AbstractNature's most brilliant hues arise from the interaction of light with multilayered‐ structures of aligned building blocks. Mimicking this hierarchical organization in highly‐ordered thin films of liquid crystalline species has attracted increasing attention for potential applications in sensors and optical switching displays. Due to its intriguing ability to organize into optically active materials, cellulose nanocrystals (CNCs) are attracting a strong interest in the scientific community. This study demonstrates that the shear‐driven convective assembly technique can be used to stratify in a controlled fashion highly ordered multilayers of rod‐like CNC embedded in a protective hydrophobic polymer matrix leading to optically active thin films. The films remain fully transparent even after stratifying 50 layers. Atomic force microscopy analysis reveals that over 87% of the CNCs in the upper layer aligned within ±20° of the withdrawal direction. Notably, the stratification does not disrupt the organization of the underlying layers. The films exhibit strong selective reflections with uniform and intense colors, dependent on the number of stratified layers. This scalable appraoch enables precise control over the optical characteristics of CNC‐polymer composite films, presenting opportunities for environmentally friendly applications in pigment‐free coatings, security papers, and optical devices.

Self-healing polymeric materials that can spontaneously repair in a perpetual manner are highly appealing to address safety and restoration issues in different key applications. Usually built from reversible moieties that require to be activated using, for example, temperature, light, or pH changes, most of these self-healing materials rely on energy-demanding processes and/or external interventions to promote self-healing. In this work, we propose to exploit rapid dynamic exchanges between urea-based moieties and moisture as an alternative to promote local and spontaneous healing responses to damage using atmospheric moisture as an external stimulus. Non-hygroscopic urea-based polyurethanes with repetitive moisture-induced healing abilities at different degrees of humidity were thus designed through coupling reactions with non-hygroscopic polypropylene glycol and urea moieties. As supported by density functional theory (DFT) calculations coupled to local FTIR experimental studies, we furthermore established that the healing mechanism is ultimately related to the formation of water-urea clusters. Obviously, this work represents a platform for designing more advanced spontaneous self-healing materials beyond the present study, which hold promise for use in a wide range of technological applications.

In recent years, shape-memory polymers (SMPs) have gained a key position in the realm of actuating applications from daily life products to biomedical and aeronautic devices. Most of these SMPs rely mainly on shape changes upon direct heat exposure or after stimulus conversion (e.g., magnetic field and light) to heat, but this concept remains significantly limited when both remote control and fine actuation are demanded. In the present study, we propose to design plasmonic silver nanoparticles (AgNPs) grafted onto cellulose nanocrystals (CNCs) as an efficient plasmonic system for fast and remote actuation. Such CNC- g-AgNPs "nanorod-like" structures thereby allowed for a long-distance and strong coupling plasmonic effect between the AgNPs along the CNC axis, thus ensuring a fast photothermal shape-recovery effect upon IR light illumination. To demonstrate the fast and remote actuation promoted by these structures, we incorporated them at low loading (1 wt %) into poly(ε-caprolactone) (PCL)-based networks with shape-memory properties. These polymer matrix networks were practically designed from biocompatible PCL oligomers end-functionalized with maleimide and furan moieties in the melt on the basis of thermoreversible Diels-Alder reactions. The as-produced materials could find application in the realm of soft robotics for remote object transportation or as smart biomaterials such as self-tightening knots with antibacterial properties related to the presence of the AgNPs.

A novel poly(epsilon-caprolactone) (PCL) supramolecular network exhibiting shape-memory behavior was successfully constructed with pendant UPy units that are highly able to dimerize. The dynamic network was obtained by a simple and versatile strategy consisting of chain-extension reaction between α,ω-dihydroxyoligoPCL and hydroxylated UPy units in the presence of hexamethylene diisocyanate as a coupling agent and further intermolecular dimerization of the UPy along the polyurethane backbone. 1H NMR analyses confirmed the dynamic features of the system, and DMTA in tensile mode was investigated to assess the SMP properties. Recyclability was also assessed by taking advantage of these supramolecular networks. Further addition of cellulose nanocrystals into the polymer network enabled adjustment of the extent of the net-points and therefore the SMP features. As confirmed by dispersion tests in solution and SEM observations, these bio-based nanofillers were homogeneously distributed in the network via supramolecular interaction between the hydroxyl groups present on their surface and UPy moieties along the polyurethane backbone. Thus, the here developed nanomaterials might reveal applicability in areas where a combination of SMP and biocompatibility is needed.

