Unique rheological behavior of chitosan-modified nanoclay at highly hydrated state.

This work attempts to explore the dynamic and steady-state rheological properties of chitosan modified clay (CMCs) at highly hydrated state. CMCs with different initial chitosan/clay weight ratios (s) were prepared from pre-exfoliated clay via electrostatic adsorption process. Thermogravimetric analysis and optical microscopy were used to determine the adsorbed content of chitosan (m) in CMCs and the microstructure of CMCs at highly hydrated state, respectively. Dynamic rheological results indicate that both stress-strain behavior and moduli of CMCs exhibit strong dependence on m. Shear-thinning behavior for all of CMCs is observed and further confirmed by steady-state shear test. Interestingly, two unique transitions, denoted as a small peak region of the shear viscosity for CMCs with m > 2.1% and a sharp drop region of the shear viscosity for CMCs with m <or= 6.3%, were observed at shear rate range of about 10 < gamma < 40 and 0.2 < gamma < 0.5 s(- 1), respectively. Further, analysis on the recovery of CMCs at rest after underwent a preshearing process was performed with an emphasis to explain the presence of these unique transitions. Thixotropic effect was observed in CMCs and showed strong dependence on m and the preshearing history. Failure to Cox-Merz rule of the rheological behavior of CMCs suggests that some preferential orientation of the initial quiescent random arrangement of CMCs particles or their tactoids occurs under the applied shearing.