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- On the influence of imidazolium ionic liquids on cellulose derived polymersPublication . Paiva, Tiago; Echeverria Zabala, Coro; Godinho, Maria Helena; Almeida, Pedro L.; Corvo, Marta C.The demand for better cellulose solvents has driven the search for new and improved materials to enable the processing of this polysaccharide. Ionic liquids have been debated for a long time as interesting alternatives, but the molecular details on the solubilization mechanism have been a matter of controversy. Herein, for the first time, the structure and dynamics of hydroxypropylcellulose (HPC) liquid crystal solutions were probed in the presence of imidazolium ionic liquids (ILs), conjugating rheological measurements with magnetic resonance spectroscopy. This study provides a characterization of the solutions macroscopic behaviour, where the liquid crystalline (LC) properties were maintained. Using ILs with different side chain lengths, the influence of the hydrophobic IL domain in the solvation abilities of ILs towards a cellulose derived polymer was accessed, providing experimental evidence on these interactions.
- Cellulose-based biomimetics and their applicationsPublication . Almeida, Ana; Canejo, João; Fernandes, Susete; Echeverria Zabala, Coro; Almeida, Pedro L.; Godinho, Maria HelenaNature has been producing cellulose since long before man walked the surface of the earth. Millions of years of natural design and testing have resulted in cellulose-based structures that are an inspiration for the production of synthetic materials based on cellulose with properties that can mimic natural designs, functions, and properties. Here, five sections describe cellulose-based materials with characteristics that are inspired by gratings that exist on the petals of the plants, structurally colored materials, helical filaments produced by plants, water-responsive materials in plants, and environmental stimuli-responsive tissues found in insects and plants. The synthetic cellulose-based materials described herein are in the form of fibers and films. Fascinating multifunctional materials are prepared from cellulose-based liquid crystals and from composite cellulosic materials that combine functionality with structural performance. Future and recent applications are outlined.
- Understanding the influence of carbon nanotubes on the flow behavior of liquid crystalline hydroxypropylcellulose: a Rheo-NMR studyPublication . Echeverria Zabala, Coro; Almeida, Pedro L.; Figueirinhas, João; Godinho, Maria HelenaHydroxypropyl celulose (HPC) is na importante celulose derivative that has been widely studied due to its water solubility, biocompatibility and biodegradability, but even more significant due to its ability to form liquid crystalline phases. HPC is able to form, under certain conditions, chiral nematic (cholesteric) structures in water solutions. Previous work confirmed that films prepared from liquid crystalline HPC/water solutions (LC-HPC) gave rise to anisotropic networks, with similar mechanical and optical characteristics of Liquid Crystalline Elastomers (LCE), capable to respond to humidity. It was also demonstrated that the incorporation of carbon nanotubes (CNTs) significantly improved the actuator responsiveness. In the work presented herein, we investigate how the incorporation of carbon nanotubes affects the flow behavior o fLC-HPC solutions, and thus the structure-properties relationship, through a detailed Rheo-NMR study. As observed from the results, when shearing the samples, the degree of order reached (maximum quadrupolar peak splitting) by LC-HPC solutions increases with CNT content. Regarding the subsequente relaxation process, only the incorporation of 0.01 wt% of CNTs (lowest content) contributes to a faster recovery of cholesteric structure.
- Two negative minima of the first normal stress difference in a cellulose-based cholesteric liquid crystal: Helix uncoilingPublication . Echeverria Zabala, Coro; Almeida, Pedro L.; Gutierrez, Oscar F. Aguilar; Rey, Alejandro D.; Godinho, Maria HelenaThe shear rate dependence of material functions such as shear viscosity (η) and the first normal stress difference (N1) were given and interpreted earlier by Kiss and Porter. Their widely accepted work revealed the possibility of having a negative minimum of N1 for polymeric liquid crystals. In this work, we disclose for the first time the evidence of two negative N1 minima on a sheared cellulosic lyotropic system. The lower shear rate minimum is ascribed to the uncoiling of the cholesteric helix, as theoretically predicted earlier. Our findings contribute also to the understanding of the other minimum already reported in the literature and attributed to the nematic director tumbling mode. Moreover, the elastic change that the LC-HPC sample undergoes during the helix unwinding of the cholesteric structure is also by means of oscillatory measurements. This study is a contribution for the understanding of the structure-properties relationship linked with the complex rheological behavior of chiral nematic cellulose-based systems and may help to improve their further processing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.