Water and Oxygen Barrier Properties of All-Cellulose Nanocomposites.

Hydroxypropyl cellulose (HPC) is potentially interesting as a biobased, rigid food packaging material, but its stiffness and strength are somewhat low, and its water and oxygen transport rates are too high. To improve these characteristics, we investigated nanocomposites of HPC and cellulose nanocrystals (CNCs). These high-aspect-ratio nanoparticles display high stiffness and strength, and their high crystallinity renders them virtually impermeable. Exchanging the counterions of sulfate-ester decorated CNCs with cetyltrimethylammonium ions affords particles that are dispersible in ethanol (CTA.CNC) and allows solvent casting of HPC/CTA.CNC nanocomposite films, which, even at a CTA.CNC content of 90 wt %, are highly transparent. The introduction of CTA.CNC considerably increases the Young's modulus (Ey) and upper tensile strength (σUTS). For example, in the nanocomposite with 90% CTA.CNC, Ey = 7.6 GPa is increased 20-fold and σUTS = 42.7 MPa is more than doubled in comparison to HPC, whereas the extensibility (1.1%) remains appreciable. Composites with a CTA.CNC content of 70 wt % or less show a lower water vapor permeability (6.4-9.2 × 10-5 g µm m-2 s-1 Pa-1) than the neat HPC (1.5 × 10-4 g µm m-2 s-1 Pa-1), whereas the oxygen permeability (5.6 × 10-7-1.3 × 10-6 cm3 µm m-2 s-1 Pa-1) is reduced by 1 order of magnitude compared to HPC (3.2 × 10-6 cm3 µm m-2 s-1 Pa-1). The biobased nanocomposites retain their mechanical integrity at a relative humidity of 75% but readily disintegrate in water.

One-Component Nanocomposites Made from Diblock Copolymer Grafted Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) are bio-based, rod-like, high-aspect-ratio nanoparticles with high stiffness and strength and are widely used as a reinforcing nanofiller in polymer nanocomposites. However, due to hydrogen-bond formation between the large number of hydroxyl groups on their surface, CNCs are prone to aggregate, especially in nonpolar polymer matrices. One possibility to overcome this problem is to graft polymers from the CNCs' surfaces and to process the resulting "hairy nanoparticles" (HNPs) into one-component nanocomposites (OCNs) in which the polymer matrix and CNC filler are covalently connected. Here, we report OCNs based on HNPs that were synthesized by grafting gradient diblock copolymers onto CNCs via surface-initiated atom transfer radical polymerization. The inner block (toward the CNCs) is composed of poly(methyl acrylate) (PMA), and the outer block comprises a gradient copolymer rich in poly(methyl methacrylate) (PMMA). The OCNs based on such HNPs microphase separate into a rubbery poly(methyl acrylate) phase that dissipates mechanical energy and imparts toughness, a glassy PMMA phase that provides strength and stiffness, and well-dispersed CNCs that further reinforce the materials. This design afforded OCNs that display a considerably higher stiffness and strength than reference diblock copolymers without the CNCs. At the same time, the extensibility remains high and the toughness is increased up to 5-fold relative to the reference materials.

Facile Method to Determine the Molecular Weight of Polymer Grafts Grown from Cellulose Nanocrystals.

One of the main challenges associated with the modification of cellulose nanocrystals (CNCs) with polymers by surface-initiated polymerization is the characterization of the resulting products, notably the molecular weight of the grafts. The solid nature of the (modified) CNC nanoparticles limits the possibility to apply solution-based characterization techniques, and the cleavage of the macromolecules from the surface of the CNCs to enable their characterization using solution-based techniques is intricate. Here, we report that 1H NMR spectroscopy of the supernatant of the heterogeneous reaction mixture can be used to approximate the molecular weight of poly(hexyl methacrylate) grafts grown from the surface of CNCs via surface-initiated atom transfer radical polymerization. This was achieved using 1H NMR spectra to determine the monomer conversion from the change of the relative ratio of monomer and solvent signals in the 1H NMR spectra, which in turn allowed determining the weight of PHMA produced. The number-average molecular weight of the grafted polymer was then estimated by assuming that standard atom transfer radical polymerization kinetics are at play and using the initiator concentration on the CNC surface determined by elemental analysis. The method was validated by comparing the results with the gravimetric data and the data of free polymers that were synthesized with a sacrificial initiator.

Nanocomposites Assembled via Electrostatic Interactions between Cellulose Nanocrystals and a Cationic Polymer.

