Most attempts to emulate the mechanical properties of strong and tough natural composites using helicoidal films of wood-derived cellulose nanocrystals (w-CNCs) fall short in mechanical performance due to the limited shear transfer ability between the w-CNCs. This shortcoming is ascribed to the small w-CNC-w-CNC overlap lengths that lower the shear transfer efficiency. Herein, we present a simple strategy to fabricate superior helicoidal CNC films with mechanical properties that rival those of the best natural materials and are some of the best reported for photonic CNC materials thus far. Assembling the short w-CNCs with a minority fraction of high aspect ratio CNCs derived from tunicates (t-CNCs), we report remarkable simultaneous enhancement of all in-plane mechanical properties and out-of-plane flexibility. The important role of t-CNCs is revealed by coarse grained molecular dynamics simulations where the property enhancement are due to increased interaction lengths and the activation of additional toughening mechanisms. At t-CNC contents greater than 5% by mass the mixed films also display UV reflecting behaviour. These damage tolerant optically active materials hold great promise for application as protective coatings. More broadly, we expect the strategy of using length-bidispersity to be adaptable to mechanically enhancing other matrix-free nanoparticle ensembles.

a laboratory scale, many polymer/CNC nano composites have been prepared and were demonstrated to exhibit a significant improvement in mechanical properties over the parent polymers. However, the technological exploitation of CNCs as reinforcing filler will hinge on the question if or how well such laboratory-scale results can be achieved by technologically viable processes. Unfortunately, systematic studies that correlate processing, structure, and mechanical properties of CNC nanocomposites are rare. In a previous study we demonstrated that once CNCs are well dispersed in amphiphilic polymers such as poly(vinyl acetate) [11] or hydrophobic polymers such as low-density polyethylene (LDPE), [16] they can be subsequently reprocessed via melt-mixing and retained similar dispersion and mechanical reinforcement, as long as highshear mixing, which caused mechanical degradation of the CNCs, was avoided.It appears to be particularly difficult to fabricate composites of the rather polar CNCs in hydrophobic polymer matrices such as LDPE, as the polarity differenceThe preparation of nanocomposites of low-density polyethylene (LDPE) and cellulose nanocrystals (CNCs) isolated from cotton or produced in situ by the dispersion of microcrystalline cellulose (MCC) is reported. The hydrophobic matrix polymer and the rather polar filler particles appear to be difficult to mix, but it is shown here that composites with significantly improved mechanical characteristics and of homogeneous appearance can be produced using an organic-solvent-free two-step process. This is achieved by first mixing an aqueous slurry of an LDPE powder with an average particle size of <600 μm with aqueous suspensions of CNCs or MCC and removing most, but not all, of the water. Compounding such water-plasticized mixtures in a roller-blade mixer and subsequent compression-molding afford highly transparent films, whose room-temperature storage modulus is increased by a factor of 2.5 upon incorporation of 15% w/w CNCs or MCC. The results demonstrate that LDPE/nanocellulose composites with improved mechanical properties can be produced by an organic solvent-free process that appears to be scalable to industrial production scale.

Building blocks made from renewable sources attract increasing attention for the design of new polymer systems. Recently, in this particular context, cellulose nanocrystals (CNCs) have gained great interest in both academic research and industry, mainly on account of their ability to reinforce range of polymer matrices and afford nanocomposites with attractive mechanical properties. The limited thermal stability of conventionally produced cellulose nanocrystals (CNCs) has, however, so far limited the range of polymers that could be used as basis for melt‐processed CNC nanocomposites. We herein show that a commercially accessible nanocrystal source, a particular grade of microcrystalline cellulose (MCC), can easily be converted into thermally stable CNCs by ultrasonication in phosphoric acid. A scalable melt‐mixing process was used to produce nanocomposites of these CNCs with a thermoplastic polyurethane (TPU) elastomer. A significant improvement of the room temperature storage modulus from 40 MPa (neat polymer) to 120 MPa (10% w/w CNC) was observed. The introduction of CNCs not only increased the stiffness of the polymer matrix, but also improved the shape memory properties of the nanocomposite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45033.

Cellulose nanocrystals (CNCs) are mechanically rigid, toxicologically benign, fiber-like nanoparticles. They can easily be extracted from renewable biosources and have attracted significant interest as reinforcing fillers in polymers. We here report the modification of CNCs with the 2-ureido-4[1H]pyrimidinone (UPy) motif as an adaptive compatibilizer, which permits the dispersion of UPy-modified CNCs in nonpolar as well as polar media. In toluene, the UPy motifs appear to form intra-CNC dimers, so that the particles are somewhat hydrophobized and well-dispersible in this nonpolar solvent. By contrast, the UPy motifs dissociate in DMF and promote dispersibility through interactions with this polar solvent. We have exploited this adaptiveness and integrated UPy-modified CNCs into nonpolar and polar host polymers, which include different poly(ethylene)s, a polystyrene-block-polybutadiene-block-polystyrene elastomer and poly(ethylene oxide-co-epichlorohydrin). All nanocomposites display an increase of stiffness and strength in comparison to the neat polymer, and some compositions retain a high elongation at break, even at a filler content of 15% w/w.

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