Shear-Coated Linear Birefringent and Chiral Cellulose Nanocrystal Films Prepared from Non-Sonicated Suspensions with Different Storage Time.

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.

Pitch profile across the cuticle of the scarab beetle Cotinis mutabilis determined by analysis of Mueller matrix measurements.

Helicoidal structures of lamellae of nanofibrils constitute the cuticle of some scarab beetles with iridescent metallic-like shine reflecting left-handed polarized light. The spectral and polarization properties of the reflected light depend on the pitch of the helicoidal structures, dispersion of effective refractive indices and thicknesses of layers in the cuticle. By modelling the outer exocuticle of the scarab beetle Cotinis mutabilis as a stack of continuously twisted biaxial slices of transparent materials, we extract optical and structural parameters by nonlinear regression analysis of variable-angle Mueller-matrix spectroscopic data. Inhomogeneities in the beetle cuticle produce depolarization with non-uniformity in cuticle thickness as the dominant effect. The pitch across the cuticle of C. mutabilis decreased with depth in a two-level profile from 380 to 335 nm and from 390 to 361 nm in greenish and reddish specimens, respectively, whereas in a yellowish specimen, the pitch decreased with depth in a three-level profile from 388 to 326 nm.

Linear Birefringent Films of Cellulose Nanocrystals Produced by Dip-Coating.

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.