On account of their high strength and stiffness and their renewable nature, cellulose nanocrystals (CNCs) are widely used as a reinforcing component in polymer nanocomposites. However, CNCs are prone to aggregation and this limits the attainable reinforcement. Here, we show that nanocomposites with a very high CNC content can be prepared by combining the cationic polymer poly[(2-(methacryloyloxy)ethyl) trimethylammonium chloride] (PMETAC) and negatively charged, carboxylated CNCs that are provided as a sodium salt (CNC-COONa). Free-standing films of the composites can be prepared by simple solvent casting from water. The appearance and polarized optical microscopy and electron microscopy images of these films suggest that CNC aggregation is absent, and this is supported by the very pronounced reinforcement observed. The incorporation of 33 wt % CNC-COONa into PMETAC allowed increasing the storage modulus of this already rather stiff, glassy amorphous matrix polymer from 1.5 ± 0.3 to 6.6 ± 0.1 GPa, while the maximum strength increased from 11 to 32 MPa. At this high CNC content, the reinforcement achieved in the PMETAC/CNC-COONa nanocomposite is much more pronounced than that observed for a reference nanocomposite made with unmodified CNCs (CNC-OH).

Heterolytic Bond Cleavage in a Scissile Triarylmethane Mechanophore.

Covalent mechanophores display the cleavage of a weak covalent bond when a sufficiently high mechanical force is applied. Three different covalent bond breaking mechanisms have been documented thus far, including concerted, homolytic, and heterolytic scission. Motifs that display heterolytic cleavage typically separate according to non-scissile reaction pathways that afford zwitterions. Here, we report a new mechanochromic triarylmethane mechanophore, which dissociates according to a scissile heterolytic pathway and displays a pronounced mechanochromic response. The mechanophore was equipped with two styrenylic handles that allowed its incorporation as a cross-linker into poly(N,N-dimethylacrylamide) and poly(methyl acrylate-co-2-hydroxyethyl acrylate) networks. These materials are originally colorless, but compression or tensile deformation renders the materials colored. By combining tensile testing and in situ transmittance measurements, we show that this effect is related to scissile cleavage leading to colored triarylmethane carbocations.

Powering Electronic Devices from Salt Gradients in AA-Battery-Sized Stacks of Hydrogel-Infused Paper.

Strongly electric fish use gradients of ions within their bodies to generate stunning external electrical discharges; the most powerful of these organisms, the Atlantic torpedo ray, can produce pulses of over 1 kW from its electric organs. Despite extensive study of this phenomenon in nature, the development of artificial power generation schemes based on ion gradients for portable, wearable, or implantable human use has remained out of reach. Previously, an artificial electric organ inspired by the electric eel demonstrated that electricity generated from ion gradients within stacked hydrogels can exceed 100 V. The current of this power source, however, was too low to power standard electronics. Here, an artificial electric organ inspired by the unique morphologies of torpedo rays for maximal current output is introduced. This power source uses a hybrid material of hydrogel-infused paper to create, organize, and reconfigure stacks of thin, arbitrarily large gel films in series and in parallel. The resulting increase in electrical power by almost two orders of magnitude compared to the original eel-inspired design makes it possible to power electronic devices and establishes that biology's mechanism of generating significant electrical power can now be realized from benign and soft materials in a portable size.

Melt Polycondensation for the Synthesis of Polyester Amides using Kneader Reactor Technology.

In this work, we discuss the process development and scale-up of the melt polycondensation of polyester amides from a laboratory scale to kg-scale in a kneader reactor. We identified and optimized the most important critical parameters and produced kg-quantities of polyester amides with Mn up to 25'000 g/mol and reproducible thermal and mechanical properties. The special kneader reactor allows safe and efficient scale-up of polymerisation reactions at high temperature and viscous melts due to good mixing and efficient mass transfer.

Mechanically switchable polymer fibers for sensing in biological conditions.

The area of in vivo sensing using optical fibers commonly uses materials such as silica and polymethyl methacrylate, both of which possess much higher modulus than human tissue. The mechanical mismatch between materials and living tissue has been seen to cause higher levels of glial encapsulation, scarring, and inflammation, leading to failure of the implanted medical device. We present the use of a fiber made from polyvinyl alcohol (PVA) for use as an implantable sensor as it is an easy to work with functionalized polymer that undergoes a transition from rigid to soft when introduced to water. This ability to switch from stiff to soft reduces the severity of the immune response. The fabricated PVA fibers labeled with fluorescein for sensing applications showed excellent response to various stimuli while exhibiting mechanical switchability. For the dry fibers, a tensile storage modulus of 4700 MPa was measured, which fell sharply to 145 MPa upon wetting. The fibers showed excellent response to changing pH levels, producing values that were detectable in a range consistent with those seen in the literature and in proposed applications. The results show that these mechanically switchable fibers are a viable option for future sensing applications.