Liquid crystalline properties of symmetric and asymmetric end-grafted cellulose nanocrystals

The hydrophilic polymer poly[2-(2-(2-methoxy ethoxy)ethoxy)ethylacrylate] (POEG3A) was grafted onto the reducing end-groups (REGs) of cellulose nanocrystal (CNC) allomorphs, and their liquid crystalline properties were investigated. The REGs on CNCs extracted from cellulose I (CNC-I) are exclusively located at one end of the crystallite, whereas CNCs extracted from cellulose II (CNC-II) feature REGs at both ends of the crystallite, so that grafting from the REGs affords asymmetrically and symmetrically decorated CNCs, respectively. To confirm the REG modification, several complementary analytical techniques were applied. The grafting of POEG3A onto the CNC REGs was evidenced by Fourier transform infrared spectroscopy, atomic force microscopy, and the coil–globule conformational transition of this polymer above 60 °C, i.e., its lower critical solution temperature. Furthermore, we investigated the self-assembly of end-tethered CNC-hybrids into chiral nematic liquid crystalline phases. Above a critical concentration, both end-grafted CNC allomorphs form chiral nematic tactoids. The introduction of POEG3A to CNC-I does not disturb the surface of the CNCs along the rods, allowing the modified CNCs to approach each other and form helicoidal textures. End-grafted CNC-II formed chiral nematic tactoids with a pitch observable by polarized optical microscopy. This is likely due to their increase in hydrodynamic radius or the introduced steric stabilization of the end-grafted polymerPeer ReviewedPostprint (author's final draft

Evaluating the use of calcium hydrogen phosphate dihydrate as a mineral-based fire retardant for application in melamine-urea-formaldehyde ( MUF )-bonded wood-based composite materials

Calcium hydrogen phosphate dihydrate (DCPD) was evaluated for its potential as a mineral fire retardant (FR) for application in melamine-urea-formaldehyde (MUF)-bonded wood composites. The efficacy as FR was studied in melamine-urea-formaldehyde (MUF)-bonded three-layer particleboard as a function of addition quantities of 10-, 20- and 30¿wt%. Resistance to fire and mechanical properties were determined by measuring the self-extinguishing time after flame exposure and internal bond strength, respectively. Combustion behavior was examined on samples with 20¿wt% DCPD addition by performing cone calorimetry experiments. The efficacy of DCPD was evaluated by determining the heat release, total heat release rate, smoke production, and smoke production rate and compared to another promising mineral-based fire-retardant composition (FRC) based on hydroxyapatite (HA) with deliquescent salt and HA alone. The effect of FR on the curing behavior of MUF in relation to mechanical properties was determined through viscosity measurements of MUF with 10 wt% addition of FR. The results confirmed the fire-retardant characteristics of DCPD in wood composites, albeit at higher application rates when compared to the FRC, however with no negative impact on resin curing time or mechanical strength. Based on the demonstrated compatibility in MUF, DCPD is considered a promising mineral extender of other FRs for application in UF-based wood composites.Peer ReviewedPostprint (author's final draft

Challenges in synthesis and analysis of asymmetrically grafted cellulose nanocrystals via atom transfer radical polymerization

When cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.Peer ReviewedPostprint (author's final draft

Biopolymer photonics: from nature to nanotechnology

Biopolymers offer vast potential for renewable and sustainable devices. While nature mastered the use of biopolymers to create highly complex 3D structures and optimized their photonic response, artificially created structures still lack nature's diversity. To bridge this gap between natural and engineered biophotonic structures, fundamental questions such as the natural formation process and the interplay of structural order and disorder must be answered. Herein, biological photonic structures and their characterization techniques are reviewed, focusing on those structures not yet artificially manufactured. Then, employed and potential nanofabrication strategies for biomimetic, bio-templated, and artificially created biopolymeric photonic structures are discussed. The discussion is extended to responsive biopolymer photonic structures and hybrid structures. Last, future fundamental physics, chemistry, and nanotechnology challenges related to biopolymer photonics are foreseen.Peer ReviewedPostprint (published version

Dynamic light scattering plus scanning electron microscopy: usefulness and limitations of a simplified estimation of nanocellulose dimensions

Measurements of nanocellulose size usually demand very high-resolution techniques and tedious image processing, mainly in what pertains to the length of nanofibers. Aiming to ease the process, this work assesses a relatively simple method to estimate the dimensions of nanocellulose particles with an aspect ratio greater than 1. Nanocellulose suspensions, both as nanofibers and as nanocrystals, are subjected to dynamic light scattering (DLS) and to field-emission scanning electron microscopy (FE-SEM). The former provides the hydrodynamic diameter, as long as the scatter angle and the consistency are adequate. Assays with different angles and concentrations compel us to recommend forward scattering (12.8°) and concentrations around 0.05–0.10 wt %. Then, FE-SEM with magnifications of ×5000–×20,000 generally suffices to obtain an acceptable approximation for the actual diameter, at least for bundles. Finally, length can be estimated by a simple geometric relationship. Regardless of whether they are collected from FE-SEM or DLS, size distributions are generally skewed to lower diameters. Width distributions from FE-SEM, in particular, are well fitted to log-normal functions. Overall, while this method is not valid for the thinnest fibrils or for single, small nanocrystals, it can be useful in lieu of very high-resolution techniques.Peer ReviewedPostprint (published version

Remote spatiotemporal control of a magnetic and electroconductive hydrogel network via magnetic fields for soft electronic applications

