaderi E (2010) Toxicity of graphene and graphene oxide nanowalls against bacteria. ACS Nano 4(10):5731–5736

  61. 61

    Lerf A, He H, Forster M, Klinowski J (1998) Structure of graphite oxide revisited. J Phys Chem B 102(23):4477–4482

  62. 62

    Ge C, Li Y, Yin JJ, Liu Y, Wang L, Zhao Y, Chen C (2012) The contributions of metal impurities and tube structure to the toxicity of carbon nanotube materials. NPG Asia Mater 4(12):e32

  63. 63

    He W, Liu Y, Wamer WG, Yin JJ (2014) Electron spin resonance spectroscopy for the study of nanomaterial-mediated generation of reactive oxygen species. J Food Drug Anal 22(1):49–63

  64. 64

    Zhang W, Wang C, Li Z, Lu Z, Li Y, Yin JJ, Zhao Y (2012) Unraveling stress induced toxicity properties of graphene oxide and the underlying mechanism. Adv Mater 24(39):5391–5397

  65. 65

    Rahman K (2007) Studies on free radicals, antioxidants, and co-factors. Clin Interv Aging 2(2):219

Download references


The authors are grateful for Prof. Mayssa Mohram for helping in the investigation of the antimicrobial properties.

Author information

Correspondence to Ahmed F. Ghanem.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Ghanem, A.F., Youssef, A.M. & Abdel Rehim, M.H. Hydrophobically modified graphene oxide as a barrier and antibacterial agent for polystyrene packaging. J Mater Sci 55, 4685–4700 (2020) doi:10.1007/s10853-019-04333-7

Download citation