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Retrieving the Coassembly Pathway of Composite Cellulose Nanocrystal Photonic Films from their Angular Optical Response.

ABSTRACT: Aqueous suspensions of cellulose nanocrystals (CNCs) are known to self-assemble into a chiral nematic liquid crystalline phase, leading to solid-state nanostructured colored films upon solvent evaporation, even in the presence of templating agents. The angular optical response of these structures, and therefore their visual appearance, are completely determined by the spatial arrangement of the CNCs when the drying suspension undergoes a transition from a flowing and liquid crystalline state to a kinetically arrested state. Here, it is demonstrated how the angular response of the final film allows for retrieval of key physical properties and the chemical composition of the suspension at the onset of the kinetic arrest, thus capturing a snapshot of the past. To illustrate this methodology, a dynamically evolving sol-gel coassembly process is investigated by adding various amounts of organosilica precursor, namely, 1,2-bis(trimethoxysilyl)ethane. The influence of organosilica condensation on the kinetic arrest can be tracked and thus explains the angular response of the resulting films. The a posteriori and in situ approach is general; it can be applied to a variety of additives in CNC-based films and it allows access to key rheological information of the suspension without using any dedicated rheological technique.

SUBMITTER: Frka-Petesic B

PROVIDER: S-EPMC7116217 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Cellulose nanocrystals (CNCs) are bio-sourced chiral nanorods that can form stable colloidal suspensions able to spontaneously assemble above a critical concentration into a cholesteric liquid crystal, with a cholesteric pitch usually in the micron range. When these suspensions are dried on a substrate, solid films with a pitch of the order of few hundreds of nanometers can be produced, leading to intense reflection in the visible range. However, the resulting cholesteric nanostructure is usually not homogeneous within a sample and comports important variations of the cholesteric domain orientation and pitch, which affect the photonic properties. In this work, we first propose a model accounting for the formation of the photonic structure from the vertical compression of the cholesteric suspension upon solvent evaporation, starting at the onset of the kinetic arrest of the drying suspension and ending when solvent evaporation is complete. From that assumption, various structural features of the films can be derived, such as the variation of the cholesteric pitch with the domain tilt, the orientation distribution density of the final cholesteric domains and the distortion of the helix from the unperturbed cholesteric case. The angular-resolved optical response of such films is then derived, including the iridescence and the generation of higher order reflection bands, and a simulation of the angular optical response is provided, including its tailoring under external magnetic fields. Second, we conducted an experimental investigation of CNC films covering a structural and optical analysis of the films. The macroscopic appearance of the films is discussed and complemented with angular-resolved optical spectroscopy, optical and electron microscopy, and our quantitative analysis shows an excellent agreement with the proposed model. This allows us to access the precise composition and the pitch of the suspension when it transited into a kinetically arrested phase directly from the optical analysis of the film. This work highlights the key role that the anisotropic compression of the kinetically arrested state plays in the formation of CNC films and is relevant to the broader case of structure formation in cast dispersions and colloidal self-assembly upon solvent evaporation.

Project description:A known deterrent to the large-scale development and use of cellulose nanocrystals (CNCs) in composite materials is their affinity for moisture, which has a profound effect on dispersion, wetting, interfacial adhesion, matrix crystallization, water uptake, and hydrothermal stability. To quantify and control the hydration and confinement of absorbed water in CNCs, we studied sulfated-CNCs neutralized with sodium cations and CNCs functionalized with less hydrophilic methyl(triphenyl)phosphonium cations. Films were cast from water suspensions at 20 °C under controlled humidity and drying rate, yielding CNC materials with distinguishably different dielectric properties and cholesteric structures. By controlling the evaporation rate, we obtained self-assembled chiral CNC films with extended uniformity, having helical modulation length (nominal pitch) tunable from 1300 to 600 nm. SEM imaging and UV-vis-NIR total reflectance spectra revealed tighter and more uniform CNC packing in films cast at slow evaporation rates or having lower surface energy when modified with phosphonium. The dielectric constant was measured by a noncontact microwave cavity perturbation method and fitted to a classical mixing model employing randomly oriented ellipsoidal water inclusions. The dielectric constant of absorbed water was found to be significantly smaller than that for free liquid indicating a limited mobility due to binding with the CNC "matrix". In the case of hydrophilic Na-modified CNCs, a decreasing pitch led to greater anisotropy in the shape of moisture inclusions (ellipsoidal to platelet-like) and greater confinement. In contrast, the structure of hydrophobic phosphonium-modified CNC films was found to have reduced pitch, yet the shape of confined water remained predominantly spherical. These results provide a useful perspective on the current state of understanding of CNC-water interactions as well as on CNC self-assembly mechanisms. More broadly, we believe that our results are beneficial for the realization of CNC-based functional materials and composites.

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Retrieving the Coassembly Pathway of Composite Cellulose Nanocrystal Photonic Films from their Angular Optical Response.

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