Skip to main content
Log in

Interplay between processing and performance in chitosan-based clay nanocomposite films

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

Abstract

Chitosan sodium montmorillonite (NaMMT) nanocomposite films, with or without addition of glycerol, are prepared by three different processing methods, i.e., solution casting, heat pressing and casting of sonicated solutions. The effect of processing is being investigated using X-ray diffraction, tensile tests, dynamic mechanical analysis, and water sorption tests. Processing plays a significant role in the hydrated crystalline structure of chitosan; however, it is less crucial for the degree of exfoliation/intercalation of NaMMT. The addition of NaMMT fillers induces substantial reinforcing effects in the chitosan/NaMMT systems with up to 160 % increase in stiffness, strength and 200 % increase in the storage modulus in comparison to the unfilled systems. Although highest stiffness and strength are achieved at different NaMMT contents for the three processing routes, the overall enhancement is similar. The addition of glycerol reduces the reinforcing efficiency of the NaMMT filler and results in plasticization by lowering the stiffness, strength, storage modulus and the glass transition temperature of chitosan (T g). In the absence of glycerol, sonication results in nanocomposite films with higher strain at break and higher T g values. Heat pressing results in a tremendous reduction (more than one order of magnitude) of the absorbed water in chitosan nanocomposite films without glycerol.

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.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Muzzarelli RAA (2012) Nanochitins and nanochitosans, paving the way to eco-friendly and energy-saving exploitation of marine resources. In: Matyjaszewski K, Moller M (eds) Polymer science: a comprehensive reference, vol 10. Elsevier BV, pp 153–164

  2. Muzzarelli RAA, Boudrant J, Meyer D, Manno N, Demarchis M, Paoletti MG (2012) Current views on fungal chitin/chitosan, human chitinases, food preservation, glucans, pectins and inulin: a tribute to Henri Braconnot, precursor of the carbohydrate polymers science, on the chitin bicentennial. Carbohydr Polym 87:995–1012

    Article  CAS  Google Scholar 

  3. Rhim J-W, Ng PKW (2007) Natural biopolymer-based nanocomposite films for packaging applications. Crit Rev Food Sci Nutr 47:411–433

    Article  CAS  Google Scholar 

  4. Shin MS, Kang HS, Park TG, Yang JW (2002) Synthesis and characterization of pH/temperature-sensitive hydrogels based on chitosan derivative. Polym Bull 47:451–456

    Article  CAS  Google Scholar 

  5. Chivrac F, Pollet E, Avérous L (2009) Progress in nano-biocomposites based on polysaccharides and nanoclays. Mater Sci Eng R67:1–17

    Article  CAS  Google Scholar 

  6. Günister E, Pestreli D, Ünlü CH, Atici O, Güngör N (2007) Synthesis and characterization of chitosan-MMT biocomposite systems. Carbohydr Polym 67:358–365

    Article  Google Scholar 

  7. Lin K-F, Hsu C-Y, Huang T-S, Chiu W-Y, Lee Y-H, Young T-H (2005) A novel method to prepare chitosan/montmorillonite nanocomposites. J Appl Polym Sci 98:2042–2047

    Article  CAS  Google Scholar 

  8. Ray SS, Bousmina M (2005) Biodegradable polymers and their layered silicate nanocomposites: in greening the 21st century materials world. Prog Mater Sci 50:962–1079

    Article  CAS  Google Scholar 

  9. Wang SF, Shen L, Tong YJ, Chen L, Phang IY, Lim PQ, Liu TX (2005) Biopolymer chitosan/montmorillonite nanocomposites: preparation and characterization. Polym Degrad Stab 90:123–131

    Article  CAS  Google Scholar 

  10. Xu Y, Ren X, Hanna MA (2006) Chitosan/clay nanocomposite film preparation and characterization. J Appl Polym Sci 99:1684–1691

    Article  CAS  Google Scholar 

  11. Essawy H, Badran A, Youssef A, Abd El-Hakim AF (2004) Synthesis of poly(methylmethacrylate)/montmorillonite nanocomposites via in situ intercalative suspension and emulsion polymerization. Polym Bull 53:9–17

    Article  CAS  Google Scholar 

  12. Farshi Azhar F, Olad A, Mirmohseni A (2014) Development of novel hybrid nanocomposites based on natural biodegradable polymer–montmorillonite/polyaniline: preparation and characterization. Polym Bull 71:1591–1610

    Article  CAS  Google Scholar 

  13. Hong SI, Lee JH, Bae HJ, Koo SY, Lee HS, Choi JH, Kim DH, Park S-H, Park HJ (2011) Effect of shear rate on structural, mechanical, and barrier properties of chitosan/montmorillonite nanocomposite film. J Appl Polym Sci 119:2742–2749

    Article  CAS  Google Scholar 

  14. Oguzlu H, Tihminlioglu F (2010) Preparation and barrier properties of chitosan-layered silicate nanocomposite films. Macromol Symp 298:91–98

    Article  CAS  Google Scholar 

  15. Potarniche CG, Vuluga Z, Donescu D, Christiansen JDC, Eugeniu V, Radovici C, Serban S, Ghiurea M, Somoghi R, Beckmann S (2012) Morphology study of layered silicate/chitosan nanohybrids. Surf Interface Anal 44:200–207

