Effect of electrostatic interaction on phase separation behaviour of chitin crystallite suspensions

Optical and electron microscopy were used to observe the dynamics of the phase separation in aqueous chitin suspensions prepared by HCl hydrolysis of crab chitin. Freeze-fracture transmission electron microscopy reveals that chitin crystallites are partially aggregated in the suspension and have an average length of 200 nm and an average width of 8 nm. They exhibit a positive surface charge of approximately 0.5 e/nm2 when fully protonated. The liquid crystal-forming aqueous suspensions of such crystallites are investigated through phase diagrams and Zeta potential measurements for different ionic strength. Exposure of the suspension to a low concentration of univalent electrolyte has a negligible effect on phase separation because of the contribution of the charged crystallites themselves to the ionic strength. The thickness of the effective repulsive layer is estimated both from the phase diagrams according to Onsager's theory and from the computed interaction energy derived from the Poisson-Boltzmann equation using the experimental Zeta potential as surface potential. When the contribution of crystallites to the ionic strength is taken into account and an hypothetical linear charge density close to the Manning limit is assumed, there is good agreement with the Debye length.