Molecular Dynamics Simulations of Cellulose and Dialcohol Cellulose under Dry and Moist Conditions

The development of wood-based thermoplastic polymers that can replace synthetic plastics is of high environmental importance, and previous studies have indicated that cellulose-rich fiber containing dialcohol cellulose (ring-opened cellulose) is a very promising candidate material. In this study, molecular dynamics simulations, complemented with experiments, were used to investigate how and why the degree of ring opening influences the properties of dialcohol cellulose, and how temperature and presence of water affect the material properties. Mechanical tensile properties, diffusion/mobility-related properties, densities, glass-transition temperatures, potential energies, hydrogen bonds, and free volumes were simulated for amorphous cellulosic materials with 0-100% ring opening, at ambient and high (150 \ub0C) temperatures, with and without water. The simulations showed that the impact of ring openings, with respect to providing molecular mobility, was higher at high temperatures. This was also observed experimentally. Hence, the ring opening had the strongest beneficial effect on “processability” (reduced stiffness and strength) above the glass-transition temperature and in wet conditions. It also had the effect of lowering the glass-transition temperature. The results here showed that molecular dynamics is a valuable tool in the development of wood-based materials with optimal thermoplastic properties

Ambient-Dried, 3D-Printable and Electrically Conducting Cellulose Nanofiber Aerogels by Inclusion of Functional Polymers

This study presents a novel, green, and efficient way of preparing crosslinked aerogels from cellulose nanofibers (CNFs) and alginate using non-covalent chemistry. This new process can ultimately facilitate the fast, continuous, and large-scale production of porous, light-weight materials as it does not require freeze-drying, supercritical CO2 drying, or any environmentally harmful crosslinking chemistries. The reported preparation procedure relies solely on the successive freezing, solvent-exchange, and ambient drying of composite CNF-alginate gels. The presented findings suggest that a highly-porous structure can be preserved throughout the process by simply controlling the ionic strength of the gel. Aerogels with tunable densities (23–38 kg m−3) and compressive moduli (97–275 kPa) can be prepared by using different CNF concentrations. These low-density networks have a unique combination of formability (using molding or 3D-printing) and wet-stability (when ion exchanged to calcium ions). To demonstrate their use in advanced wet applications, the printed aerogels are functionalized with very high loadings of conducting poly(3,4-ethylenedioxythiophene):tosylate (PEDOT:TOS) polymer by using a novel in situ polymerization approach. In-depth material characterization reveals that these aerogels have the potential to be used in not only energy storage applications (specific capacitance of 78 F g−1), but also as mechanical-strain and humidity sensors

Small palladium islands embedded in palladium-tungsten bimetallic nanoparticles form catalytic hotspots for oxygen reduction

The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium: tungsten = 1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are similar to 1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions

Electron Spin Density Distribution in the Polymer Phase of CsC 60 : Assignment of the NMR Spectrum

We present high resolution 133 Cs-13 C double resonance NMR data and 13 C-13 C NMR correlation spectra of 13 C enriched samples of the polymeric phase of CsC 60 . These data lead to a partial assignment of the lines in the 13 C NMR spectrum of CsC 60 to the carbon positions on the C 60 molecule. A plausible completion of the assignment can be made on the basis of an ab initio calculation. The data support the view that the conduction electron density is concentrated at the C 60 "equator," away from the interfullerene bonds. PACS numbers: 71.20.Tx, 76.70.Fz The electronic and magnetic properties of the alkali intercalated fullerides, A n C 60 , are still only partly understood. The case A Rb, Cs, n 1 has attracted particular interest The basic structural features of the polymer phase, such as the dimensions of the unit cell, C 60 center positions, and the 2 1 2 cycloaddition polymerization along the crystallographic a axis are widely supported through x-ray diffraction However the degree of deformation of the C 60 balls [25] and the rotational orientation of the polymer chains are less well characterized. Neutron diffraction NMR has proven a useful probe of structure and electronic properties both for the broader class of alkali intercalated fulleride materials In order to obtain sufficient sensitivity, samples of CsC 60 were synthesized using 13 C enriched fullerenes. These were prepared by packing and sintering 13 C enriched amorphous carbon into graphite tubes to create 13 C enriched carbon rods. The fullerenes were subsequently produced by arcing a 60 A, 25 V dc current between an ordinar

Aggregation of lignin derivatives under alkaline conditions. Kinetics and aggregate structure

The kinetics of kraft lignin (KL) aggregation at alkaline conditions was studied by quasi-elastic light scattering (QELS) and turbidity measurements. Stability ratios (W) for HL were obtained at 70 degreesC and various concentrations of sodium chloride. By analyzing the early-time evolution data of aggregate growth obtained from QELS, fractal dimensions of flocs formed in both reaction-limited cluster-cluster aggregation regimes and diffusion-limited cluster-cluster aggregation regimes were determined. Correlations between the fractal dimension and the W-ratio were found in accordance to recent studies of a system containing monodisperse polystyrene colloids. By cryogenic transmission electron microscopy, the fractality of KL aggregate structures in the system was also shown. It was seen from stability studies of KL solutions that the effects of specific co- and counterions follow the Hofmeister series. From the outcome of the investigation, different modes of aggregation occurring in a KL system are proposed. Starting from the macromolecular state of KL and evolving through larger aggregates, the KL clusters finally exhibit a supramolecular structure similar to what earlier has been proposed for native softwood lignin

A physical cross-linking process of cellulose nanofibril gels with shear-controlled fibril orientation

Cellulose nanofibrils constitute the smallest fibrous components of wood, with a width of approximately 4 nm and a length in the micrometer range. They consist of aligned linear cellulose chains with crystallinity exceeding 60%, rendering stiff, high-aspect-ratio rods. These properties are advantageous in the reinforcement components of composites. Cross-linked networks of fibrils can be used as templates into which a polymer enters. In the semi-concentrated regime (i.e. slightly above the overlap concentration), carboxy methylated fibrils dispersed in water have been physically cross-linked to form a volume-spanning network (a gel) by reducing the pH or adding salt, which diminishes the electrostatic repulsion between fibrils. By applying shear during or after this gelation process, we can orient the fibrils in a preferred direction within the gel, for the purpose of fully utilizing the high stiffness and strength of the fibrils as reinforcement components. Using these gels as templates enables precise control of the spatial distribution and orientation of the dispersed phase of the composites, optimizing the potentially very large reinforcement capacity of the nanofibrils