No abstract

Transparent films of cellulose nanocrystals (CNC) are prepared by dip-coating on glass substrates from aqueous suspensions of hydrolyzed filter paper. Dragging forces acting during films’ deposition promote a preferential alignment of the rod-shaped CNC. Films that are 2.8 and 6.0 µm in thickness show retardance effects, as evidenced by placing them between a linearly polarized light source and a linear polarizer sheet in the extinction configuration. Transmission Mueller matrix spectroscopic ellipsometry measurements at normal incidence as a function of sample rotation were used to characterize polarization properties. A differential decomposition of the Mueller matrix reveals linear birefringence as the unique polarization parameter. These results show a promising way for obtaining CNC birefringent films by a simple and controllable method.

We report a simple route to produce chitin films with different crystalline structures.

Nanocelluloses are very attractive materials for creating structured films with unique optical properties using different preparation techniques. Evaporation-induced self-assembly of cellulose nanocrystals (CNC) aqueous suspensions produces iridescent films with selective circular Bragg reflection. Blade coating of sonicated CNC suspensions leads to birefringent CNC films. In this work, fabrication of both birefringent and chiral films from non-sonicated CNC suspensions using a shear-coating method is studied. Polarization optical microscopy and steady-state viscosity profiles show that non-sonicated CNC suspensions (concentration of 6.5 wt%) evolve with storage time from a gel-like shear-thinning fluid to a mixture of isotropic and chiral nematic liquid crystalline phases. Shear-coated films prepared from non-sonicated fresh CNC suspensions are birefringent, whereas films prepared from suspensions stored several weeks show reflection of left-handed polarized light. Quantification of linear and circular birefringence as well circular dichroism in the films is achieved by using a Mueller matrix formalism.

Evaporation-induced-self-assembly is widely used to produce chiral cellulose nanocrystal (CNC) free-standing films reflecting left-handed polarized light. Research on supported chiral CNC films is rather scarce. The reflection and/or transmission of unpolarized light are the most common optical techniques used to characterize the selective reflection of CNC films whereas the use of techniques to quantify chiral properties is limited. Here, the fabrication of chiral CNC films supported on glass substrates by a shear-coating method, as well as a full characterization of their polarization properties, are reported. Optical chirality is evidenced in films, showing a brilliant blue structural color when viewed through a left-handed polarizer and darkness through a right-handed polarizer. Mueller-matrix data in the reflection and transmission modes are used to quantitatively characterize the structural origin of color in the films. The quantification of the linear and circular birefringence, as well as circular dichroism, is performed by analytical inversion of the Mueller matrix data in the transmission mode and regression analysis using Tellegen constitutive equations. The equivalence of the two methods to quantify the structural chirality in CNC films is demonstrated. The swelling of films in water and kinetics during drying is studied by reflection spectroscopy.