    Article  CAS  Google Scholar 

  16. Wang SF, Shen L, Zhang WD, Tong YJ (2005) Preparation and mechanical properties of chitosan/carbon nanotubes composites. Biomacromolecules 6:3067–3072

    Article  CAS  Google Scholar 

  17. Lavorgna M, Piscitelli F, Mangiacapra P, Buonocore GG (2010) Study of the combined effect of both clay and glycerol plasticizer on the properties of chitosan films. Carbohydr Polym 82:291–298

    Article  CAS  Google Scholar 

  18. Ogawa K (1991) Effect of heating an aqueous suspension of chitosan on the crystallinity and polymorphs. Agric Biol Chem 55:2375–2379

    Article  CAS  Google Scholar 

  19. Ogawa K, Yui T, Miya M (1992) Dependence on the preparation procedure of the polymorphism and crystallinity of chitosan membranes. Biosci Biotechnol Biochem 56:858–862

    Article  CAS  Google Scholar 

  20. Mayachiew P, Devahastin S (2008) Comparative evaluation of physical properties of edible chitosan films prepared by different drying methods. Drying Technol 26:176–185

    Article  CAS  Google Scholar 

  21. Thakhiew W, Devahastin S, Soponronnarit S (2010) Effects of drying methods and plasticizer concentration on some physical and mechanical properties of edible chitosan films. J Food Eng 99:216–224

    Article  CAS  Google Scholar 

  22. Giannakas A, Grigoriadi K, Leontiou A, Barkoula N-M, Ladavos A (2014) Preparation, characterization, mechanical and barrier properties investigation of chitosan-clay nanocomposites. Carbohydr Polym 108:103–111

    Article  CAS  Google Scholar 

  23. Rhim J-W, Hong S-I, Park H-M, Ng PKW (2006) Preparation and characterization of chitosan-based nanocomposite films with antimicrobial activity. J Agric Food Chem 54:5814–5822

    Article  CAS  Google Scholar 

  24. Tang C, Chen N, Zhang Q, Wang K, Fu Q, Zhang X (2009) Preparation and properties of chitosan nanocomposites with nanofillers of different dimensions. Polym Degrad Stab 94:124–131

    Article  CAS  Google Scholar 

  25. Gartner C, Löpez BL, Sierra L, Graf R, Spiess HW, Gaborieau M (2011) Interplay between structure and dynamics in chitosan films investigated with solid-state NMR, dynamic mechanical analysis, and X-ray diffraction. Biomacromolecules 12:1380–1386

    Article  CAS  Google Scholar 

  26. Ziani K, Oses J, Coma V, Maté JI (2008) Effect of the presence of glycerol and tween 20 on the chemical and physical properties of films based on chitosan with different degree of deacetylation LWT Food. Sci Technol 41:2159–2165

    CAS  Google Scholar 

  27. Epure V, Griffon M, Pollet E, Avérous L (2011) Structure and properties of glycerol-plasticized chitosan obtained by mechanical kneading. Carbohydr Polym 83:947–952

    Article  CAS  Google Scholar 

  28. Xie DF, Martino VP, Sangwan P, Way C, Cash GA, Pollet E, Dean KM, Halley PJ, Avérous L (2013) Elaboration and properties of plasticised chitosan-based exfoliated nano-biocomposites. Polymer 54:3654–3662

    Article  CAS  Google Scholar 

  29. Suyatma NE, Tighzert L, Copinet A, Coma V (2005) effects of hydrophilic plasticizers on mechanical, thermal, and surface properties of chitosan films. J Agric Food Chem 53:3950–3957

    Article  CAS  Google Scholar 

  30. Zhang JP, Wang AQ (2009) Synergistic effects of Na+-montmorillonite and multi-walled carbon nanotubes on mechanical properties of chitosan film. Expr Polym Lett 3:302–308

    Article  CAS  Google Scholar 

  31. Petrova VA, Nud’Ga LA, Bochek AM, Yudin VE, Gofman IV, Elokhovskii VYu, Dobrovol’Skaya IP (2012) Specific features of chitosan-montmorillonite interaction in an aqueous acid solution and properties of related composite films. Polym Sci Ser A Polym Phys 54:224–230

    Article  CAS  Google Scholar 

  32. Quijada-Garrido I, Iglesias-González V, Mazón-Arechederra JM, Barrales-Rienda JM (2007) The role played by the interactions of small molecules with chitosan and their transition temperatures. Glass-forming liquids: 1,2,3-propantriol (glycerol). Carbohydr Polym 68:173–186

    Article  CAS  Google Scholar 

  33. Ogura K, Kanamoto T, Itoh M, Miyashiro H, Tanaka K (1980) Dynamic mechanical behavior of chitin and chitosan. Polym Bull 2:301–304

    Article  CAS  Google Scholar 

  34. Rao Y, Pochan JM (2007) Mechanics of polymer-clay nanocomposites. Macromolecules 40:290–296

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Nektaria-Marianthi Barkoula.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Grigoriadi, K., Giannakas, A., Ladavos, A.K. et al. Interplay between processing and performance in chitosan-based clay nanocomposite films. Polym. Bull. 72, 1145–1161 (2015). https://doi.org/10.1007/s00289-015-1329-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-015-1329-0

Keywords

Navigation