Multifunctional hydrogels are a class of materials offering new opportunities for interfacing living organisms with machines due to their mechanical compliance, biocompatibility, and capacity to be triggered by external stimuli. Here, we report a dual magnetic- and electric-stimuli-responsive hydrogel with the capacity to be disassembled and reassembled up to three times through reversible cross-links. This allows its use as an electronic device (e.g., temperature sensor) in the cross-linked state and spatiotemporal control through narrow channels in the disassembled state via the application of magnetic fields, followed by reassembly. The hydrogel consists of an interpenetrated polymer network of alginate (Alg) and poly(3,4-ethylenedioxythiophene) (PEDOT), which imparts mechanical and electrical properties, respectively. In addition, the incorporation of magnetite nanoparticles (Fe3O4 NPs) endows the hydrogel with magnetic properties. After structural, (electro)chemical, and physical characterization, we successfully performed dynamic and continuous transport of the hydrogel through disassembly, transporting the polymer–Fe3O4 NP aggregates toward a target using magnetic fields and its final reassembly to recover the multifunctional hydrogel in the cross-linked state. We also successfully tested the PEDOT/Alg/Fe3O4 NP hydrogel for temperature sensing and magnetic hyperthermia after various disassembly/re-cross-linking cycles. The present methodology can pave the way to a new generation of soft electronic devices with the capacity to be remotely transported.Peer ReviewedPostprint (author's final draft

Effect of functional mineral additive on processability and material properties of wood-fiber reinforced poly(lactic acid) (PLA) composites

This study examines the use of alkenyl succinic anhydride (ASA)-surface treated calcium carbonate as a functional mineral additive for application in wood fiber (WF)-reinforced PLA composites. The influence of addition quantity on the material properties of PLA composites with 40 wt% fiber reinforcement was examined at mineral addition levels of 10 wt%, 20 wt% and 30 wt%, respectively. The benefits of ASA surface-treated calcium carbonate over untreated mineral were exemplified by comparing the thermomechanical properties of PLA composites at an addition level of 10 wt%. The results demonstrate that the addition of ASA-treated calcium carbonate has distinctive advantages over untreated mineral, in terms of both processability and material properties. First, it enables better control of the process by reducing the flowability of the PLA matrix. Furthermore, it improves the fiber adhesion with the PLA, allowing for a substantial reduction of PLA content in the composite formulation while maintaining material properties.Peer ReviewedPostprint (author's final draft

Stiffness-changing of polymer nanocomposites with cellulose nanocrystals and polymeric dispersant

Bio-inspired, water-responsive, mechanically adaptive nanocomposites are reported based on cellulose nanocrystals (CNCs), poly(ethylene oxide-co-epichlorohydrin) (EO-EPI), and a small amount of poly(vinyl alcohol) (PVA), which is added to aid the dispersion of the CNCs. In the dry state, the CNCs form a reinforcing network within the polymer matrix, and the substantial stiffness increase relative to the neat polymer is thought to be the result of hydrogen-bonding interactions between the nanocrystals. Exposure to water, however, causes a large stiffness reduction, due to competitive hydrogen bonding of water molecules and the CNCs. It is shown here that the addition of PVA to the EO-EPI/CNC nanocomposite increases the modulus difference between the dry and the wet state by a factor of up to four compared to the nanocomposites without the PVA. The main reason is that the PVA leads to a substantial increase of the stiffness in the dry state; for example, the storage modulus E ' increased from 2.7 MPa (neat EO-EPI) to 50 MPa upon introduction of 10% CNCs, and to 200 MPa when additionally 5% of PVA was added. By contrast, the incorporation of PVA only led to moderate increases of the equilibrium water swelling and the E ' in the wet state.Peer ReviewedPostprint (author's final draft

Liquid crystalline thermosets based on anisotropic phases of cellulose nanocrystals

A new class of liquid crystalline thermosets (LCTs) was successfully produced containing lyotropic cellulose nanocrystals (CNCs) as the primary mesogenic component (up to 72 wt%) by the addition of non-mesogenic epoxy monomers. Cellulose-based LCTs were produced by totally aqueous processing methods and ultimately cured at elevated temperatures to produce ordered networks of ‘frozen’ liquid crystalline (LC) phases. Various degrees of birefringence were obtained via self-assembly of CNCs into oriented phases as observed by polarized optical microscopy and transmission electron microscopy. X-ray diffraction measurements highlighted the effects of texture of CNCs within LCT films compared to lyophilized CNCs. Cellulose-based LCT films uniquely exhibited thermo-mechanical properties of both traditional LCTs and LC elastomers, such as high elastic modulus (~1 GPa) under ambient conditions and low glass transition temperature (~-25 °C), respectively. The development of LCTs based on CNCs and aqueous processing methods provides a renewable pathway for designing high performance composites with ordered network structures and unique optical properties.Peer ReviewedPostprint (author's final draft

A variational solution of the time-dependent Schrodinger equation by a restricted superposition of frozen Gaussian wavepackets

We present a variational solution of the time-dependent Schrodinger equation formed from a restricted superposition of frozen Gaussian wavepackets. The trial function is comprised of a set of frozen Gaussian wavepackets and a set of three time-dependent variational parameters. The trial wavefunction is subjected to the McLachlan variational principle which leads to a set of equations for the optimal time-evolution of the variational parameters. We present numerical results for the time-evolution of the trial wavefunction on a single-dimensional anharmonic potential energy and compare to the results to the exact time-evolution. Finally, we derive a multi-dimensional generalization of the algorithm.Peer ReviewedPostprint (published version