All-biobased and biodegradable nanocomposites consisting of poly(l-lactide) (PLLA) and starch nanoplatelets (SNPs) were prepared via a new strategy involving supramolecular chemistry, i.e., stereocomplexation and hydrogen-bonding interactions. For this purpose, a poly(d-lactide)-b-poly(glycidyl methacrylate) block copolymer (PDLA-b-PGMA) was first synthesized via the combination of ring-opening polymerization and atom-transfer radical polymerization. NMR spectroscopy and size-exclusion chromatography analysis confirmed a complete control over the copolymer synthesis. The SNPs were then mixed up with the copolymer for producing a PDLA-b-PGMA/SNPs masterbatch. The masterbatch was processed by solvent casting for which a particular attention was given to the solvent selection to preserve SNPs morphology as evidenced by transmission electron microscopy. Near-infrared spectroscopy was used to highlight the copolymer-SNPs supramolecular interactions mostly via hydrogen bonding. The prepared masterbatch was melt-blended with virgin PLLA and then thin films of PLLA/PDLA-b-PGMA/SNPs nanocomposites (ca. 600 μm) were melt-processed by compression molding. The resulting nanocomposite films were deeply characterized by thermogravimetric analysis and differential scanning calorimetry. Our findings suggest that supramolecular interactions based on stereocomplexation between the PLLA matrix and the PDLA block of the copolymer had a synergetic effect allowing the preservation of SNPs nanoplatelets and their morphology during melt processing. Quartz crystal microbalance and dynamic mechanical thermal analysis suggested a promising potential of the stereocomplex supramolecular approach in tuning PLLA/SNPs water vapor uptake and mechanical properties together with avoiding PLLA/SNPs degradation during melt processing.

(Thermo-)Mechanical properties It has been reported that the crystallization behavior of polymers connected with UPy end group via a urethane linker is influenced by the UPy stacking. The additional presence of urethane moieties stabilizes the stacks in the lateral direction via additional hydrogen bonding [66]. At contrast, bulky groups near to the UPy moieties can disrupt this crystallization. It was demonstrated that good mechanical properties of the formed network were dependent of the presence on the crystalline stacks. As shown in Table 1, PU (3) which presents the lower PCLcontent, exhibits a low molecular weight, i.e. ~ 15 000 g mol-1, meaning that its mechanical properties are most probably close to the oligo-PCL precursors, especially in terms of brittleness. Indeed, PU (3) based compressed films were very brittle, preventing any further characterizations. Therefore, only PU (1) and PU (2) were considered as candidates for supramolecular SMP design.

Herein a unique strategy for cellulose nanocrystal functionalization is presented in the form of surface functionalization of cellulose nanocrystals. Cellulose nanocrystals were prepared from acid hydrolysis of ramie fibers and then further subjected to amine functionalization with an amino trimethoxy silane (APTMS). The introduction of surface amine functionality to the cellulose nanocrystal allowed for an additional reaction with a biobased epoxy resin derived from diphenolic acid. The resulting thermo-mechanical properties of epoxy nanocomposites with amine functionalized cellulose nanocrystal were on average more than 7 times improved. Specifically, the storage modulus at 160 degrees C increased from 19.5 MPa for the neat resin to 151.5 MPa for the composite with 10 wt% APTMS modified CNC. The results reported herein demonstrate that amine functionalized cellulose nanocrystals provide excellent dispersion in epoxy resin systems and are a viable route to utilization of both biobased nanofillers and biobased epoxy resins. (C) 2017 Elsevier Ltd. All rights reserved.

A novel poly(epsilon-caprolactone) (PCL) supramolecular network exhibiting shape-memory behavior was successfully constructed with pendant UPy units that are highly able to dimerize. The dynamic network was obtained by a simple and versatile strategy consisting of chain-extension reaction between a,udihydroxyoligoPCL and hydroxylated UPy units in the presence of hexamethylene diisocyanate as a coupling agent and further intermolecular dimerization of the UPy along the polyurethane backbone. H NMR analyses confirmed the dynamic features of the system, and DMTA in tensile mode was investigated to assess the SMP properties. Recyclability was also assessed by taking advantage of these supramolecular networks. Further addition of cellulose nanocrystals into the polymer network enabled adjustment of the extent of the net-points and therefore the SMP features. As confirmed by dispersion tests in solution and SEM observations, these bio-based nanofillers were homogeneously distributed in the network via supramolecular interaction between the hydroxyl groups present on their surface and UPy moieties along the polyurethane backbone. Thus, the here developed nanomaterials might reveal applicability in areas where a combination of SMP and biocompatibility is needed.

Poly(ε-caprolactone)/MWCNT bilayer actuators produced by reactive extrusion techniques with solvent, vapor and electrical-responsiveness for soft robotics application.

