Rheologica Acta

, Volume 56, Issue 11, pp 941–953 | Cite as

Rheology and structural changes of plasticized zeins in the molten state

  • Laurent ChaunierEmail author
  • Guy Della Valle
  • Michèle Dalgalarrondo
  • Denis Lourdin
  • Didier Marion
  • Eric Leroy
Original Contribution


Zeins, storage proteins from maize, are suitable for making biobased thermoplastic materials. The rheological behavior of a commercial zein plasticized with 20 w% glycerol was studied in the molten state by steady-state flow experiments in extrusion conditions and oscillatory rheometry. For low residence times, a shear-thinning viscoelastic behavior was observed, with G″ exceeding G′. After 300 s at 130 °C, the complex viscosity |η | = 7 × 103 ω −0.46 was found to be similar to that of thermoplastic polymer melts used in fused deposition modeling. However, the ratio between the exponents of the power laws describing G′(ω) and G″(ω) did not meet the typical value of 2 for entangled polymer melts. Moreover, for longer residence times, the viscosity increased and a gelation phenomenon was observed with a crossing over of G′(ω) and G″(ω). Gel times ranged from 6000 s at 120 °C to 1700 s at 150 °C. The evolution of the macromolecular structure assessed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and high-performance size exclusion chromatography suggested that this gelation phenomenon involves various types of covalent and non-covalent cross-links. Disulfide bonds played a significant role in gelation kinetics despite a very low cysteine residue content in the protein primary structure (about 1 mol%). These results suggested that plasticized zeins initially behave like a low-viscosity non-entangled polymer melt, before cross-linking progressively led to a continuous network.


Complex viscosity Cross-linking Disulfide bond Fused deposition modeling Gel point Maize protein 



The authors would like to thank Bénédicte Bakan and Roselyne Désirest (INRA, Nantes) for their helpful discussions and experimental trials.

Supplementary material

397_2017_1045_MOESM1_ESM.pdf (525 kb)
ESM 1 (PDF 525 kb)


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Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.INRA, UR1268 BIA Biopolymers Interactions and AssembliesNantesFrance
  2. 2.CNRS, GEPEA UMR-CNRS-6144, CRTTSt-Nazaire CedexFrance

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