Cellulose nanocrystal (CNC)-reinforced poly(lactic acid) (PLA) nanocomposites were prepared by twin-screw extrusion followed by injection-molding using a masterbatch approach. Noncovalent modification of CNCs was performed with two different poly(l-lactide) (PLLA)-based surfactants to improve the filler/matrix compatibility. They both have a PLLA block that is expected to improve the compatibility with the PLA matrix and differ by the polar head. It consists of either a poly(ethylene glycol) (PEG) block (PEG-b-PLLA) or an imidazolium group (Im-PLLA), that is able to interact with the surface of the CNCs. The morphological, structural, thermal, rheological, and mechanical properties of the nanocomposites were investigated. The different modes of interaction of the polar head of the surfactant lead to different properties. However, the global decrease in the molecular weight of PLA, induced by the short PLLA blocks from the surfactants and the possible degradation during melt processing, results in a plasticization effect and impacts the crystallization of the matrix.

The present study focuses on the use of cellulose nanocrystals (CNC) as the main constituent of a nanocomposite material and takes advantage of hydroxyl groups, characteristic of the CNC chemical structure, to thermally cross-link an epoxy resin. An original and simple approach is proposed, based on the collective sticking of CNC building blocks with the help of a DGEBA/TGPAP-based epoxy resin. Scientific findings suggest that hydroxyl groups act as a toxic-free cross-linking agent of the resin. The enhanced protection against water degradation as compared to neat CNC film and the improvement of mechanical properties of the synthesized films are attributed to a good compatibility between the CNC and the resin. Moreover, the preservation of CNC optical properties at high concentrations opens the way to applying these materials in photonic devices.

The present chapter emphasizes the preparation of new nanocomposite coatings based on an acrylic polymeric matrix loaded with cellulose nanocrystals (CNCs). Solvent casting and convective assembly were used as processing methods to prepare, respectively, thick and thin coatings with various CNC loadings. Strong interactions between the polymeric matrix and CNCs were revealed, contributing to a significant improvement of the thermal stability and mechanical properties of both nanocomposite films. More importantly, shear-convective assembly was used herein to create nanostructured coatings of rod-like CNCs embedded in a protective hydrophobic polymer matrix. The possibility to control CNC alignments opens the door to these renewable building blocks in coating applications such as scratch-resistant, pigment-free coatings, security papers, and optical devices.

Recent demands for polymers with autonomous self-healing properties are being constantly raised due to the need for high-performance and reliable materials.

In the present work, sustainable flame retardant polylactide (PLA) compositions, containing cellulose-phosphorus combinations, have been studied. The effect of combining MicroCrystalline Cellulose (MCC) or NanoCrystalline Cellulose (NCC) with phosphorus, on thermal stability and flame retardant properties of PLA was investigated by thermogravimetric analysis (TGA), cone calorimeter and UL-94 tests. Phosphorus was introduced either by chemical grafting on cellulose or by coadditive melt blending by using a bio-based phosphorous agent, i.e., aluminum phytate. In both cases, the charring effect of cellulose was enhanced.The phosphorylation process used allowed grafting 16.5 wt% of P as determined by Inductively Coupled Plasma analysis (ICP). However, this process led to the generation of water soluble cellulose and to the loss of the nanometric particle shape. For this reason, the phosphorylation of cellulose has been performed only on the microcrystalline particles. Using 20 wt% of phosphorylated MCC (MCC-P) allowed reaching VO at UL-94 test but did not result in significant reduction of pHRR. Significant pHRR reduction was obtained only when aluminum phytate was combined with phosphorylated MCC (P-MCC). As far as NCC was concerned, the use of a phosphorylated-NCC was not required since the simple combination of aluminum phytate and NCC allowed reaching significant decrease of the pHRR actually at the level of the value found when MCC-P was used in combination with aluminum phytate. The high specific surface area of NCC proved very useful to promote the formation of a better insulating charred layer. (C) 2015 Elsevier Ltd. All rights reserved.

Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. Accepted Manuscript Journal of Materials Chemistry A

With the advances in science and engineering in the second part of the 20th century, emerging plasma-based technologies continuously find increasing applications in the domain of polymer chemistry, among others. Plasma technologies are predominantly used in two different ways: for the treatment of polymer substrates by a reactive or inert gas aiming at a specific surface functionalization or for the synthesis of a plasma polymer with a unique set of properties from an organic or mixed organic-inorganic precursor. Plasma polymer films (PPFs), often deposited by plasma-enhanced chemical vapor deposition (PECVD), currently attract a great deal of attention. Such films are widely used in various fields for the coating of solid substrates, including membranes, semiconductors, metals, textiles, and polymers, because of a combination of interesting properties such as excellent adhesion, highly cross-linked structures, and the possibility of tuning properties by simply varying the precursor and/or the synthesis parameters. Among the many appealing features of plasma-synthesized and -treated polymers, a highly reactive surface, rich in free radicals arising from deposition/treatment specifics, offers a particular advantage. When handled carefully, these reactive free radicals open doors to the controllable surface functionalization of materials without affecting their bulk properties. The goal of this review is to illustrate the increasing application of plasma-based technologies for tuning the surface properties of polymers, principally through free-radical chemistry.